JPH0244848B2 - TOSOYONET SUKOKASEIJUSHISOSEIBUTSU - Google Patents
TOSOYONET SUKOKASEIJUSHISOSEIBUTSUInfo
- Publication number
- JPH0244848B2 JPH0244848B2 JP15156085A JP15156085A JPH0244848B2 JP H0244848 B2 JPH0244848 B2 JP H0244848B2 JP 15156085 A JP15156085 A JP 15156085A JP 15156085 A JP15156085 A JP 15156085A JP H0244848 B2 JPH0244848 B2 JP H0244848B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- added
- polyepoxide
- amino
- coating
- 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.)
- Expired - Lifetime
Links
- 229920000647 polyepoxide Polymers 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 239000006185 dispersion Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004070 electrodeposition Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 15
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 15
- -1 2-hydroxynaphthyl Chemical group 0.000 description 14
- 125000002091 cationic group Chemical group 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000011976 maleic acid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 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 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 7
- 229910000165 zinc phosphate Inorganic materials 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229940011182 cobalt acetate Drugs 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 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
- 238000005292 vacuum distillation Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- AFPIWWDEGJLLCL-UHFFFAOYSA-N 1,3,2,4$l^{2}-dioxasilaplumbetane 2-oxide Chemical compound [Pb+2].[O-][Si]([O-])=O AFPIWWDEGJLLCL-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 description 1
- VXDHQYLFEYUMFY-UHFFFAOYSA-N 2-methylprop-2-en-1-amine Chemical compound CC(=C)CN VXDHQYLFEYUMFY-UHFFFAOYSA-N 0.000 description 1
- ZDRSNHRWLQQICP-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 ZDRSNHRWLQQICP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- ZGZVGZCIFZBNCN-UHFFFAOYSA-N 4,4'-(2-Methylpropylidene)bisphenol Chemical compound C=1C=C(O)C=CC=1C(C(C)C)C1=CC=C(O)C=C1 ZGZVGZCIFZBNCN-UHFFFAOYSA-N 0.000 description 1
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GTOCDKHWXAPBAR-PAMPIZDHSA-N CC(O)CO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O Chemical compound CC(O)CO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O GTOCDKHWXAPBAR-PAMPIZDHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 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
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 1
- XKTYDGQXZVTUFO-SPIKMXEPSA-N OCCCCCCO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O Chemical compound OCCCCCCO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O XKTYDGQXZVTUFO-SPIKMXEPSA-N 0.000 description 1
- GKASRLVPWBWUCI-PAMPIZDHSA-N OCCO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O Chemical compound OCCO.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O GKASRLVPWBWUCI-PAMPIZDHSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- IGEIPFLJVCPEKU-UHFFFAOYSA-N pentan-2-amine Chemical compound CCCC(C)N IGEIPFLJVCPEKU-UHFFFAOYSA-N 0.000 description 1
- PQPFFKCJENSZKL-UHFFFAOYSA-N pentan-3-amine Chemical compound CCC(N)CC PQPFFKCJENSZKL-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
本発明は、カチオン電着塗装及びその他の塗装
に適した熱硬化性樹脂組成物に関するものであ
る。
The present invention relates to a thermosetting resin composition suitable for cationic electrodeposition coating and other coatings.
カチオン電着塗装は、その塗膜性能が従来のア
ニオン電着塗装に比べて、被塗体の防錆力等に関
し著しく優れている為、自動車工業分野を含む多
くの産業分野で、近年その使用が増加してきてい
る。
このようなカチオン電着塗装に用いられる樹脂
組成物についても、種々のものが提案されている
が、その主流をなすものは、例えば特開昭48−
51924号、特開昭51−126225号等に開示されてい
るように、ビスフエノールＡ／エピクロルヒドリ
ン縮合形のエポキシ樹脂に、第一アミン又は第二
アミンを反応させた後、部分的なブロツク化ポリ
イソシアネートを反応させ、ついで水分散性とし
たものである。
Cationic electrodeposition coatings have significantly superior coating performance compared to conventional anionic electrodeposition coatings in terms of rust prevention and other properties of the coated object, and have recently been used in many industrial fields, including the automobile industry. is increasing. Various resin compositions have been proposed for use in such cationic electrodeposition coatings, but the most popular one is, for example, disclosed in Japanese Patent Application Laid-Open No.
51924, JP-A No. 51-126225, etc., after reacting a bisphenol A/epichlorohydrin condensation type epoxy resin with a primary amine or a secondary amine, a partially blocked polyester resin is prepared. It is made to react with isocyanate and then made water dispersible.
ブロツク化ポリイソシアネート硬化形のカチオ
ン電着塗装は、その塗装被膜が耐蝕性に有利な塩
基性を有している事、及びその塗料樹脂成分とし
て多量のエポキシ樹脂を用いているため、従来の
アニオン電着塗料に比べて、その塗装鋼板は極め
て高い耐蝕性を有する半面、焼付温度が160〜180
℃と高いという問題点を有している。
Blocked polyisocyanate cure type cationic electrodeposition coating has a basicity that is advantageous for corrosion resistance, and a large amount of epoxy resin is used as the paint resin component, so it is different from conventional anionic electrodeposition coating. Compared to electrodeposition paint, the coated steel sheet has extremely high corrosion resistance, but the baking temperature is 160-180℃.
The problem is that the temperature is as high as ℃.
