JPH0244849B2 - JIKOKOKASEIJUSHINOSEIZOHOHO - Google Patents
JIKOKOKASEIJUSHINOSEIZOHOHOInfo
- Publication number
- JPH0244849B2 JPH0244849B2 JP18828685A JP18828685A JPH0244849B2 JP H0244849 B2 JPH0244849 B2 JP H0244849B2 JP 18828685 A JP18828685 A JP 18828685A JP 18828685 A JP18828685 A JP 18828685A JP H0244849 B2 JPH0244849 B2 JP H0244849B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- self
- resin
- michael
- 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
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 22
- -1 amine imide Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 34
- 238000001723 curing Methods 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 28
- 229920000768 polyamine Polymers 0.000 description 23
- 238000004070 electrodeposition Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 125000002091 cationic group Chemical group 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 150000004658 ketimines Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 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
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-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
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-UHFFFAOYSA-N 0.000 description 1
- FNVOFDGAASRDQY-UHFFFAOYSA-N 3-amino-2,2-dimethylpropan-1-ol Chemical compound NCC(C)(C)CO FNVOFDGAASRDQY-UHFFFAOYSA-N 0.000 description 1
- LPUBRQWGZPPVBS-UHFFFAOYSA-N 3-butoxypropan-1-amine Chemical compound CCCCOCCCN LPUBRQWGZPPVBS-UHFFFAOYSA-N 0.000 description 1
- TWXCJZHSMRBNGO-UHFFFAOYSA-N 3-decoxypropan-1-amine Chemical compound CCCCCCCCCCOCCCN TWXCJZHSMRBNGO-UHFFFAOYSA-N 0.000 description 1
- ZRJOUVOXPWNFOF-UHFFFAOYSA-N 3-dodecoxypropan-1-amine Chemical compound CCCCCCCCCCCCOCCCN ZRJOUVOXPWNFOF-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- UTOXFQVLOTVLSD-UHFFFAOYSA-N 3-propoxypropan-1-amine Chemical compound CCCOCCCN UTOXFQVLOTVLSD-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 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
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- QFUSOYKIDBRREL-UHFFFAOYSA-N but-2-en-1-amine Chemical compound CC=CCN QFUSOYKIDBRREL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000000539 dimer Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 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
- VPPWQRIBARKZNY-UHFFFAOYSA-N oxo(diphenyl)tin Chemical compound C=1C=CC=CC=1[Sn](=O)C1=CC=CC=C1 VPPWQRIBARKZNY-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- IAWXHEPLJXAMSG-UHFFFAOYSA-N pent-2-en-1-amine Chemical compound CCC=CCN IAWXHEPLJXAMSG-UHFFFAOYSA-N 0.000 description 1
- IGEIPFLJVCPEKU-UHFFFAOYSA-N pentan-2-amine Chemical compound CCCC(C)N IGEIPFLJVCPEKU-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
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The present invention relates to a method for producing a water-dispersible, low-temperature-curing self-curing resin suitable for cationic electrodeposition coating.
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Cationic electrodeposition coating has superior anti-corrosion properties for coated objects compared to conventional anionic electrodeposition coating, and therefore its use has been increasing in recent years, mainly in the automotive coating field. Various resins have been proposed for use in such cationic electrodeposition coatings, one of which is disclosed in Japanese Patent Application No. 72924/1983. The invention provides the following formula by introducing an amine imide group pendant into a polyamine resin having an amino group or an imino group. After the amine imide group is thermally decomposed at a low temperature of 120°C to 170°C, preferably 140 to 160°C, the tertiary amine is eliminated by rearrangement and an isocyanate group is generated, and the generated isocyanate group is It reacts with the hydroxyl group, amino group, or imino group in the resin to form a three-dimensional structure to obtain an infusible and insoluble cured coating, and the amine imide group is neutralized with acid to become an acylhydrazinium base. In particular, by taking advantage of the fact that a stable aqueous dispersion of a cationic resin can be obtained, the resin composition is made suitable for cationic electrodeposition coating.
