JPH10147734A - Electrodepositon coating material composition - Google Patents
Electrodepositon coating material compositionInfo
- Publication number
- JPH10147734A JPH10147734A JP30666596A JP30666596A JPH10147734A JP H10147734 A JPH10147734 A JP H10147734A JP 30666596 A JP30666596 A JP 30666596A JP 30666596 A JP30666596 A JP 30666596A JP H10147734 A JPH10147734 A JP H10147734A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- polyol
- acid
- production example
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title abstract description 54
- 239000011248 coating agent Substances 0.000 title abstract description 51
- 239000000463 material Substances 0.000 title abstract description 4
- 229920005862 polyol Polymers 0.000 claims abstract description 91
- 150000003077 polyols Chemical class 0.000 claims abstract description 84
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 7
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims description 49
- 239000008199 coating composition Substances 0.000 claims description 42
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 13
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 45
- 239000004925 Acrylic resin Substances 0.000 abstract description 30
- 229920000178 Acrylic resin Polymers 0.000 abstract description 30
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- 150000002763 monocarboxylic acids Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 65
- 239000007787 solid Substances 0.000 description 33
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 24
- 125000000129 anionic group Chemical group 0.000 description 23
- 125000002091 cationic group Chemical group 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- -1 Cyclopentyl norbornene Chemical compound 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920000877 Melamine resin Polymers 0.000 description 10
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004640 Melamine resin Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 229920003270 Cymel® Polymers 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 4
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- UDBVMAQJOPTWLF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid Chemical compound OCC(C)(CO)C(O)=O.OCC(C)(CO)C(O)=O UDBVMAQJOPTWLF-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-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
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- KLJLTMLUYWDVRY-UHFFFAOYSA-N cyclohex-2-en-1-yl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCC=C1 KLJLTMLUYWDVRY-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電着塗料組成物に関
し、特に、耐温水性と耐候性に優れた電着塗料組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition coating composition, and more particularly to an electrodeposition coating composition excellent in warm water resistance and weather resistance.
【０００２】[0002]
【従来の技術】自動車車体及びホイール等環境条件に直
接晒される自動車部品には高い耐食性が要求される。と
ころが、これらは金属製であり、水分や酸の付着により
劣化し易い性質を有する。電着塗装は、このような製品
の耐食性を高めるために行われ、金属地の上に電着塗膜
が形成される。2. Description of the Related Art High corrosion resistance is required for automotive parts such as automobile bodies and wheels that are directly exposed to environmental conditions. However, these are made of metal and have a property of being easily deteriorated by adhesion of moisture or acid. Electrodeposition coating is performed to enhance the corrosion resistance of such products, and an electrodeposition coating film is formed on a metal substrate.
【０００３】このように、被塗物に耐食性を付与するこ
とは電着塗膜に要求される基本的な特性である。電着塗
膜の耐食性を高める方法には、防錆顔料のような防錆剤
を配合する方法等もあるが、有効な方法として、高いガ
ラス転移温度（Ｔｇ）を有する硬質樹脂を電着塗料に組
み込む方法が用いられてきた。As described above, imparting corrosion resistance to an object to be coated is a basic characteristic required for an electrodeposition coating film. As a method of improving the corrosion resistance of the electrodeposition coating film, there is a method of incorporating a rust inhibitor such as a rust-preventive pigment, and an effective method is to use a hard resin having a high glass transition temperature (Tg) as an electrodeposition paint. Have been used.
【０００４】この方法によれば、電着塗膜中に硬質成分
が導入されるので塗膜の耐食性が向上する。また、塗膜
の透明性を保つこともできるので、車両のアルミホイー
ル等に適用可能なクリヤー電着塗膜を提供するために好
都合である。According to this method, a hard component is introduced into the electrodeposition coating film, so that the corrosion resistance of the coating film is improved. Further, since the transparency of the coating film can be maintained, it is convenient to provide a clear electrodeposition coating film applicable to an aluminum wheel of a vehicle or the like.
【０００５】従来からビスフェノールＡ型エポキシ樹脂
を主成分として変性された種々のポリオールが電着塗料
用の硬質樹脂として用いられてきた。ビスフェノールＡ
型エポキシ樹脂は硬質成分として有効な高いＴｇの塗膜
を形成し、その含有量を高めることにより電着塗膜の耐
食性が高められる。[0005] Conventionally, various polyols modified with a bisphenol A type epoxy resin as a main component have been used as hard resins for electrodeposition coatings. Bisphenol A
The type epoxy resin forms a coating film having a high Tg effective as a hard component, and by increasing the content thereof, the corrosion resistance of the electrodeposition coating film is enhanced.