本発明者らは、上記のような問題点を解決する
ため鋭意研究を重ねた結果、ポリエポキシドを２
個のカルボニル基と共役するエチレン性不飽和結
合を有する二塩基酸化合物で連結した後、そのエ
チレン性不飽和結合及び残存するエポキシ基に、
低沸点の第一モノアミン又は第二モノアミンを付
加して得られるアミノ変性ポリエポキシドを酸で
中和し、水分散した水性塗料を用い、自動車用鋼
板を被塗体としてカチオン電着塗装して得られる
塗装被膜は、その後の加熱によつて不安定となつ
たマイケル形付加結合から、第一モノアミン又は
第二モノアミンが離脱し、且つ揮散すると同時に
活性なエチレン性不飽和結合が再生して熱重合硬
化すること、しかもその硬化性は、鉛、スズ、コ
バルト、マンガン、亜鉛等の金属塩を、前記アミ
ノ変性ポリエポキシド水分散液中に硬化促進剤と
して含有させることによつて著しく向上し、100
〜160℃、好ましくは140〜160℃で焼付ける事に
よつて充分硬化可能な低温硬化性を示すと共に、
得られる硬化被膜も、硬さ、耐溶剤性及び耐蝕性
に優れること、及び前記アミノ変性ポリエポキシ
ドと上記硬化促進剤との混合物を水で希釈するこ
とによつて、電着塗装や浸漬塗装として用いるこ
とができるだけでなく、適当な有機溶剤で希釈す
ることによつて、それ以外の塗装方法にも適用で
きることを見い出し本発明を完成するに至つたも
のである。
即ち、本発明は、ポリエポキシドを２個のカル
ボニル基と共役するエチレン性不飽和結合を有す
る二塩基酸化合物で連結した後、そのエチレン性
不飽和結合及び残存するエポキシ基に沸点が100
℃以下の第一モノアミン又は第二モノアミンを付
加して得られた数平均分子量1100〜10000のアミ
ノ変性ポリエポキシドと、当該アミノ変性ポリエ
ポキシド固形分100重量部に対して、0.1〜20重量
部の硬化促進剤とを含んで成る塗装用熱硬化性樹
脂組成物に関するものである。
本発明に用いられるアミノ変性ポリエポキシド
は、ポリエポキシドを２個のカルボニル基と共役
するエチレン性不飽和結合を有する二塩基酸化合
物によつて連結した後、残存するエポキシ基及び
エチレン性不飽和結合に低沸点の第一モノアミン
又は第二モノアミンを付加させることによつて合
成されるものである。
アミノ変性ポリエポキシドの合成に用いられる
ポリエポキシドとしては、１，２エポキシ基を２
以上有する化合物であつて、そのようなポリエポ
キシドとしては、まず、ポリフエノールのポリグ
リシジルエーテル、ポリフエノールのエチレンオ
キシド付加物やプロピレンオキシド付加物のよう
なオキシアルキル化付加物のポリグリシジルエー
テル、ノボラツク系フエノール樹脂のポリグリシ
ジルエーテル等があげられる。
ここで、ポリフエノールとしては、例えばビス
フエノールＡ〔２，２−ビス（４−ヒドロキシフ
エニル）プロパン〕、１，１−ビス（４−ヒドロ
キシフエニル）エタン、２−メチル−１，１−ビ
ス（４−ヒドロキシフエニル）プロパン、２，２
−ビス（４−ヒドロキシ−３−ｔ−ブチルフエニ
ル）プロパン、ビス（２−ヒドロキシナフチル）
メタン、１，５−ジヒドロキシナフタレン等があ
げられる。
ついで、その他のポリエポキシドとしては、エ
ポキシ化ポリアルカジエン系樹脂やグリシジルア
クリレート共重合体系樹脂、グリシジルメタアク
リレート共重合体系樹脂、水酸基含有樹脂のポリ
グリシジルエーテル、カルボキシル基含有樹脂の
ポリグリシジルエステル等があげられる。
次にポリエポキシドの連結剤として用いられる
２個のカルボニル基と共役するエチレン性不飽和
結合を有する二塩基酸化合物としては、マレイン
酸、フマル酸又は無水マレイン酸とグリコールと
の反応によつて合成されるグリコール−ビス−マ
レイン酸があげられる。
グリコール−ビス−マレイン酸としては、例え
ばエチレングリコール−ビス−マレイン酸、プロ
ピレングリコール−ビス−マレイン酸、１，３−
ブチレングリコール−ビス−マレイン酸、１，６
−ヘキサンジオール−ビス−マレイン酸、２，５
−ヘキサンジオール−ビス−マレイン酸、ネオペ
ンチルグリコール−ビス−マレイン酸、水素化ビ
スフエノールＡ−ビス−マレイン酸、ビスフエノ
ールジヒドロキシプロピルエーテル−ビス−マレ
イン酸等や、上記グリコール−ビス−マレイン酸
中のグリコールがポリ縮合化したグリコールと無
水マレイン酸との反応によつて合成されるグリコ
ール−ビス−マレイン酸があり、このようなグリ
コール−ビス−マレイン酸としては、一般式が
で示されるポリエチレングリコール−ビス−マレ
イン酸や、一般式が
で示されるポリプロピレングリコール−ビス−マ
レイン酸等があげられる。
次に、２個のカルボニル基と共役するエチレン
性不飽和結合を有する二塩基酸化合物によつて連
結されたポリエポキシド中の、エチレン性不飽和
結合及び残存するエポキシ基に付加させる第一モ
ノアミン又は第二モノアミンとしては、１分子中
にアミノ基又はイミノ基を１個有するものであつ
て、且つ沸点が100℃以下のものでありそのよう
な第一モノアミン又は第二モノアミンとしては、
例えばメチルアミン、エチルアミン、ｎ−プロピ
ルアミン、イソプロピルアミン、ｎ−ブチルアミ
ン、ｓ−ブチルアミン、イソブチルアミン、ｔ−
ブチルアミン、ｎ−アミルアミン、２−アミノペ
ンタン、３−アミノペンタン、イソアミルアミ
ン、ｔ−アミルアミン、アリルアミン、メタリル
アミン等の炭素数１〜５の第一モノアミンや、ジ
メチルアミン、ジエチルアミン、メチルエチルア
ミン、メチル−ｎ−プロピルアミン、メチルイソ
プロピルアミン、メチル−ｎ−ブチルアミン、メ
チルイソブチルアミン、エチル−ｎ−プロピルア
ミン、エチルイソプロピルアミン、アリルメチル
アミン等の炭素数１〜５の第二モノアミン等があ
げられる。
ここで、100℃を超える沸点を有する第一モノ
アミン又は第二モノアミンを用いた場合は、その
得られる塗装被膜樹脂中のマイケル形付加結合が
加熱焼付下でも安定となるため、第一モノアミン
又は第二モノアミンの離脱及び揮散による活性な
エチレン性不飽和結合が再生しにくくなり、充分
な低温硬化性が得られなくなり好ましくない。
次に、本発明に用いられるアミノ変性ポリエポ
キシドの合成方法について述べる。
まず、ポリエポキシドを、２個のカルボニル基
と共役するエチレン性不飽和結合を有する二塩基
酸化合物で連結する方法について説明する。
反応容器にポリエポキシド及び適当な有機溶剤
を仕込み、不活性ガス気流下に徐々に加熱しなが
ら撹拌して均一な液状物とする。
ついで、上記の均一な液状物を100℃以下の適
当な温度で不活性ガス気流下に撹拌しながら、２
個のカルボニル基と共役するエチレン性不飽和二
塩基酸化合物を添加し、充分撹拌して均一な液状
物とした後、適当な触媒を添加して100℃以下、
好ましくは80〜100℃で、樹脂酸価が１以下にな
るまで２〜６時間反応を継続する。
この段階で用いられる適当な有機溶剤として
は、例えばトルエン、キシレン、メチルイソブチ
ルケトン、ジイソプロピルケトン、ミネラルスピ
リツト、エチレングリコールモノエチルエーテル
アセテート、ジエチレングリコールジメチルエー
テル、酢酸ブチル等が好ましい。
又、この段階で用いられる適当な触媒として
は、ジメチルエタノールアミン、テトラメチルア
ンモニウムクロライド等の第三アミンや第四級ア
ンモニウム塩等である。
次に、２個のカルボニル基と共役するエチレン
性不飽和結合を有する二塩基酸化合物によつて連
結されたポリエポキシドと、第一モノアミン又は
第二モノアミンとの付加反応方法について説明す
る。
この反応は、前記の反応に引き続いて行われる