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æ§èœçãäœäžããåŸåãããã[Problems to be Solved by the Invention] The method for producing an amine imide group-containing amino-modified polyepoxide (hereinafter referred to as a self-curing resin) described in JP-A No. 60-72924 involves the step of manufacturing a polyepoxide and a polyepoxide in the first step. A polyamine resin is obtained by reacting with a first monoamine or a ketimine-blocked amino group-containing polyamine, and then in a second step, the polyamine resin and an ethylenically unsaturated compound having an amine imide group (hereinafter referred to as an amine imide compound) are produced.
This is done by reacting with. However, in this manufacturing process, the proportion of the polyamine resin in the first step in the self-curing resin is very large, so it is not possible to manufacture several batches of polyamine resin in advance using a manufacturing device with a fixed volume. First, it is necessary to produce polyamine resin for each batch. In addition, in order to obtain a polyamine resin, it is necessary to introduce into the resin a nitrogen-containing group having an active hydrogen that is capable of Michael-type addition. Polyamines containing blocked amino groups or mixtures thereof must be used. In this case, if the primary monoamine is used, it must be used in large excess to prevent gelation with the polyepoxide, and unreacted amine must be removed after the reaction. In addition, the ketimine-blocked amino group-containing polyamine does not gel at the stage of reaction with the epoxy group because it contains imino groups, but since the polyamine is used, the concentration of nitrogen-containing groups in the resin may be higher than necessary. There is a tendency for the coating film performance to deteriorate due to the increase in the amount of water.
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In order to solve the above-mentioned problems, the present inventors have conducted intensive research and have produced a Michael-type adduct of an amine imide compound and a primary monoamine, and then converted this Michael-type adduct to polyepoxide. By adding this, a self-curing resin can be easily obtained, and as a result, the manufacturing process of the self-curing resin can be simplified and shortened, and at the same time, the concentration of nitrogen-containing groups in the resin can be increased. The present inventors have discovered that since the amount does not increase beyond that level, the properties of the coating film are not adversely affected, leading to the completion of the present invention. That is, the present invention adds a primary monoamine to an ethylenically unsaturated compound having an amine imide group to form the following general formula: (In the formula, R1 represents an alkyl group, alkoxyalkyl group, alkenyl group, hydroxyalkyl group, or aryl group having 2 to 30 carbon atoms, R2, R3, R4
each represents an alkyl group or a hydroxyalkyl group having 1 to 8 carbon atoms. The present invention relates to a method for producing a self-curing resin, which is characterized by obtaining a Michael type adduct of ) and further adding the Michael type adduct to a polyepoxide to obtain an amino-modified polyepoxide containing an amine imide group. Examples of the ethylenically unsaturated compound having an amine imide group used in the present invention include 1, 1,
1-trimethylamine methacrylimide, 1,1
-dimethyl-1-ethylamine methacrylimide, 1,1-dimethyl-1-(2-hydroxypropyl)amine methacrylimide, and the like. Next, the first monoamine used in the present invention may have an alkyl group, an alkoxylalkyl group, an alkenyl group, a hydroxyalkyl group, or an aryl group having 2 to 30 carbon atoms, for example,
ethylamine, propylamine, butylamine,
1-methylbutylamine, hexylamine, 2-
Ethylhexylamine, 3-methoxypropylamine, 3-ethoxypropylamine, propoxypropylamine, butoxypropylamine, 2-
Ethylhexyloxypropylamine, decyloxypropylamine, dodecyloxypropylamine,
1-amino-2-propene, 1-amino-2-butene, 1-amino-2-pentene, oleylamine, 2-aminoethanol, 2-amino-1-propanol, 2,2-dimethyl-3-amino-propanol , phenylamine, benzylamine,
Examples include α-phenethylamine and β-phenethylamine. The primary monoamine undergoes Michael addition to the amine imide compound to form an imino group useful for subsequent reaction with the polyepoxide. The amine added to polyepoxide is
If desired, a conventionally known secondary amine may be used in combination with the Michael type adduct obtained by adding a primary monoamine to the above-mentioned amine imide compound. Such secondary amines may have one or more imino groups in one molecule, such as diethylamine, diisopropylamine, diethanolamine, methylethanolamine, diisopropanolamine, N,N'-dimethylethylenediamine, etc. Examples include secondary monoamines and polyamines produced by blocking all amino groups with ketimine. Examples of ketimine-blocked amino group-containing polyamines include monomethylaminopropylamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetriamine, and other polyamines in which amino groups are combined with ketones such as acetone, methylethylketone, and methylisobutylketone. Examples include those converted to ketimine by the following reaction. Next, the polyepoxide used in the present invention is a compound having two or more 1,2 epoxy groups, such as polyglycidyl ether of polyphenol. Here, as the polyphenol, for example, bisphenol A