【０００６】しかし、この塗膜は耐候性に劣り環境条件
での使用において黄変し易いという問題がある。更に、
この塗膜は耐温水性にも劣り昇温下での水の付着により
剥離し易いという問題もある。従って、このような塗膜
は、環境条件に直接晒され、昇温下で水が付着する条件
では使用できない。However, there is a problem that this coating film is inferior in weather resistance and easily yellows when used under environmental conditions. Furthermore,
This coating film also has a problem that it is inferior to hot water resistance and easily peels off due to adhesion of water at an elevated temperature. Therefore, such coatings are directly exposed to environmental conditions and cannot be used under conditions where water adheres at elevated temperatures.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記従来の問
題を解決するものであり、その目的とするところは、耐
食性、耐候性及び耐温水性に優れた塗膜を形成しうる電
着塗料組成物を提供することにある。An object of the present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide an electrodeposition paint capable of forming a coating film having excellent corrosion resistance, weather resistance and hot water resistance. It is to provide a composition.
【０００８】[0008]
【課題を解決するための手段】本発明は、（ａ）分子量
４００〜３０００、エポキシ当量２００〜１５００の環
状脂肪族部分を有するエポキシ樹脂をモノカルボン酸と
反応させ、ついで、残存する水酸基をε−カプロラクト
ンと反応させることにより得られる、１級水酸基を有す
る低分子量ポリオール；及び（ｃ）架橋剤；を含有する
電着塗料組成物を提供するものであり、そのことにより
上記目的が達成される。According to the present invention, (a) an epoxy resin having a cycloaliphatic moiety having a molecular weight of 400 to 3000 and an epoxy equivalent of 200 to 1500 is reacted with a monocarboxylic acid, and then the remaining hydroxyl groups are converted to ε. -To provide an electrodeposition coating composition comprising a low molecular weight polyol having a primary hydroxyl group, obtained by reacting with caprolactone; and (c) a crosslinking agent, whereby the above object is achieved. .
【０００９】本発明の電着塗料組成物は樹脂成分と添加
剤成分とが水性媒体中に分散された形で提供される。樹
脂成分は水酸基を有するポリマーであるポリオール成分
とこれを架橋させる架橋剤成分とを含有する。ポリオー
ル成分は、比較的低分子量でＴｇが高い低分子量ポリオ
ール（ａ）を含有する。The electrodeposition coating composition of the present invention is provided in a form in which a resin component and an additive component are dispersed in an aqueous medium. The resin component contains a polyol component, which is a polymer having a hydroxyl group, and a crosslinking agent component for crosslinking the polyol component. The polyol component contains a low molecular weight polyol (a) having a relatively low molecular weight and a high Tg.
【００１０】本発明の低分子量ポリオール（ａ）は、環
状脂肪族部分を有するエポキシ樹脂とビスフェノールＡ
とを重合してポリエポキシドとし、残存するエポキシ基
をモノカルボン酸と反応させ、ついで、水酸基をε−カ
プロラクトンと反応させることにより得られる。The low molecular weight polyol (a) of the present invention comprises an epoxy resin having a cycloaliphatic moiety and bisphenol A
Into a polyepoxide by reacting the remaining epoxy group with a monocarboxylic acid, and then reacting a hydroxyl group with ε-caprolactone.
【００１１】環状脂肪族部分を有するエポキシ樹脂にお
いて、環状脂肪族部分は主鎖中に存在することが好まし
い。また、環状脂肪族部分の炭素数は特に限定的ではな
いが炭素数３〜８個、特に５〜７個であることが好まし
い。特に好ましい環状脂肪族部分は、芳香族環を水素添
加して得られるものである。In the epoxy resin having a cycloaliphatic moiety, the cycloaliphatic moiety is preferably present in the main chain. The number of carbon atoms in the cycloaliphatic moiety is not particularly limited, but is preferably 3 to 8, particularly preferably 5 to 7 carbon atoms. Particularly preferred cycloaliphatic moieties are those obtained by hydrogenating an aromatic ring.
【００１２】好ましい環状脂肪族部分の具体例は、シク
ロペンチレン、シクロヘキシレン、シクロヘプチレン、
シクロペンチルノルボルネン、シクロヘキシルノルボル
ネン、シクロヘプチルノルボルネン及びシクロオクチル
ノルボルネン等である。Specific examples of preferred cycloaliphatic moieties include cyclopentylene, cyclohexylene, cycloheptylene,
Cyclopentyl norbornene, cyclohexyl norbornene, cycloheptyl norbornene, cyclooctyl norbornene and the like.