反応であり、２個のカルボニル基と共役するエチ
レン性不飽和結合を有する二塩基酸化合物によつ
て連結された、ポリエポキシドからなる均一な液
状物へ添加される第一モノアミン又は第二モノア
ミンの量は、反応を促進し且つゲル化を防止する
ため必要量の1.2〜２倍量が好ましい。又添加す
る方法は、適当な温度で不活性ガス気流下に撹拌
しながら行われ、第一モノアミンの場合はゲル化
を防止するため全量仕込み、第二モノアミンの場
合は全量仕込み、分割仕込み、滴下仕込み等の方
法によつて行われる。この段階での反応条件は、
70〜100℃で１〜４時間で行つても良いが、低沸
点のアミンを用いること、及び２個のカルボニル
基と共役するエチレン性不飽和結合に対する第一
モノアミン又は第二モノアミンの付加がポリエポ
キシドのエポキシ基に対する付加に比べ、低温か
らでも極めて早く起ることから、まず30〜80℃、
好ましくは40〜70℃で１〜２時間反応させた後、
70〜100℃で１〜３時間反応させて反応を完結さ
せ、反応容器内の気圧を−30〜−60cmHgに減圧
し、60〜100℃で0.5〜１時間減圧蒸留を行い未反
応のアミン及び有機溶剤を除去し、反応容器内を
大気圧下に戻し、その後の水分散に適する溶剤、
例えばエチレングリコールモノブチルエーテル、
エチレングリコールモノエチルエーテル、ブチル
アルコール、イソプロピルアルコール、ジアセト
ンアルコール等の溶剤を添加し、樹脂溶液状のア
ミノ変性ポリエポキシドを得る。
ここで、得られるアミノ変性ポリエポキシドの
分子量は、数平均分子量で1100〜10000が好まし
く、数平均分子量が1100未満の場合は、硬度、耐
溶剤性及び耐蝕性に関し充分な性能を有する硬化
被膜が得られず、又10000を超える場合は塗膜外
観の良好な硬化被膜が得られない。
又、アミノ変性ポリエポキシドに含まれる２個
のカルボニル基と共役するエチレン性不飽和結合
の数は、低温硬化性を左右する重要なものであ
り、140〜160℃の焼付温度で充分な硬化性及び耐
蝕性を有する硬化被膜を得るためには、少なくと
もアミノ変性ポリエポキシド1000ｇ中、0.5個以
上有することが好ましい。
上記アミノ変性ポリエポキシドと共に、本発明
を構成するもう一つの重要な成分である硬化促進
剤としては、例えば、鉛、スズ、ニツケル、コバ
ルト、亜鉛、マンガン、鉄、ジルコニウム等のナ
フテン酸塩、オレイン酸塩、オクチル酸塩、酢酸
塩、トール油脂肪酸塩、亜麻仁油脂肪酸塩のよう
な金属塩や、例えばジメチルアニリン、フエニル
モルホリン等のアミン類や、バナジルアセチルア
セトナート、アルミニウムアセチルアセトナート
等の金属キレート化合物等があげられる。特に好
ましいものとしては、酢酸マンガン、酢酸コバル
ト、ナフテン酸マンガン、ナフテン酸コバルト等
の金属塩である。
上記の硬化促進剤は、アミノ変性ポリエポキシ
ド100重量部に対して、0.1〜20重量部添加すれば
良く、添加量が、0.1重量部未満又は20重量部を
超える場合は、硬度、耐溶剤性及び耐蝕性に関し
充分な性能を有する硬化被膜が得られない。
又、硬化促進剤の添加方法としては、アミノ変
性ポリエポキシドの樹脂溶液に混入した後、充分
撹拌するか、又はアミノ変性ポリエポキシドの水
分散液又は樹脂溶液をつくるのに用いられる水又
は有機溶剤に充分溶解させて用いる２つの方法が
適当である。
本発明による塗装用熱硬化性樹脂組成物は、基
本的には、アミノ変性ポリエポキシドと、硬化促
進剤とからなるが、その混合物中の第二アミン又
は第三アミンを、例えば蟻酸、酢酸、乳酸、リン
酸等の有機酸又は無機酸で中和することで、カチ
オン性塩基への変換が可能となり、更に水で希釈
することによりカチオン電着塗装又は浸漬塗装に
適した水分散液を得ることができる。
又、当該樹脂組成物を適当な有機溶剤で希釈す
ることによつて、上記以外の塗装方法、例えば噴
霧塗装、流れ塗装、回転塗装等に適した樹脂溶液
を得ることができる。
上記の水分散液又は樹脂溶液には、その他の成
分として、可塑剤、界面活性剤、顔料（例えば二
酸化チタン、カーボンブラツク、タルク、カオリ
ン、シリカ、ケイ酸鉛、塩基性クロム酸鉛、リン
酸亜鉛等の着色顔料、体質顔料、防錆顔料等）、
有機溶剤（例えば、ブチルアルコール、イソプロ
ピルアルコール、ジアセトンアルコール、エチレ
ングリコールモノエチルエーテル、エチレングリ
コールモノブチルエーテル等の親水性又は半親水
性の溶剤や、トルエン、キシレン、メチルエチル
ケトン、メチルイソブチルケトン等の疎水性の溶
剤等）、水等を適宜に加え、塗料の製造に通常用
いられているデゾルバー、ホモミキサー、サンド
グラインドミル、アトライター、ロールミル等の
混合機や分散機等によつて、均一に混合、分散
し、樹脂分の固形分がおよそ10〜30重量％の水分
散液であるカチオン形電着塗料や浸漬塗料、及び
樹脂分の固形分がおよそ30〜70重量％の溶液であ
る噴霧塗装、流れ塗装、回転塗装に適する塗料を
得ることができる。
このような塗料によつて塗装される被塗体とし
ては、特に鋼、アルミニウム、銅等の金属ばかり
でなく、金属化プラスチツク、電導性カーボン被
塗体や、非金属性被塗体であるガラス、木材、プ
ラスチツク等があげられる。
As a result of intensive research to solve the above problems, the inventors of the present invention discovered that polyepoxide
After linking with a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups, the ethylenically unsaturated bond and the remaining epoxy group,
Obtained by neutralizing amino-modified polyepoxide obtained by adding a low boiling point primary monoamine or secondary monoamine with an acid, and applying cationic electrodeposition coating to an automotive steel plate using a water-based paint dispersed in water. The paint film is thermally polymerized and hardened by the regeneration of active ethylenically unsaturated bonds as the primary monoamine or secondary monoamine is released and volatilized from the Michael-type addition bonds that have become unstable due to subsequent heating. Moreover, its hardenability is significantly improved by incorporating metal salts such as lead, tin, cobalt, manganese, zinc, etc. into the amino-modified polyepoxide aqueous dispersion as a hardening accelerator.