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ãã[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. Also used are, for example, oxyalkyl adducts of polyphenols such as ethylene oxide adducts and propylene oxide adducts, and polyglycidyl ethers such as novolac type phenol resins and polyphenol resins similar to these. Next, as other polyepoxides,
Examples 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. The polyepoxide may be further reacted to undergo chain extension to increase its molecular weight. In this case, chain extenders include active hydrogen-containing compounds that are reactive with epoxy groups, such as glycols, diamines, polyether polyols, dimer acids, hydantoins, bisphenol A, polyaminoamides, hydroxyl groups and amino groups such as amino acids, Examples include compounds containing imino groups, thiol groups, carboxyl groups, and the like. Next, a method for producing a self-curing resin, which is a feature of the present invention, will be explained. First, in the Michael type addition reaction method between a primary monoamine and an amine imide compound, the primary monoamine and an organic solvent are charged into a reaction vessel, and the mixture is stirred at an appropriate temperature, preferably 70°C or higher and 120°C or lower, under an inert gas flow. while adding the amine imide compound. The reason for keeping the temperature below 120°C is to prevent thermal decomposition of the amine imide compound during the reaction. The amine imide compound can be added by a method of adding the entire amount at once, a method of adding in several portions, a method of adding dropwise, or the like. In addition, the reaction between an amine imide compound and a primary monoamine is not possible in the presence of an acid because the acylhydrazinium base whose amine imide group is neutralized with an acid is more effective in increasing the reactivity with the primary monoamine. It is preferable to do so. The acid used for this purpose may be any conventionally known organic acid 2 useful for dispersing the self-curing resin obtained in the present invention in water, as long as it is an inorganic acid, and the amount thereof is determined per mole of the amine imide compound. It is 0.5 to 1 mole. Further, at this stage, heating, cooling, refluxing of volatile components, addition of an organic solvent, etc. can be performed. After the addition of the amine imide compound is completed, the reaction is continued at an appropriate temperature and time as necessary, and then dilution with an organic solvent, filtration, and other steps are performed to obtain a resinous solution of the Michael adduct. Here, the organic solvent is an organic solvent used in the Michael addition reaction between the primary monoamine and the amine imide compound and the subsequent addition reaction between the Michael adduct and polyepoxide; For example, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, and ether alcohols such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether are preferable, and the organic solvent used in the latter reaction is, 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 are preferred. Next, in the method of addition reaction between the obtained Michael adduct and polyepoxide, part or all of the polyepoxide is charged into a reaction vessel and mixed under an inert gas flow to form a uniform liquid. If necessary in this step, heating, addition of a suitable organic solvent, preliminary reaction of the polyepoxide with other components such as bisphenol A, etc. can be carried out. Next, the Michael adduct is added to the homogeneous liquid while stirring the mixture at an appropriate temperature and under a stream of inert gas. Addition of the Michael type adduct can be carried out by adding the entire amount at once, adding it in several portions, dropping it, etc. Depending on the timing of the process, the type and amount of the Michael type adduct can be added. can be changed. At this stage, heating, cooling, refluxing of volatile components, addition of a portion of polyepoxide, an organic solvent, etc. can be performed. After the addition of the Michael type adduct is completed, the reaction is continued at an appropriate temperature and time as required, and then dilution with an organic solvent, distillation, filtration, etc. are performed to obtain a self-curing resin. The proportion of the Michael type adduct in the self-curing resin is preferably 5 to 35% by weight as a solid content, and if it is less than 5% by weight, it will not be curable at low temperature and the physical properties of the resulting coating will deteriorate. If the amount exceeds 35% by weight, problems will arise in the electrodeposition properties of the resulting aqueous dispersion and in the physical properties of the resulting coating film. The self-curing resin produced according to the present invention already contains an acylhydrazinium base, but if necessary, the remaining amine imide groups can also be neutralized with an acid to convert them into acylhydrazinium bases. conversion is possible and further dilution with water allows the formation of an aqueous dispersion.