【００１３】環状脂肪族部分を有するエポキシ樹脂は数
平均分子量（Ｍｎ）４００〜３０００、好ましくは４５
０〜２０００を有する。分子量が３０００を上回ると増
粘して乳化不可能となり、４００を下回ると耐温水性が
低下する。The epoxy resin having a cycloaliphatic moiety has a number average molecular weight (Mn) of 400 to 3,000, preferably 45.
0-2000. If the molecular weight exceeds 3,000, the viscosity increases and emulsification becomes impossible. If the molecular weight is less than 400, warm water resistance decreases.
【００１４】また、環状脂肪族部分を有するエポキシ樹
脂はエポキシ当量２００〜１５００、好ましくは２３０
〜１１００を有する。エポキシ当量が１５００を上回る
と外観が低下し、２００を下回ると耐温水性が低下す
る。The epoxy resin having a cyclic aliphatic moiety has an epoxy equivalent of 200 to 1500, preferably 230
１1100. When the epoxy equivalent exceeds 1500, the appearance is reduced, and when it is less than 200, the hot water resistance is reduced.
【００１５】環状脂肪族部分を有するエポキシ樹脂は種
々市販されている。本発明に用いるのに好ましい市販品
は、東都化成社製の「サントートＳＴ−３０００」、
「サントートＳＴ−４０００」、「サントートＳＴ−４
１００」、「サントートＳＴ−５１００」である。特に
好ましいものは、「サントートＳＴ−４１００」及び
「サントートＳＴ−５１００」である。Various epoxy resins having a cyclic aliphatic moiety are commercially available. Commercial products preferred for use in the present invention are "Santoto ST-3000" manufactured by Toto Kasei,
"Suntote ST-4000", "Suntote ST-4"
100 "and" Suntote ST-5100 ". Particularly preferred are "Santote ST-4100" and "Santeote ST-5100".
【００１６】分子量が小さい環状脂肪族部分を有するエ
ポキシ樹脂を、ついで、ビスフェノールＡと重合するこ
とによりポリエポキシドを得ることもできる。A polyepoxide can also be obtained by polymerizing an epoxy resin having a cyclic aliphatic moiety having a low molecular weight with bisphenol A.
【００１７】この重合は、エポキシ樹脂中のエポキシ基
とビスフェノールＡ中の水酸基とが繰り返し開環付加す
る反応であり、具体的な方法及び条件は当業者に周知で
ある。ポリエポキシドは数平均分子量４００〜３０００
及びエポキシ当量２００〜１５００、特に２５０〜１０
００とすることが好ましい。This polymerization is a reaction in which the epoxy group in the epoxy resin and the hydroxyl group in bisphenol A are repeatedly ring-opened, and specific methods and conditions are well known to those skilled in the art. Polyepoxide has a number average molecular weight of 400 to 3000
And an epoxy equivalent of 200 to 1500, particularly 250 to 10
00 is preferable.
【００１８】ポリエポキシドの分子量が４００を下回る
と耐温水性が低下し、３０００を上回ると増粘して乳化
不可能となる。If the molecular weight of the polyepoxide is less than 400, the resistance to warm water decreases, and if it exceeds 3000, the viscosity increases and the emulsification becomes impossible.
【００１９】ポリエポキシド中のエポキシ基は塗料組成
物中で中和剤として用いている酸化合物や塩基化合物と
反応して乳化したエマルションがこわれ、塗料の安定性
が低下する為、反応しないよう封鎖してポリオールとす
ることが好ましい。The epoxy group in the polyepoxide reacts with an acid compound or a base compound used as a neutralizing agent in the coating composition to break an emulsified emulsion, thereby lowering the stability of the coating. It is preferable to use a polyol.
【００２０】エポキシ基の封鎖は、一般に酸化合物、ア
ルコール、塩基化合物等を用いて行いうるが、エポキシ
基との反応性制御の観点からモノカルボン酸を用いるこ
とが好ましい。The blocking of the epoxy group can be generally carried out by using an acid compound, an alcohol, a basic compound or the like, but it is preferable to use a monocarboxylic acid from the viewpoint of controlling the reactivity with the epoxy group.
【００２１】好ましいモノカルボン酸は、安息香酸、ジ
メチロールブタン酸、ジメチロールプロピオン酸及びグ
リコール酸からなる群から選択される。特に好ましいモ
ノカルボン酸は、安息香酸である。エポキシ基との反応
性が良好であり、生成した分子構造がエマルションの乳
化性を向上させるからである。Preferred monocarboxylic acids are selected from the group consisting of benzoic acid, dimethylolbutanoic acid, dimethylolpropionic acid and glycolic acid. A particularly preferred monocarboxylic acid is benzoic acid. This is because the reactivity with the epoxy group is good, and the generated molecular structure improves the emulsifiability of the emulsion.