In addition to exhibiting low-temperature curability that can be sufficiently cured by baking at ~160℃, preferably 140-160℃,
The resulting cured film also has excellent hardness, solvent resistance, and corrosion resistance, and by diluting the mixture of the amino-modified polyepoxide and the curing accelerator with water, it can be used as an electrodeposition coating or a dipping coating. The present invention has been completed based on the discovery that not only can it be applied, but also that it can be applied to other coating methods by diluting it with an appropriate organic solvent. That is, in the present invention, after connecting polyepoxide with a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups, the ethylenically unsaturated bond and the remaining epoxy group have a boiling point of 100
Amino-modified polyepoxide with a number average molecular weight of 1,100 to 10,000 obtained by adding a primary monoamine or a secondary monoamine of 0.1 to 20 parts by weight of curing acceleration per 100 parts by weight of the solid content of the amino-modified polyepoxide. The present invention relates to a thermosetting resin composition for coating, comprising: The amino-modified polyepoxide used in the present invention is produced by linking polyepoxides with a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups, and then reducing the remaining epoxy groups and ethylenically unsaturated bonds. It is synthesized by adding a primary monoamine or a secondary monoamine at a boiling point. The polyepoxide used for the synthesis of amino-modified polyepoxide has 1,2 epoxy groups
Examples of such polyepoxides include polyglycidyl ethers of polyphenols, polyglycidyl ethers of oxyalkylated adducts such as ethylene oxide adducts and propylene oxide adducts of polyphenols, and novolak phenols. Examples include polyglycidyl ether of resin. Here, as the polyphenol, for example, bisphenol A [2,2-bis(4-hydroxyphenyl)propane], 1,1-bis(4-hydroxyphenyl)ethane, 2-methyl-1,1- Bis(4-hydroxyphenyl)propane, 2,2
-Bis(4-hydroxy-3-t-butylphenyl)propane, bis(2-hydroxynaphthyl)
Examples include methane and 1,5-dihydroxynaphthalene. Examples of other polyepoxides include epoxidized polyalkadiene resins, glycidyl acrylate copolymer resins, glycidyl methacrylate copolymer resins, polyglycidyl ethers of hydroxyl group-containing resins, and polyglycidyl esters of carboxyl group-containing resins. It will be done. Next, a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups and used as a linking agent for polyepoxide is synthesized by the reaction of maleic acid, fumaric acid, or maleic anhydride with glycol. Examples include glycol-bis-maleic acid. Examples of glycol-bis-maleic acid include ethylene glycol-bis-maleic acid, propylene glycol-bis-maleic acid, 1,3-
Butylene glycol-bis-maleic acid, 1,6
-hexanediol-bis-maleic acid, 2,5
-hexanediol-bis-maleic acid, neopentyl glycol-bis-maleic acid, hydrogenated bisphenol A-bis-maleic acid, bisphenol dihydroxypropyl ether-bis-maleic acid, and the above-mentioned glycol-bis-maleic acids. There is glycol-bis-maleic acid, which is synthesized by the reaction of polycondensed glycol with maleic anhydride. Such glycol-bis-maleic acid has the general formula: Polyethylene glycol-bis-maleic acid represented by Examples include polypropylene glycol-bis-maleic acid represented by: Next, a first monoamine or a second monoamine is added to the ethylenically unsaturated bond and the remaining epoxy group in the polyepoxide linked by a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups. Dimonoamines have one amino group or imino group in one molecule and have a boiling point of 100°C or less, and such primary monoamines or secondary monoamines include:
For example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, t-
Primary monoamines having 1 to 5 carbon atoms such as butylamine, n-amylamine, 2-aminopentane, 3-aminopentane, isoamylamine, t-amylamine, allylamine, methallylamine, dimethylamine, diethylamine, methylethylamine, methyl-n Examples include secondary monoamines having 1 to 5 carbon atoms, such as -propylamine, methylisopropylamine, methyl-n-butylamine, methylisobutylamine, ethyl-n-propylamine, ethylisopropylamine, and allylmethylamine. Here, when a primary monoamine or a secondary monoamine having a boiling point exceeding 100°C is used, the Michael type addition bond in the resulting paint coating resin becomes stable even under heat baking, so the primary monoamine or secondary monoamine is used. This is not preferable because active ethylenically unsaturated bonds due to separation and volatilization of the dimonoamine become difficult to regenerate, making it impossible to obtain sufficient low-temperature curability. Next, a method for synthesizing the amino-modified polyepoxide used in the present invention will be described. First, a method for linking polyepoxides with a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups will be described. A reaction vessel is charged with polyepoxide and a suitable organic solvent, and the mixture is stirred while being gradually heated under a stream of inert gas to form a uniform liquid. Next, the above homogeneous liquid was stirred at an appropriate temperature of 100°C or less under an inert gas stream for 2 hours.
Add an ethylenically unsaturated dibasic acid compound conjugated with carbonyl groups, stir thoroughly to make a homogeneous liquid, add an appropriate catalyst, and heat at 100℃ or below.
Preferably, the reaction is continued at 80 to 100°C for 2 to 6 hours until the resin acid value becomes 1 or less. Suitable organic solvents used in this step include, for example, toluene, xylene, methyl isobutyl ketone, diisopropyl ketone, mineral spirits, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, butyl acetate, and the like. Suitable catalysts used in this step include tertiary amines and quaternary ammonium salts such as dimethylethanolamine and tetramethylammonium chloride. Next, a method of addition reaction between a polyepoxide linked by a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups and a first monoamine or a second monoamine will be described. This reaction is a reaction that is carried out subsequent to the above reaction, and produces a homogeneous liquid consisting of polyepoxide linked by a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups. The amount of the first monoamine or second monoamine added is preferably 1.2 to 2 times the required amount in order to promote the reaction and prevent gelation. The addition method is carried out at an appropriate temperature with stirring under an inert gas stream.In the case of primary monoamines, the entire amount is added to prevent gelation, and in the case of secondary monoamines, the entire amount is added, portions are added, and dripping is performed. This is done by methods such as preparation. The reaction conditions at this stage are:
It may be carried out at 70 to 100°C for 1 to 4 hours, but it is important to use a low boiling point amine and to add a primary monoamine or a secondary monoamine to an ethylenically unsaturated bond conjugated with two carbonyl groups. Compared to addition to epoxy groups, it occurs extremely quickly even at low temperatures.