Here, the acid is an organic acid or an inorganic acid, such as formic acid, acetic acid, lactic acid, phosphoric acid, and the like. In addition, the proportion of acylhydrazinium base in the self-curing resin obtained by neutralizing the amine imide group,
The structures and molecular weights of the various components must be mutually adjusted by taking into account dispersion stability, electrodepositivity, crosslinking curability, coating film performance, etc. when the self-curing resin is mixed with water. By immersing an anode and a cathode consisting of a conductive coating material in an aqueous dispersion of a self-curing resin, that is, a cationic electrodeposition paint bath, and applying a voltage between the two electrodes, the electrocoatable resin is coated. It is deposited as a film on the cathode surface. Such cationic electrodeposition coating techniques are well known in the art; however, the deposited coating can be applied to the surface of the coated material to such an extent that it is not washed off by water washing after removal from the cationic electrodeposition paint bath. It must have staying power. The self-curing resin produced in the present invention basically consists of an amino-modified polyepoxide containing an amine imide group and an acid as a neutralizing agent, and other components include those used in ordinary cationic electrodeposition coatings. plasticizer; surfactant; such as titanium dioxide, carbon black, talc, kaolin,
Pigments such as color pigments such as silica, lead silicate, basic lead chromate, and zinc phosphate, extender pigments, and antirust pigments;
For example, hydrophilic/semi-hydrophilic organic solvents such as isopropyl alcohol, butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diacetone alcohol;
For example, curing catalysts such as dibutyltin dilaurate, dibutyltin dioxide, diphenyltin oxide; water, etc. are added as appropriate, and are commonly used in the manufacture of paints, such as resolvers, homomixers, sand grind mills, attritors, and roll mills. The mixture is uniformly mixed and dispersed using a mixer or a dispersing machine such as the above, to form a cationic electrodeposition paint bath which is an aqueous dispersion having a resin solid content of 10 to 25% by weight.
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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. âExample 1 In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet, 300 parts of 2-ethylhexylamine was charged under a nitrogen gas stream, and the temperature was gradually raised to 90°C. Next, the following mixture was added dropwise over about 1 hour while maintaining the temperature at 90°C. 1,1,1-Trimetalamine methacrylimide 329 parts Acetic acid 111 parts Ethylene glycol monobutyl ether 329 parts After the dropwise addition, the reaction was continued at 90°C for 2 hours to form a pale yellow transparent Michael adduct with a solid content of 58.8%. Obtained. In addition, 950 parts of polyepoxide (trade name: Epicote 1004, manufactured by Yuka Ciel Epoxy Co., Ltd.) and 282 parts of methyl isobutyl ketone were charged into another reaction vessel similar to the above under a nitrogen gas stream, and the temperature was gradually raised to 110°C. and dissolved. Then the Michael adduct
369 parts and 38 parts of ketimine (obtained from 1 mol of monomethylaminopropylamine and 1 mol of methyl isobutyl ketone, a methyl isobutyl ketone solution with a solid content of 90.0%) were added, and the mixture was heated under a nitrogen gas stream.