【００２２】ポリエポキシドに含まれるエポキシ基の量
と用いられるモノカルボン酸の量との当量比は、１／
０．９〜１／１とすることが好ましい。この当量比が
０.９を下回ると塗料組成物の安定性が悪くなり、１／
１を上回ると塗膜の耐温水性が悪くなる。The equivalent ratio of the amount of the epoxy group contained in the polyepoxide to the amount of the monocarboxylic acid used is 1 /
It is preferably 0.9 to 1/1. When the equivalent ratio is less than 0.9, the stability of the coating composition deteriorates, and 1 /
When it exceeds 1, the warm water resistance of the coating film is deteriorated.
【００２３】ついで、得られたポリオールをε−カプロ
ラクトンと反応させて本発明の低分子量ポリオール
（ａ）を得る。この反応により本発明の低分子量ポリオ
ール（ａ）に１級水酸基が導入され、得られる塗膜の密
着性が向上する。また、その結果、塗膜の耐温水性も向
上する。ポリオールに含まれる水酸基の量と用いられる
ε−カプロラクトンの量とのモル比は、１／０．５〜１
／１である。このモル比が０．５を下回ると塗膜の耐食
性が悪くなり、１／１を上回ると塗膜の耐温水性が悪く
なる。Next, the obtained polyol is reacted with ε-caprolactone to obtain the low molecular weight polyol (a) of the present invention. By this reaction, a primary hydroxyl group is introduced into the low molecular weight polyol (a) of the present invention, and the adhesion of the resulting coating film is improved. As a result, the warm water resistance of the coating film is also improved. The molar ratio between the amount of hydroxyl groups contained in the polyol and the amount of ε-caprolactone used is from 1 / 0.5 to 1
/ 1. When the molar ratio is less than 0.5, the corrosion resistance of the coating film is deteriorated. When the molar ratio is more than 1/1, the warm water resistance of the coating film is deteriorated.
【００２４】低分子量ポリオール（ａ）は、数平均分子
量１０００〜４０００、特に１５００〜３０００、水酸
基価３０〜２５０、特に５０〜２００重量％を有するこ
とが好ましい。分子量が１０００を下回ると耐温水性が
低下し、４０００を上回ると乳化性が低下する。水酸基
価が５０を下回ると耐食性が低下し、２５０を上回ると
耐温水性が低下する。The low molecular weight polyol (a) preferably has a number average molecular weight of 1,000 to 4,000, especially 1500 to 3,000, and a hydroxyl value of 30 to 250, especially 50 to 200% by weight. When the molecular weight is less than 1,000, the hot water resistance is reduced, and when it is more than 4000, the emulsifying property is reduced. If the hydroxyl value is less than 50, the corrosion resistance decreases, and if it exceeds 250, the hot water resistance decreases.
【００２５】低分子量ポリオール（ａ）は、ポリオール
成分中に５〜３５重量％、好ましくは１０〜３０重量％
の量で含有される。低分子量ポリオール（ａ）の含有量
が５重量％を下回ると塗料組成物の安定性が悪くなり、
３５重量％を上回ると塗膜の耐温水性が悪くなる。The low molecular weight polyol (a) accounts for 5 to 35% by weight, preferably 10 to 30% by weight in the polyol component.
It is contained in the amount of. When the content of the low-molecular-weight polyol (a) is less than 5% by weight, the stability of the coating composition deteriorates,
If it exceeds 35% by weight, the warm water resistance of the coating film will be poor.
【００２６】本発明のポリオール成分は、上記低分子量
ポリオール（ａ）の他にも種々のポリオールを含みう
る。低分子量ポリオール（ａ）以外のポリオールとして
特に好ましいものは、比較的高分子量でＴｇが低い高分
子量ポリオール（ｂ）である。The polyol component of the present invention may contain various polyols in addition to the low molecular weight polyol (a). Particularly preferred as the polyol other than the low molecular weight polyol (a) is a high molecular weight polyol (b) having a relatively high molecular weight and a low Tg.