Preferably, after reacting at 40 to 70°C for 1 to 2 hours,
The reaction is completed by reacting at 70 to 100°C for 1 to 3 hours, the pressure inside the reaction vessel is reduced to -30 to -60 cmHg, and vacuum distillation is carried out at 60 to 100°C for 0.5 to 1 hour to remove unreacted amine and After removing the organic solvent and returning the inside of the reaction vessel to atmospheric pressure, a solvent suitable for subsequent water dispersion,
For example, ethylene glycol monobutyl ether,
A solvent such as ethylene glycol monoethyl ether, butyl alcohol, isopropyl alcohol, diacetone alcohol, etc. is added to obtain an amino-modified polyepoxide in the form of a resin solution. The number average molecular weight of the obtained amino-modified polyepoxide is preferably 1,100 to 10,000. If the number average molecular weight is less than 1,100, a cured film with sufficient performance in terms of hardness, solvent resistance, and corrosion resistance can be obtained. If it exceeds 10,000, a cured film with a good appearance cannot be obtained. In addition, the number of ethylenically unsaturated bonds conjugated with the two carbonyl groups contained in the amino-modified polyepoxide is an important factor that influences low-temperature curability. In order to obtain a cured film having corrosion resistance, it is preferable that at least 0.5 or more of the amino-modified polyepoxides are present in 1000 g of the amino-modified polyepoxide. In addition to the above amino-modified polyepoxide, curing accelerators that are another important component of the present invention include naphthenates such as lead, tin, nickel, cobalt, zinc, manganese, iron, and zirconium, and oleic acid. Metal salts such as salts, octolates, acetates, tall oil fatty acid salts, and linseed oil fatty acid salts, amines such as dimethylaniline and phenylmorpholine, and metals such as vanadyl acetylacetonate and aluminum acetylacetonate. Examples include chelate compounds. Particularly preferred are metal salts such as manganese acetate, cobalt acetate, manganese naphthenate, and cobalt naphthenate. The above curing accelerator may be added in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the amino-modified polyepoxide. A cured film with sufficient corrosion resistance cannot be obtained. In addition, the curing accelerator can be added by mixing it into the resin solution of amino-modified polyepoxide and stirring thoroughly, or adding it to the water or organic solvent used to make the aqueous dispersion or resin solution of amino-modified polyepoxide. Two methods are suitable for use in solution. The thermosetting resin composition for coating according to the present invention basically consists of an amino-modified polyepoxide and a curing accelerator. By neutralizing with an organic or inorganic acid such as phosphoric acid, it is possible to convert it into a cationic base, and by further diluting it with water, an aqueous dispersion suitable for cationic electrodeposition coating or dip coating can be obtained. Can be done. Furthermore, by diluting the resin composition with an appropriate organic solvent, a resin solution suitable for coating methods other than those described above, such as spray coating, flow coating, rotation coating, etc., can be obtained. The above aqueous dispersion or resin solution may contain other ingredients such as plasticizers, surfactants, pigments (e.g. titanium dioxide, carbon black, talc, kaolin, silica, lead silicate, basic lead chromate, phosphoric acid). Coloring pigments such as zinc, extender pigments, anti-rust pigments, etc.),
Organic solvents (e.g. hydrophilic or semi-hydrophilic solvents such as butyl alcohol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc., and hydrophobic solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone) (solvent, etc.), water, etc. as appropriate, and mix uniformly using a mixer or dispersion machine such as a dissolver, homo mixer, sand grind mill, attritor, roll mill, etc., which are commonly used in the manufacture of paints. Cationic electrodeposition paints and dip paints that are dispersed in water and have a solid resin content of approximately 10 to 30% by weight, and spray coatings that are solutions that have a solid resin content of approximately 30 to 70% by weight. A paint suitable for flow coating and rotational coating can be obtained. The objects to be coated with such paints include not only metals such as steel, aluminum, and copper, but also metallized plastics, conductive carbon objects, and non-metallic objects such as glass. , wood, plastic, etc.
次に、実施例、比較例を挙げて本発明を更に詳
細に説明する。例中、部は重量部、％は重量％で
ある。
◇実施例 １
温度計、撹拌機、還流冷却器、滴下ロート及び
窒素ガス吹込口を取り付けた反応容器に、窒素ガ
ス気流下、ポリエポキシドＡ（エピコート828油化
シエルエポキシ株式会社製）433部、エチレング
リコール−ビス−マレイン酸200部及びメチルイ
ソブチルケトン422部を仕込み、80℃まで徐々に
昇温して溶解した。ついで、80℃でジメチルエタ
ノールアミン３部を加え、徐々に昇温して90〜
100℃にした後、90〜100℃に保つて酸価が１以下
になるまで約４時間反応を継続した後、メチルイ
ソブチルケトン54部を加えて直ちに冷却し、温度
を60℃に下げた。ついで、60℃でジエチルアミン
227部を加え、60℃に保つて１時間反応を継続し
た後80℃まで昇温し、80℃に温度を保つて３時間
反応させた。ついで、窒素ガスの供給をとめた
後、反応容器内の気圧を−30〜−60cmHgに減圧
し、60〜80℃で40分間減圧蒸留し、未反応のアミ
ン及びメチルイソブチルケトンを除去した後、反
応容器内を大気圧下に戻し、80℃でエチレングリ
コールモノエチルエーテル161部を加え、充分撹
拌して、茶褐色透明な固形分80.3％、数平均分子
量2050のアミノ変性ポリエポキシド樹脂溶液(1)を
得た。
ついで、得られたアミノ変性ポリエポキシド樹
脂溶液(1)249部に対して酢酸８部を加えて充分混
合した後、硬化促進剤として酢酸マンガン3.6部
（マンガン金属として0.8部）を脱イオン水1739.4
部で溶解した酢酸マンガン水溶液1743部を徐々に
加えて希釈し、半透明なカチオン電着塗装に適し
た固形分10.0％の水分散液を得た。
ついで、燐酸亜鉛処理鋼板をこの水分散液中