The reaction was carried out at 90° C. for 2 hours to obtain a self-curing resin having a number average molecular weight of 2370 and a solid content of 73.3%. 136 parts of the obtained self-curing resin was diluted with deionized water to obtain an aqueous dispersion having a resin solid content of 10%. The obtained aqueous fraction was transferred to a polyvinyl chloride electrodeposition tank having an internal volume of about 1 liter, the temperature was adjusted to 25°C, and a zinc phosphate-treated steel plate was connected to the cathode as the object to be coated. Next, a carbon plate was inserted into the aqueous dispersion as an anode, and a cationic electrodeposition coating was performed by applying a direct current of 80 volts for 2 minutes while stirring the aqueous dispersion. After washing with water, bake at 150â for 30 minutes to obtain a dry film thickness.
A cured coating film of 19ÎŒ was obtained. The test results of the obtained cured coating films are shown in Table 1 below. âExample 2 In a reaction vessel similar to Example 1, under a nitrogen gas stream,
Prepare 150 parts of 2-amino-1-propanol,
The temperature was gradually raised to 70°C. Next, while maintaining the temperature at 70â, add about 1 cup of the following mixture.
It took some time to drip. 1,1-Dimethyl-1-(2-hydroxypropyl)amine methacrylimide 372 parts Acetic acid 120 parts Ethylene glycol monobutyl ether 372 parts After dropping, the reaction was continued at 70°C for 1 hour to give a light yellow transparent solid content of 51.5%. Michael-shaped adducts were obtained. In addition, 950 parts of polyepoxide (trade name: Epiyute 1004 manufactured by Yuka Ciel Epoxy Co., Ltd.) and 244 parts of methyl isobutyl ketone were charged into a reaction vessel similar to that in Example 1 under a nitrogen gas stream, and the temperature was gradually raised to 110°C. and dissolved. Then the Michael adduct
506 parts were added, and the reaction was carried out at 90° C. for 2 hours under a nitrogen gas stream to obtain a self-curing resin with a number average molecular weight of 2380 and a solid content of 71.2%. 140 parts of the obtained self-curing resin was diluted with deionized water to obtain an aqueous dispersion having a resin solid content of 10%. The obtained aqueous dispersion was treated in the same manner as in Example 1,
Cationic electrodeposition painting was performed. After washing with water, bake at 150â for 30 minutes, dry film thickness: 19ÎŒ
A cured coating film was obtained. The test results of the obtained cured coating films are shown in Table 1 below. âExample 3 In a reaction vessel similar to Example 1, 534 parts of oleylamine (trade name: Amine OB, manufactured by NOF Corporation) was charged under a nitrogen gas flow, and the temperature was gradually raised to 80°C. Next, the following mixture was added dropwise over a period of about 1 hour while maintaining the temperature at 80°C. 1,1-dimethyl-1-(2-hydroxypropyl)amine methacrylimide 372 parts Acetic acid 96 parts Ethylene glycol monobutyl ether 372 parts After dropping, the reaction was continued at 80°C for 2 hours to give a yellowish brown transparent solid content of 65.9%. Michael-shaped adducts were obtained. In addition, polyepoxide (trade name: Epicoat 1004
950 parts (manufactured by Yuka Ciel Epoxy Co., Ltd.) and 244 parts of methyl isobutyl ketone were charged, and the temperature was gradually raised to 110°C to dissolve them. Then, the Michael type adduct
687 parts were added and reacted for 2 hours at 90°C under a nitrogen gas stream to obtain a self-curing resin with a number average molecular weight of 2800 and a solid content of 74.6%. 134 parts of the obtained self-curing resin was diluted with deionized water to obtain an aqueous dispersion having a resin solid content of 10%. The obtained aqueous dispersion was treated in the same manner as in Example 1,
Cationic electrodeposition coating was performed. After washing with water, bake at 150â for 30 minutes to obtain a dry film thickness.