【００２７】本発明で好適に用いうる高分子量ポリオー
ル（ｂ）は、電着塗料組成物に主として造膜性を付与す
る樹脂成分である。従来から電着塗料組成物用の造膜成
分として用いられているイオン性樹脂であれば特に限定
されないが、ベンゼン部分及びナフタレン部分のような
ハードセグメントを主鎖中に有しないものが好ましい。The high molecular weight polyol (b) which can be suitably used in the present invention is a resin component which mainly gives film forming properties to the electrodeposition coating composition. It is not particularly limited as long as it is an ionic resin conventionally used as a film-forming component for an electrodeposition coating composition, but those having no hard segment such as a benzene portion and a naphthalene portion in a main chain are preferable.
【００２８】特に好ましい高分子量ポリオール（ｂ）は
アクリル樹脂である。得られる塗膜の耐候性が向上する
ためである。このアクリル樹脂は好ましくは０〜１００
℃、更に好ましくは１０〜６０℃のＴｇを有する。アク
リル樹脂のＴｇが０℃を下回ると耐温水性が低下し、１
００℃を上回ると外観が不良となる。Particularly preferred high molecular weight polyols (b) are acrylic resins. This is because the weather resistance of the obtained coating film is improved. This acrylic resin is preferably from 0 to 100
C, more preferably from 10 to 60C. When the Tg of the acrylic resin falls below 0 ° C., the hot water resistance decreases,
If the temperature exceeds 00 ° C., the appearance becomes poor.
【００２９】また、アクリル樹脂は好ましくは３０００
〜２０００００、さらに好ましくは５０００〜１５００
０の数平均分子量を有する。アクリル樹脂の数平均分子
量が上記の範囲を逸脱すると塗膜の平滑性が悪くなる。The acrylic resin is preferably 3000
~ 200000, more preferably 5000-1500
It has a number average molecular weight of zero. When the number average molecular weight of the acrylic resin is out of the above range, the smoothness of the coating film becomes poor.
【００３０】電着塗料用のアクリル樹脂はイオン性であ
るが、本発明で用いるアクリル樹脂はアニオン性でもカ
チオン性でもよい。但し、耐候性が特に要求される場合
には、アニオン性アクリル樹脂を用いることが好まし
い。The acrylic resin for the electrodeposition paint is ionic, but the acrylic resin used in the present invention may be anionic or cationic. However, when weather resistance is particularly required, it is preferable to use an anionic acrylic resin.
【００３１】カチオン性アクリル樹脂はアクリル樹脂骨
格にカチオン性基が結合したものであればよい。カチオ
ン性基には、オニウム塩基、例えばアンモニウム塩基、
ホスホニウム塩基等が挙げられる。アクリル樹脂骨格に
カチオン性基を導入する方法は公知である。The cationic acrylic resin may be any resin in which a cationic group is bonded to the acrylic resin skeleton. Cationic groups include onium bases, such as ammonium bases,
And phosphonium bases. Methods for introducing a cationic group into an acrylic resin skeleton are known.
【００３２】例えば、アミノ基含有アクリル樹脂は、グ
リシジル基含有アクリル樹脂と１、２、３級アミン、ポ
リアミン及びアルカノールアミンのような塩基性アミノ
化合物とを反応させることにより得られる。グリシジル
基含有アクリル樹脂は、例えば、グリシジル基含有(メ
タ)アクリルエステル系モノマー、水酸基含有(メタ)ア
クリルエステル系モノマー、その他の重合性モノマー及
びラジカル重合開始剤の混合物を滴下しながら、２〜５
時間(100〜150℃)かけて溶液重合することにより得られ
る。For example, an amino group-containing acrylic resin is obtained by reacting a glycidyl group-containing acrylic resin with a basic amino compound such as a primary, secondary, tertiary amine, polyamine and alkanolamine. Glycidyl group-containing acrylic resin, for example, glycidyl group-containing (meth) acrylic ester-based monomer, hydroxyl group-containing (meth) acrylic ester-based monomer, while dropping a mixture of other polymerizable monomers and radical polymerization initiator, 2-5
It is obtained by performing solution polymerization over time (100 to 150 ° C.).
【００３３】カチオン性アクリル樹脂は４０〜１３０me
q／１００ｇ（固形分）、好ましくは６０〜１２０meq／
１００ｇ（固形分）のアミン価、及び２０〜１２０の水
酸基価を有する。The cationic acrylic resin is 40 to 130 me.
q / 100g (solid content), preferably 60-120meq /
It has an amine value of 100 g (solid content) and a hydroxyl value of 20 to 120.