で、130ボルトで60秒間電着して塗膜外観の良好
な被膜を得た。得られた被膜を150℃で30分間焼
付けて、膜厚28μの硬化被膜を得た。
得られた硬化被膜の試験結果を下記の第１表に
示す。
◇実施例 ２
実施例１で得られたアミノ変性ポリエポキシド
樹脂溶液(1)249部に対し、硬化促進剤として実施
例１で用いたと同じ酢酸マンガン3.6部を脱イオ
ン水13.2部及びイソプロピルアルコール135部に
溶解させて得られた酢酸マンガン水溶液を、
151.8部徐々に加えて希釈し赤褐色透明な噴霧塗
装に適した固形分50.0％の樹脂溶液を得た。
ついで得られた希釈溶液を用いて燐酸亜鉛処理
鋼板上に噴霧塗装し、10分間静置した後140℃で
30分間焼付けて、膜厚20〜30μの塗膜外観の良好
な硬化被膜を得た。
得られた硬化被膜の試験結果を下記の第１表に
示す。
◇実施例 ３
実施例１と同様な反応容器に、窒素ガス気流
下、ポリエポキシドＢ（エピコート1001油化シエ
ルエポキシ株式会社製）473部、実施例１で使用
したポリエポキシドA60部、ジプロピレングリコ
ール−ビス−マレイン酸106部、水素化ビスフエ
ノールＡ−ビス−マレイン酸70部及びメチルイソ
ブチルケトン473部を仕込み、80℃まで徐々に昇
温して溶解した。ついで、80℃でジメチルエタノ
ールアミン２部を加え、徐々に昇温して90〜100
℃にした後、90〜100℃に保つて酸価が１以下に
なるまで約４時間反応を継続した後、メチルイソ
ブチルケトン26部を加えて直ちに冷却し、温度を
60℃に下げた。ついで、60℃でジエチルアミン
129部を加え、60℃に保つて１時間反応を継続し
た後80℃まで昇温し、80℃に保つて３時間反応さ
せた。ついで、窒素ガスの供給を止めた後、反応
容器内の気圧を−30〜−60cmHgに減圧し、60〜
80℃で40分間減圧蒸溜し、未反応のジエチルアミ
ン及びメチルイソブチルケトンを除去し、反応容
器内を大気圧下に戻した後80℃でエチレングリコ
ールモノエチルエーテル161部を加え、充分撹拌
して茶褐色透明な固形分80.0％、数平均分子量
5000のアミノ変性ポリエポキシド樹脂溶液(2)を得
た。
ついで、得られたアミノ変性ポリエポキシド樹
脂溶液(2)250部に対して酢酸８部を加えて充分混
合した後、硬化促進剤として酢酸コバルト3.4部
（コバルト金属として0.8部）を脱イオン水1735.6
部で溶解させて得られた酢酸コバルト水溶液1739
部を徐々に加えて希釈し、半透明なカチオン電着
塗装に適した固形分10.0％の水分散液を得た。
ついで、燐酸亜鉛処理鋼板をこの水分散液中
で、実施例１と同様にして電着して塗膜外観の良
好な被膜を得た。得られた被膜を160℃で20分間
焼付けて、膜厚32μの硬化被膜を得た。得られた
硬化被膜の試験結果を下記第１表に示す。
◇実施例 ４
実施例３で得られたアミノ変性ポリエポキシド
樹脂溶液(2)250部に対して、硬化促進剤として実
施例３で用いたと同じ酢酸コバルト2.6部を脱イ
オン水20部及びイソプロピルアルコール60部に溶
解させて得られた酢酸コバルト溶液82.6部を加え
て、赤褐色透明な流れ塗装に適した固形分60.3％
の樹脂溶液を得た。ついで、得られた樹脂溶液を
用いて、燐酸亜鉛処理鋼板上に３ミル塗布棒で塗
布し、10分間静置した後、150℃で30分間焼付け
て、膜厚20〜30μの塗膜外観の良好な硬化被膜を
得た。得られた硬化被膜の試験結果を下記第１表
に示す。
◇実施例 ５
実施例１と同様な反応容器に、窒素ガス気流
下、実施例３で使用したと同じポリエポキシドＢ
385部、数平均分子量400のポリエチレングリコ
ールを用いて得られたポリエチレングリコール−
ビス−マレイン酸210部及びメチルイソブチルケ
トン595部を仕込み、80℃まで徐々に昇温して溶
解した。ついで、80℃でジメチエタノールアミン
１部を加え、徐々に昇温して90〜100℃にした後、
90〜100℃に保つて酸価１以下になるまで約４時
間反応を継続した後、メチルイソブチルケトン33
部を加えて直ちに冷却し温度を60℃に下げた。つ
いで、60℃でジエチルアミン80部を加え、60℃に
保つて１時間反応を継続した後、80℃まで昇温し
80℃に保つて３時間反応させた。ついで窒素ガス
の供給をやめ、反応容器内の気圧を−30〜−60cm
Hgに減圧し、60〜80℃で40分間減圧蒸溜し、未
反応のアミン及びメチルイソブチルケトンを除去
した後、反応容器内を大気圧に戻し、80℃でエチ
レングリコールモノエチルエーテル196部を加え、
充分撹拌して、茶褐色透明な固形分74.0％、数平
均分子量8300のアミノ変性ポリエポキシド樹脂溶
液(3)を得た。
ついで、得られたアミノ変性ポリエポキシド樹
脂溶液(3)270部に対して酢酸６部及び硬化促進剤
としてナフテン酸コバルト16部（コバルト金属と
して1.6部）を加えて充分混合した後、脱イオン
水1706部を徐々に加えて希釈し、半透明なカチオ
ン電着塗装に適した固形分10.0％水分散液を得
た。
ついで、燐酸亜鉛処理鋼板をこの水分散液中
で、実施例１と同様にして電着して塗膜外観の良
好な被膜を得た。
得られた被膜を140℃で30分間焼付けて、膜厚
19μの硬化被膜を得た。
得られた硬化被膜の試験結果を下記第１表に示
す。
◇実施例 ６
実施例５で得られたアミノ変性ポリエポキシド
樹脂溶液(3)270部に対して酢酸６部及び硬化促進
剤としてナフテン酸マンガン18.4部（マンガン金
属として1.1部）を加えて充分混合した後、脱イ
オン水703部を徐々に加えて希釈し、半透明な浸
漬塗装に適した円形分20.0％の水分散液を得た。
ついで燐酸亜鉛処理鋼板をこの水分散液中に浸
漬し、得られた被膜を150℃で30分間焼付けて膜
厚20〜30μの塗膜外観の良好な硬化被膜を得た。
得られた硬化被膜の試験結果を下記第１表に示
す。
◇比較例 １
実施例１と同様な反応容器に２，４−トリレン
ジイソシアネート652部、メチルイソブチルケト
ン50部を仕込み、撹拌し、30℃以下に保つて、２
−エチルヘキサノール488部を約５時間かけて滴
下し、２，４−トリレンジイソシアネートの２−
エチルヘキサノール半ブロツク化物を得た。
又、別の実施例１と同様な反応容器に、ポリエ
ポキシド（エピコート1001油化シエルエポキシ株
式会社製）507部及びキシレン24部を加え、140〜
150℃まで徐々に昇温し、ポリエポキシド中に存
在する水を除去した。
ついで、110℃まで冷却し、メチルイソブチル
ケトン50部及び上記の２，４−トリレンジイソシ
アネートの２−エチルヘキサノール半ブロツク化
物180部を加え、120℃で１時間加熱した。
ついで、ポリカプロラクトンジオール
（PCPO200ユニオンカーバイド社製）130部及び
ベンジルジメチルアミン0.4部を加え、130℃で４
時間加熱した後、メチルイソブチルケトン260部
を加えた。
ついで、80℃まで冷却し、ジエチレントリアミ
ン１モルとメチルイソブチルケトン２モルから作
られたジケチミン35部及びジエチルアミン31部を
加え、115℃で３時間加熱した後、エチレングリ
コールモノエチルエーテル157部を加え、60℃ま
で冷却してブロツク化イソシアネート硬化型ポリ
アミン樹脂溶液を得た。
得られたポリアミン樹脂溶液100部に対して、
硬化触媒としてジブチルスズジラウレート1.1部
及び酢酸７部を加え、充分撹拌した後、脱イオン
水425部を加えて半透明な固形分13.0％のカチオ
ン電着塗装に適した水分散液を得た。
ついで、燐酸亜鉛処理鋼板をこの水分散液中
で、180ボルトで90秒間電着して、塗膜外観の良
好な被膜を得た。この被膜を140〜160℃で焼付け
ることによつて外観の良好な膜厚22μの硬化被膜
を得た。
得られた硬化被膜の試験結果を上記実施例１乃
至６で得られた結果と共に第１表に示す。
Next, the present invention will be explained in more detail by giving Examples and Comparative Examples. In the examples, parts are parts by weight, and % is % by weight. ◇Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet, 433 parts of polyepoxide A (Epicote 828 manufactured by Yuka Ciel Epoxy Co., Ltd.) and ethylene were added under a nitrogen gas stream. 200 parts of glycol-bis-maleic acid and 422 parts of methyl isobutyl ketone were charged, and the temperature was gradually raised to 80°C to dissolve them. Next, 3 parts of dimethylethanolamine was added at 80°C, and the temperature was gradually raised to 90°C.
After the temperature was raised to 100°C, the reaction was continued for about 4 hours while maintaining the temperature at 90 to 100°C until the acid value became 1 or less, and then 54 parts of methyl isobutyl ketone was added and immediately cooled, and the temperature was lowered to 60°C. Then, diethylamine was added at 60°C.
After adding 227 parts and continuing the reaction at 60°C for 1 hour, the temperature was raised to 80°C, and the reaction was continued for 3 hours while maintaining the temperature at 80°C. Then, after stopping the supply of nitrogen gas, the pressure inside the reaction vessel was reduced to -30 to -60 cmHg, and vacuum distillation was performed at 60 to 80°C for 40 minutes to remove unreacted amine and methyl isobutyl ketone. Return the inside of the reaction vessel to atmospheric pressure, add 161 parts of ethylene glycol monoethyl ether at 80°C, and stir thoroughly to obtain a brown-brown transparent amino-modified polyepoxide resin solution (1) with a solid content of 80.3% and a number average molecular weight of 2050. Obtained. Next, 8 parts of acetic acid was added to 249 parts of the obtained amino-modified polyepoxide resin solution (1) and mixed thoroughly, and then 3.6 parts of manganese acetate (0.8 parts as manganese metal) was added to 1739.4 parts of deionized water as a curing accelerator.