A cured coating film of 20ÎŒ was obtained. The test results of the obtained cured coating films are shown in Table 1 below. âComparative Example 1 In a reaction vessel similar to Example 1, 950 parts of polyepoxide (trade name Epicoat 1004 manufactured by Yuka Ciel Epoxy Co., Ltd.) and 336 parts of methyl isobutyl ketone were charged under a nitrogen gas flow, and the mixture was gradually raised to 110°C. Warm and dissolve. Next, 118 parts of propylamine was charged, and the mixture was reacted at 50° C. for 5 hours under a nitrogen gas stream. Next, the temperature was raised to 120°C and nitrogen gas was blown vigorously to remove unreacted amine, yielding a pale yellow transparent polyamine resin with a solid content of 76.6%. The following mixture was added dropwise to the resulting polyamine resin over a period of about 1 hour while maintaining the temperature at 70°C. 1,1-dimethyl-1-(2-hydroxypropyl)amine acrylamide 138 parts Ethylene glycol monobutyl ether 138 parts After dropping, the reaction was continued at 70°C for 2 hours to achieve a self-curing product with a number average molecular weight of 2200 and a solid content of 72.0%. A synthetic resin was obtained. 2 parts of acetic acid per 138 parts of the self-curing resin obtained.
After adding 1.0 parts and thoroughly mixing, the mixture was diluted with deionized water to obtain an aqueous dispersion having a resin solids content of 10%. The obtained aqueous dispersion was treated in the same manner as in Example 1,
Cationic electrodeposition coating was performed. 30 at 150â after washing with water
After baking for a minute, a cured coating film with a dry film thickness of 18 ÎŒm was obtained. The test results of the obtained cured coating films are shown in Table 1 below. âComparative Example 2 In a reaction vessel similar to Example 1, 950 parts of polyepoxide (trade name Epicoat 1004 manufactured by Yuka Ciel Epoxy Co., Ltd.) and 355 parts of methyl isobutyl ketone were charged under a nitrogen gas flow, and the mixture was gradually heated to 110°C. It was heated and dissolved. Next, ketimine (obtained from 1 mol of monomethylaminopropylamine and 1 mol of methyl isobutyl ketone, solid content 90.0%)
Add 188 parts of methyl isobutyl ketone solution),
The reaction was carried out at 90°C for 2 hours under a nitrogen gas stream to obtain a pale yellow transparent polyamine resin with a solid content of 76.2%. While maintaining the obtained polyamine resin at 90°C, 27 parts of deionized water and 20 parts of ethylene glycol monobutyl ether were gradually added, and then the following mixture was added dropwise over about 1 hour. 1,1,1-trimethylamine acrylimide
128 parts ethylene glycol monobutyl ether 128 parts After the dropwise addition, the reaction was continued at 90°C for 2 hours to obtain a self-curing resin with a number average molecular weight of 2330 and a solid content of 65.0%. 2 parts of acetic acid per 154 parts of the self-curing resin obtained.
After adding 1.0 parts and thoroughly mixing, the mixture was diluted with deionized water to obtain an aqueous dispersion having a resin solids content of 10%. The obtained aqueous dispersion was treated in the same manner as in Example 1,
Cationic electrodeposition coating was performed. 30 at 150â after washing with water
After baking for a minute, a cured coating film with a dry film thickness of 19 ÎŒm was obtained. The test results of the obtained cured coating films are shown in Table 1 below. Table 1 below also shows the amine values, proportions in the self-curing resin, and manufacturing times of the electrodeposition coating films obtained in Examples 1 to 3 and Comparative Examples 1 to 2.