【００３４】カチオン性アクリル樹脂のアミン価が６０
meq／１００ｇ（固形分）を下回ると塗料組成物の安定
性が悪くなり、１３０meq／１００ｇ（固形分）を上回
ると塗膜の耐食性が悪くなる。カチオン性樹脂の水酸基
価が２０を下回ると塗膜の耐食性が悪くなり、１２０を
上回ると塗膜の平滑性が悪くなる。The amine value of the cationic acrylic resin is 60
If it is less than meq / 100 g (solid content), the stability of the coating composition will be poor. If it exceeds 130 meq / 100 g (solid content), the corrosion resistance of the coating film will be poor. When the hydroxyl value of the cationic resin is less than 20, the corrosion resistance of the coating film becomes poor, and when it exceeds 120, the smoothness of the coating film becomes poor.
【００３５】このようなカチオン性アクリル樹脂は、例
えば、特開平０７−１６６１２号公報に具体的に記載さ
れている。Such a cationic acrylic resin is specifically described in, for example, JP-A-07-16612.
【００３６】カチオン性アクリル樹脂は酸で中和して水
分散型または水可溶性にして使用される。好ましい酸に
は、酢酸、乳酸、ギ酸、スルファミン酸及びプロピオン
酸等の有機酸、及び硫酸及びリン酸等の無機酸が使用さ
れる。The cationic acrylic resin is used after being neutralized with an acid and dispersed in water or made water-soluble. Preferred acids include organic acids such as acetic acid, lactic acid, formic acid, sulfamic acid and propionic acid, and inorganic acids such as sulfuric acid and phosphoric acid.
【００３７】アニオン性アクリル樹脂はアクリル樹脂骨
格にアニオン性基が結合したものであればよい。アニオ
ン性基には、カルボキシレート基、リン酸基、スルホン
酸基等が挙げられる。アクリル樹脂骨格にアニオン性基
を導入する方法は公知である。The anionic acrylic resin may be any resin in which an anionic group is bonded to an acrylic resin skeleton. Examples of the anionic group include a carboxylate group, a phosphate group, and a sulfonic group. A method for introducing an anionic group into an acrylic resin skeleton is known.
【００３８】例えば、カルボキシレート基含有アクリル
樹脂は、アクリル酸及びメタクリル酸等を共重合するこ
とにより調製される。For example, the carboxylate group-containing acrylic resin is prepared by copolymerizing acrylic acid and methacrylic acid.
【００３９】アニオン性アクリル樹脂は２０〜１５０、
好ましくは２５〜８０の酸価、及び１８〜１１０の水酸
基価を有する。アニオン性アクリル樹脂の酸価が２５を
下回ると塗料組成物の安定性が悪くなり、８０を上回る
と塗膜の耐食性が悪くなる。カチオン性樹脂の水酸基価
が１８を下回ると塗膜の耐食性が悪くなり、１１０を上
回ると塗膜の平滑性が悪くなる。The anionic acrylic resin is 20 to 150,
It preferably has an acid value of 25 to 80 and a hydroxyl value of 18 to 110. If the acid value of the anionic acrylic resin is less than 25, the stability of the coating composition will be poor, and if it is more than 80, the corrosion resistance of the coating film will be poor. When the hydroxyl value of the cationic resin is less than 18, the corrosion resistance of the coating film becomes poor, and when it exceeds 110, the smoothness of the coating film becomes poor.
【００４０】このようなアニオン性アクリル樹脂は、例
えば、特開平８−１７００３６号公報、同８−１７００
３７号公報等に記載されている。特に好ましいアニオン
性アクリル樹脂には、東レ社製塗料用アクリル樹脂「コ
ータックス」等が挙げられる。Such anionic acrylic resins are described, for example, in JP-A-8-170036 and JP-A-8-1700.
No. 37, for example. Particularly preferred anionic acrylic resin includes acrylic resin “COTAX” for paint manufactured by Toray Industries, Inc.
【００４１】得られたアニオン性アクリル樹脂は、アミ
ン、好ましくは高級アミンのような塩基で中和して水分
散型または水可溶性にして使用される。好ましい塩基に
は、トリエチルアミン及びジメチルエタノールアミン等
の有機塩基、及びＫＯＨ及びＮaＯＨ等の無機塩基等が
挙げられる。The obtained anionic acrylic resin is used after being neutralized with a base such as an amine, preferably a higher amine, and made water-dispersible or water-soluble. Preferred bases include organic bases such as triethylamine and dimethylethanolamine, and inorganic bases such as KOH and NaOH.