1,743 parts of an aqueous solution of manganese acetate dissolved in 100 parts was gradually added to dilute the mixture to obtain a translucent aqueous dispersion with a solid content of 10.0% suitable for cationic electrodeposition coating. Then, a zinc phosphate-treated steel sheet was electrodeposited in this aqueous dispersion at 130 volts for 60 seconds to obtain a film with a good appearance. The obtained film was baked at 150° C. for 30 minutes to obtain a cured film with a thickness of 28 μm. The test results of the obtained cured film are shown in Table 1 below. ◇Example 2 To 249 parts of the amino-modified polyepoxide resin solution (1) obtained in Example 1, 3.6 parts of manganese acetate, the same as that used in Example 1, was added as a curing accelerator, 13.2 parts of deionized water, and 135 parts of isopropyl alcohol. Manganese acetate aqueous solution obtained by dissolving it in
151.8 parts were gradually added and diluted to obtain a reddish-brown transparent resin solution with a solid content of 50.0% suitable for spray coating. The resulting diluted solution was then sprayed onto a zinc phosphate treated steel plate, left to stand for 10 minutes, and then heated to 140°C.
After baking for 30 minutes, a cured film with a thickness of 20 to 30 μm and a good appearance was obtained. The test results of the obtained cured film are shown in Table 1 below. ◇Example 3 In a reaction vessel similar to Example 1, under a nitrogen gas flow, 473 parts of polyepoxide B (Epicote 1001 manufactured by Yuka Ciel Epoxy Co., Ltd.), 60 parts of polyepoxide A used in Example 1, and dipropylene glycol-bis were added. -106 parts of maleic acid, 70 parts of hydrogenated bisphenol A-bis-maleic acid, and 473 parts of methyl isobutyl ketone were charged, and the temperature was gradually raised to 80°C to dissolve them. Next, 2 parts of dimethylethanolamine was added at 80℃, and the temperature was gradually raised to 90-100℃.
℃, keep the temperature at 90-100℃ and continue the reaction for about 4 hours until the acid value becomes 1 or less, then add 26 parts of methyl isobutyl ketone, cool immediately, and lower the temperature.
The temperature was lowered to 60℃. Then, diethylamine was added at 60°C.
After adding 129 parts and continuing the reaction at 60°C for 1 hour, the temperature was raised to 80°C, and the reaction was continued at 80°C for 3 hours. Next, after stopping the supply of nitrogen gas, the pressure inside the reaction vessel was reduced to -30 to -60 cmHg, and the pressure was reduced to 60 to -60 cmHg.
Distillation under reduced pressure was carried out at 80℃ for 40 minutes to remove unreacted diethylamine and methyl isobutyl ketone, and after returning the inside of the reaction vessel to atmospheric pressure, 161 parts of ethylene glycol monoethyl ether was added at 80℃, and the mixture was thoroughly stirred to give a brownish-brown color. Clear solids content 80.0%, number average molecular weight
5,000 amino modified polyepoxide resin solution (2) was obtained. Next, 8 parts of acetic acid was added to 250 parts of the obtained amino-modified polyepoxide resin solution (2) and mixed thoroughly, and then 3.4 parts of cobalt acetate (0.8 parts as cobalt metal) was added to 1735.6 parts of deionized water as a curing accelerator.
Cobalt acetate aqueous solution obtained by dissolving 1739 parts
A translucent aqueous dispersion with a solid content of 10.0% suitable for cationic electrodeposition coating was obtained. Next, a zinc phosphate-treated steel sheet was electrodeposited in this aqueous dispersion in the same manner as in Example 1 to obtain a film with a good appearance. The obtained film was baked at 160° C. for 20 minutes to obtain a cured film with a thickness of 32 μm. The test results of the obtained cured film are shown in Table 1 below. ◇Example 4 To 250 parts of the amino-modified polyepoxide resin solution (2) obtained in Example 3, 2.6 parts of the same cobalt acetate used in Example 3 as a curing accelerator was added to 20 parts of deionized water and 60 parts of isopropyl alcohol. Add 82.6 parts of cobalt acetate solution obtained by dissolving in 1 part to obtain a reddish-brown transparent color with a solid content of 60.3% suitable for flow coating.
A resin solution was obtained. Next, the resulting resin solution was applied onto a zinc phosphate-treated steel plate with a 3 mil applicator rod, left to stand for 10 minutes, and then baked at 150°C for 30 minutes to obtain a coating with a thickness of 20 to 30 μm. A good cured film was obtained. The test results of the obtained cured film are shown in Table 1 below. ◇Example 5 The same polyepoxide B used in Example 3 was placed in a reaction vessel similar to Example 1 under a nitrogen gas stream.
Polyethylene glycol obtained using 385 parts of polyethylene glycol with a number average molecular weight of 400.
210 parts of bis-maleic acid and 595 parts of methyl isobutyl ketone were charged, and the temperature was gradually raised to 80°C to dissolve them. Next, 1 part of dimethyethanolamine was added at 80°C, and the temperature was gradually raised to 90-100°C.
After maintaining the temperature at 90 to 100℃ and continuing the reaction for about 4 hours until the acid value becomes 1 or less, methyl isobutyl ketone 33
was added and immediately cooled to lower the temperature to 60°C. Next, 80 parts of diethylamine was added at 60°C, the reaction was continued for 1 hour at 60°C, and then the temperature was raised to 80°C.
The mixture was kept at 80°C and reacted for 3 hours. Then, stop supplying nitrogen gas and reduce the pressure inside the reaction vessel to -30 to -60 cm.
After reducing the pressure to Hg and distilling under reduced pressure at 60 to 80°C for 40 minutes to remove unreacted amine and methyl isobutyl ketone, the inside of the reaction vessel was returned to atmospheric pressure, and 196 parts of ethylene glycol monoethyl ether was added at 80°C. ,
After thorough stirring, a brown, transparent amino-modified polyepoxide resin solution (3) having a solid content of 74.0% and a number average molecular weight of 8,300 was obtained. Next, 6 parts of acetic acid and 16 parts of cobalt naphthenate (1.6 parts as cobalt metal) as a curing accelerator were added to 270 parts of the obtained amino-modified polyepoxide resin solution (3) and mixed thoroughly, followed by 1706 parts of deionized water. A translucent aqueous dispersion with a solid content of 10.0% suitable for cationic electrodeposition coating was obtained. Next, a zinc phosphate-treated steel sheet was electrodeposited in this aqueous dispersion in the same manner as in Example 1 to obtain a film with a good appearance. The resulting film was baked at 140℃ for 30 minutes to determine the film thickness.