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In the manufacturing process of Examples 1 to 3, the average proportion of Michael adducts in the self-curing resin was
Because it is as small as 29.2%, it is possible to manufacture and store several batches of Michael-shaped adducts in advance in a fixed-volume manufacturing device, and use a portion each time self-curing resin is manufactured. be. On the other hand, in the manufacturing process of Comparative Examples 1 and 2, the ratio of polyamine resin in the self-curing resin in the first step is as high as 81.8% on average, so the polyamine resin is prepared in advance in several batches using a manufacturing device with a fixed volume. It is not possible to produce the polyamine resin in batches, and it is necessary to produce the polyamine resin in batches. Therefore, when manufacturing the self-curing resin in Examples 1 to 3, the manufacturing time was only 3 hours, making it possible to simplify and shorten the manufacturing process, whereas in Comparative Examples 1 to 2
When manufacturing self-curing resin, the manufacturing time is 6
It takes a long time, ~9 hours. In addition, the resin produced according to the present invention can always keep the concentration of nitrogen-containing groups in the resin to the minimum necessary, so there is no drawback that the concentration of nitrogen-containing groups increases and deteriorates coating performance. There is no. In addition, electrodeposition was carried out using the cationic electrodeposition paint bath obtained according to the present invention, using the conductive object as a cathode, in the same manner as ordinary cationic electrodeposition, and after washing with water, it was heated at 130 to 160°C. A cured coating is obtained by baking for 20-40 minutes. The cured coating film thus obtained is excellent in pencil hardness, adhesion, impact resistance, flexibility, acetone rubbing resistance, water resistance, corrosion resistance, acid resistance, etc. However, in the known method of obtaining the resin by adding an amine imide compound to the polyamine resin, the cured coating film tends to be inferior in water resistance, corrosion resistance, and acid resistance due to the high amine value of the electrodeposited coating film.
Claims (1)
åç©ã«ç¬¬äžã¢ãã¢ãã³ãä»å ãããŠãäžèšäžè¬åŒ ïŒåŒäžãR1ã¯ççŽ æ°ïŒã30ã®ã¢ã«ãã«åºãã¢
ã«ã³ãã·ã¢ã«ãã«åºãã¢ã«ã±ãã«åºãããããã·
ã¢ã«ãã«åºåã¯ã¢ãªãŒã«åºãè¡šããR2ïŒR3ïŒR4
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城ãšããèªå·±ç¡¬åæ§æš¹èã®è£œé æ¹æ³ã ïŒ ã¢ãã³ã€ããåºãæãããšãã¬ã³æ§äžé£œåå
åç©ã¯ãã¢ãã³ã€ããäžéšåã¯å šéšãææ©é žåã¯
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ïŒé èšèŒã®èªå·±ç¡¬åæ§æš¹èã®è£œé æ¹æ³ã[Claims] 1. A first monoamine is added to an ethylenically unsaturated compound having an amine imide group to obtain the following general formula: (In the formula, R 1 represents an alkyl group, alkoxyalkyl group, alkenyl group, hydroxyalkyl group, or aryl group having 2 to 30 carbon atoms, and R 2 , R 3 , R 4
each represents an alkyl group or a hydroxyalkyl group having 1 to 8 carbon atoms. 1. A process for producing a self-curing resin, which comprises obtaining a Michael-type adduct of ) and further adding the Michael-type adduct to a polyepoxide to obtain an amino-modified polyepoxide containing an amine imide group. 2. The ethylenically unsaturated compound having an amine imide group is one in which part or all of the amine imide is neutralized with an organic acid or an inorganic acid. A method for producing a self-curing resin according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP18828685A JPH0244849B2 (en) | 1985-08-27 | 1985-08-27 | JIKOKOKASEIJUSHINOSEIZOHOHO |
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Application Number | Priority Date | Filing Date | Title |
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JP18828685A JPH0244849B2 (en) | 1985-08-27 | 1985-08-27 | JIKOKOKASEIJUSHINOSEIZOHOHO |
Publications (2)
Publication Number | Publication Date |
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JPS6248720A JPS6248720A (en) | 1987-03-03 |
JPH0244849B2 true JPH0244849B2 (en) | 1990-10-05 |
Family
ID=16220973
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JP18828685A Expired - Lifetime JPH0244849B2 (en) | 1985-08-27 | 1985-08-27 | JIKOKOKASEIJUSHINOSEIZOHOHO |
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CA2000649A1 (en) * | 1988-10-17 | 1990-04-17 | Tsuyoshi Inoue | Electrocoating composition |
US10351661B2 (en) | 2015-12-10 | 2019-07-16 | Ppg Industries Ohio, Inc. | Method for producing an aminimide |
US10377928B2 (en) | 2015-12-10 | 2019-08-13 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
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1985
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