【００４２】高分子量ポリオール（ｂ）は、ポリオール
成分中に９５〜６５重量％、好ましくは９０〜７０重量
％の量で含有される。高分子量ポリオール（ａ）の含有
量が６５重量％を下回ると得られる塗料の安定性が悪化
する。また、９５重量％を上回ると得られる塗料の耐温
水性が悪化する。The high molecular weight polyol (b) is contained in the polyol component in an amount of 95 to 65% by weight, preferably 90 to 70% by weight. If the content of the high-molecular-weight polyol (a) is less than 65% by weight, the stability of the obtained paint will be deteriorated. On the other hand, when the content exceeds 95% by weight, the warm water resistance of the obtained paint deteriorates.
【００４３】好ましい態様では、本発明の電着塗料組成
物中、ポリオール成分は、低分子量ポリオール（ａ）
と、高分子量ポリオール（ｂ）とから構成される。ポリ
オール成分中に、低分子量ポリオール（ａ）は５〜３５
重量％、好ましくは１０〜３０重量％、高分子量ポリオ
ール（ｂ）は９５〜６５重量％、好ましくは９０〜７０
重量％含有される。低分子量ポリオール（ａ）の含有量
が５重量％を下回ると塗料組成物の安定性が悪くなり、
３５重量％を上回ると塗膜の耐温水性が悪くなる。In a preferred embodiment, in the electrodeposition coating composition of the present invention, the polyol component is a low molecular weight polyol (a)
And a high molecular weight polyol (b). In the polyol component, the low-molecular-weight polyol (a) contains 5-35
%, Preferably 10 to 30% by weight, and the high molecular weight polyol (b) is 95 to 65% by weight, preferably 90 to 70% by weight.
% By weight. When the content of the low-molecular-weight polyol (a) is less than 5% by weight, the stability of the coating composition deteriorates,
If it exceeds 35% by weight, the warm water resistance of the coating film will be poor.
【００４４】本発明の架橋剤成分には、ポリオール成分
を硬化させる電着塗料用硬化剤として公知の化合物を用
いうる。例えば、ブロック化ポリイソシアネート及びメ
ラミン樹脂等が挙げられる。As the crosslinking agent component of the present invention, a compound known as a curing agent for an electrodeposition paint for curing a polyol component can be used. For example, a blocked polyisocyanate, a melamine resin and the like can be mentioned.
【００４５】ブロック化ポリイソシアネートは、ポリイ
ソシアネートのイソシアネート基をブロック化剤でブロ
ックすることにより得られる。ポリイソシアネート及び
ブロック化剤としては、従来から電着塗料に用いられて
きた全てのものを用いうる。イソシアネート基をブロッ
ク化剤でブロックする方法は当業者に周知である。The blocked polyisocyanate is obtained by blocking the isocyanate group of the polyisocyanate with a blocking agent. As the polyisocyanate and the blocking agent, all those conventionally used for electrodeposition coatings can be used. Methods for blocking isocyanate groups with a blocking agent are well known to those skilled in the art.
【００４６】好ましいブロック化ポリイソシアネート
は、解離温度１００℃〜１８０℃、特に１２０〜１６０
℃のものである。解離温度を調節するために解離触媒を
用いても良い。Preferred blocked polyisocyanates have a dissociation temperature of 100 ° C. to 180 ° C., especially 120 to 160 ° C.
° C. A dissociation catalyst may be used to adjust the dissociation temperature.
【００４７】ブロック化ポリイソシアネートの解離温度
が１００℃未満であると塗膜の流動性が非常に悪いため
平面部の平滑性が低下し、好ましくない。また、塗料の
安定性にも問題がある。他方、解離温度が１８０℃を越
えると現行の多くの塗装ラインにおける焼付け条件では
硬化性が不足し、防食性が低下する。If the dissociation temperature of the blocked polyisocyanate is less than 100 ° C., the fluidity of the coating film is very poor, and the smoothness of the flat portion is undesirably reduced. There is also a problem with the stability of the paint. On the other hand, if the dissociation temperature exceeds 180 ° C., the curability is insufficient under the baking conditions in many current coating lines, and the corrosion resistance is reduced.
【００４８】メラミン樹脂は、一般に、メラミンとホル
ムアルデヒドとを反応させて得られる熱硬化性樹脂をい
い、種々市販されている。メラミン樹脂としては、従来
から電着塗料に用いられてきた全てのものを用いうる。The melamine resin generally refers to a thermosetting resin obtained by reacting melamine with formaldehyde, and is commercially available in various forms. As the melamine resin, all of those conventionally used for electrodeposition paints can be used.
【００４９】本発明で用いるのに好ましいメラミン樹脂
はメチル化メラミン樹脂、ブチル化メラミン樹脂を使用
できる。好ましいメラミン樹脂には、三井サイテック社
製「サイメル２３５」等が挙げられる。As the preferred melamine resin for use in the present invention, a methylated melamine resin and a butylated melamine resin can be used. Preferred melamine resins include "Cymel 235" manufactured by Mitsui Cytec.