A cured film of 19μ was obtained. The test results of the obtained cured film are shown in Table 1 below. ◇Example 6 To 270 parts of the amino-modified polyepoxide resin solution (3) obtained in Example 5, 6 parts of acetic acid and 18.4 parts of manganese naphthenate as a curing accelerator (1.1 parts as manganese metal) were added and mixed thoroughly. Thereafter, 703 parts of deionized water was gradually added to dilute the dispersion to obtain a 20.0% round aqueous dispersion suitable for translucent dip coating. A zinc phosphate-treated steel plate was then immersed in this aqueous dispersion, and the resulting coating was baked at 150°C for 30 minutes to obtain a cured coating with a thickness of 20 to 30 μm and a good coating appearance. The test results of the obtained cured film are shown in Table 1 below. ◇Comparative Example 1 652 parts of 2,4-tolylene diisocyanate and 50 parts of methyl isobutyl ketone were placed in the same reaction vessel as in Example 1, stirred, and kept at 30°C or below.
- 488 parts of ethylhexanol was added dropwise over about 5 hours, and the 2-
A semi-blocked product of ethylhexanol was obtained. In addition, 507 parts of polyepoxide (Epicoat 1001 manufactured by Yuka Ciel Epoxy Co., Ltd.) and 24 parts of xylene were added to a reaction vessel similar to that in Example 1, and 140 to
The temperature was gradually raised to 150°C to remove water present in the polyepoxide. Then, the mixture was cooled to 110°C, 50 parts of methyl isobutyl ketone and 180 parts of the above 2-ethylhexanol semi-blocked product of 2,4-tolylene diisocyanate were added, and the mixture was heated at 120°C for 1 hour. Next, 130 parts of polycaprolactone diol (PCPO200 manufactured by Union Carbide) and 0.4 parts of benzyldimethylamine were added, and the mixture was heated at 130°C for 4 hours.
After heating for an hour, 260 parts of methyl isobutyl ketone were added. Then, it was cooled to 80°C, 35 parts of diketimine made from 1 mole of diethylenetriamine and 2 moles of methyl isobutyl ketone and 31 parts of diethylamine were added, and after heating at 115°C for 3 hours, 157 parts of ethylene glycol monoethyl ether was added. The solution was cooled to 60°C to obtain a blocked isocyanate-curable polyamine resin solution. For 100 parts of the obtained polyamine resin solution,
1.1 parts of dibutyltin dilaurate and 7 parts of acetic acid were added as a curing catalyst, and after thorough stirring, 425 parts of deionized water was added to obtain a translucent aqueous dispersion having a solid content of 13.0% and suitable for cationic electrodeposition coating. Then, a zinc phosphate-treated steel sheet was electrodeposited in this aqueous dispersion at 180 volts for 90 seconds to obtain a film with a good appearance. By baking this film at 140 to 160°C, a hardened film with a thickness of 22 μm and a good appearance was obtained. The test results of the obtained cured films are shown in Table 1 together with the results obtained in Examples 1 to 6 above.
【表】【table】
【表】【table】
第１表の実施例１〜６に示された結果から容易
に理解されるように、本発明の塗装用熱硬化性樹
脂組成物によれば、比較例１に示される従来のブ
ロツク化ポリイソシアネート硬化形組成物に比
べ、20℃低い焼付け温度でも充分硬化できる低温
硬化性を有すると共に、その得られる硬化被膜
も、硬さ、耐溶剤性及び耐蝕性に優れることがわ
かる。
即ち本発明において得られる塗装用熱硬化性樹
脂組成物をカチオン電着塗装及びその他の塗装方
法によつて塗装し、得られた被膜を140〜160℃で
20〜40分間焼付けることによつて硬化被膜が得ら
れる。
この焼付条件は、従来のブロツク化ポリイソシ
アネート形組成物の焼付条件である、160〜180
℃、20〜40分間に比べて、約20℃程度低く、省エ
ネルギー効果、生産性の向上に大きく寄与する許
りでなく、以上のようにして得られた本発明の硬
化塗膜は、従来のものに比べ硬さ、耐溶剤性及び
耐蝕性に格段の優位差を認めることができる。
As can be easily understood from the results shown in Examples 1 to 6 in Table 1, the thermosetting resin composition for coating of the present invention can be used in comparison with the conventional blocked polyisocyanate shown in Comparative Example 1. It can be seen that the composition has low-temperature curability that can be sufficiently cured even at a baking temperature 20°C lower than that of the curable composition, and the resulting cured film also has excellent hardness, solvent resistance, and corrosion resistance. That is, the thermosetting resin composition for coating obtained in the present invention is applied by cationic electrodeposition coating or other coating methods, and the resulting film is heated at 140 to 160°C.
A hardened film is obtained by baking for 20-40 minutes. This baking condition is 160 to 180, which is the baking condition for conventional blocked polyisocyanate type compositions.
The cured coating film of the present invention obtained as described above is approximately 20°C lower than that of the conventional cured coating film, which contributes significantly to energy saving effects and improved productivity. It can be seen that there is a significant difference in hardness, solvent resistance, and corrosion resistance compared to other materials.
Claims (1)
役するエチレン性不飽和結合を有する二塩基酸化
合物で連結した後、そのエチレン性不飽和結合及
び残存するエポキシ基に、沸点が100℃以下の第
一モノアミン又は第二モノアミンを付加して得ら
れた数平均分子量1100〜10000のアミノ変性ポリ
エポキシドと、当該アミノ変性ポリエポキシド固
形分100重量部に対して、0.1〜20重量部の硬化促
進剤とを含んで成る塗装用熱硬化性樹脂組成物。1 After linking polyepoxide with a dibasic acid compound having an ethylenically unsaturated bond conjugated with two carbonyl groups, a primary monoamine with a boiling point of 100°C or less is added to the ethylenically unsaturated bond and the remaining epoxy group. or an amino-modified polyepoxide with a number average molecular weight of 1,100 to 10,000 obtained by adding a second monoamine, and 0.1 to 20 parts by weight of a curing accelerator based on 100 parts by weight of the solid content of the amino-modified polyepoxide. Thermosetting resin composition for painting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15156085A JPH0244848B2 (en) | 1985-07-10 | 1985-07-10 | TOSOYONET SUKOKASEIJUSHISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15156085A JPH0244848B2 (en) | 1985-07-10 | 1985-07-10 | TOSOYONET SUKOKASEIJUSHISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6211776A JPS6211776A (en) | 1987-01-20 |
| JPH0244848B2 true JPH0244848B2 (en) | 1990-10-05 |
Family
ID=15521194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15156085A Expired - Lifetime JPH0244848B2 (en) | 1985-07-10 | 1985-07-10 | TOSOYONET SUKOKASEIJUSHISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0244848B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07505038A (en) * | 1992-01-10 | 1995-06-01 | フィッシャー エレクトリック モーター テクノロジー インコーポレイテッド | Lightweight, high-power electric motor/generator |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4865316B2 (en) * | 2005-12-08 | 2012-02-01 | 古河電気工業株式会社 | Level wound coil package |
-
1985
- 1985-07-10 JP JP15156085A patent/JPH0244848B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07505038A (en) * | 1992-01-10 | 1995-06-01 | フィッシャー エレクトリック モーター テクノロジー インコーポレイテッド | Lightweight, high-power electric motor/generator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6211776A (en) | 1987-01-20 |
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