【００５０】架橋剤の配合量は、ポリオール成分に含有
される水酸基及びカルボキシル基のような官能基と架橋
剤に含有されるブロック化ポリイソシアネート及びアミ
ノ基のような官能基とが等モル量となるように決定され
る。配合量の決定法は当業者に周知である。The amount of the crosslinking agent is such that the functional groups such as hydroxyl group and carboxyl group contained in the polyol component and the functional groups such as blocked polyisocyanate and amino group contained in the crosslinking agent are equimolar. It is determined to be. The method for determining the amount is well known to those skilled in the art.
【００５１】一般に、架橋剤はポリオール成分(ａ)及び
(ｂ)の合計１００重量部に対して２０〜１００重量部、
好ましくは２５〜７０重量部の量で電着塗料組成物に含
有される。架橋剤の含有量が２０重量部を下回ると塗膜
の耐温水性が悪くなり、１００重量部を上回ると塗料組
成物の安定性が悪くなる。Generally, the crosslinking agent comprises the polyol component (a) and
(b) 20 to 100 parts by weight with respect to 100 parts by weight in total;
It is preferably contained in the electrodeposition coating composition in an amount of 25 to 70 parts by weight. When the content of the crosslinking agent is less than 20 parts by weight, the coating film has poor warm water resistance, and when it exceeds 100 parts by weight, the stability of the coating composition is poor.
【００５２】本発明の電着塗料組成物は、上記成分の他
に必要に応じ種々の添加剤成分を含むことができる。The electrodeposition coating composition of the present invention can contain various additive components as required in addition to the above components.
【００５３】添加剤成分の例としては、紫外線吸収剤の
ような耐候性付与剤、界面活性剤のような分散補助剤を
使用できる。これらの添加剤の濃度は、通常、電着塗料
中の樹脂固形分に対し０.１〜１５重量％、好ましくは
０.１〜５重量％である。Examples of the additive component include a weather resistance imparting agent such as an ultraviolet absorber and a dispersing aid such as a surfactant. The concentration of these additives is usually 0.1 to 15% by weight, preferably 0.1 to 5% by weight, based on the solid content of the resin in the electrodeposition paint.
【００５４】使用しうる紫外線吸収剤の例としてはサリ
チル酸類(例えば、フェニルサリチレート、p−t−ブチ
ルフェニルサリチレート及びp−オクチルフェニルサリ
チレート)、ベンゾフェノン類(例えば、２,４−ジヒド
ロベンゾフェノン、２−ヒドロキシ−４−メトキシベン
ゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフ
ェノン、２−ヒドロキシ−４−ドデシロキシベンゾフェ
ノン、２,２'−ジヒドロキシ−４−メトキシベンゾフェ
ノン及び２−ヒドロキシ−４−メトキシ−５−スルホベ
ンゾフェノン)、ベンゾトリアゾール類(例えば、２−
(２'−ヒドロキシ−５'−メチルビニル)ベンゾトリアゾ
ール)、シアノアクリレート類(例えば、２−エチルヘキ
シル−２−シアノ−３,３'−ジフェニルアクリレート及
びエチル−２−シアノ−３,３'−ジフェニルアクリレー
ト)などが挙げられる。Examples of ultraviolet absorbers that can be used include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate and p-octylphenyl salicylate), benzophenones (eg, 2,4 -Dihydrobenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2-hydroxy- 4-methoxy-5-sulfobenzophenone), benzotriazoles (e.g., 2-
(2'-hydroxy-5'-methylvinyl) benzotriazole), cyanoacrylates (for example, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenyl Acrylate).
【００５５】市販品の例には、チバガイギー社製の「チ
ヌビン１１３０」及び旭電化工業社製の「アデカスタブ
ＬＡ−６２」等が挙げられる。Examples of commercially available products include "Tinuvin 1130" manufactured by Ciba-Geigy and "ADEKA STAB LA-62" manufactured by Asahi Denka Kogyo.
【００５６】紫外線吸収剤はポリオール成分(ａ)及び
(ｂ)の合計１００重量部に対して０．５〜１０重量部、
好ましくは１.０〜５.０重量部の量で電着塗料組成物に
含有される。紫外線吸収剤の含有量が０．５重量部を下
回ると塗膜の耐候性が悪くなり、１０重量部を上回って
含有させても耐候性の向上が得られない。The ultraviolet absorber is composed of the polyol component (a) and
(b) 0.5 to 10 parts by weight with respect to 100 parts by weight in total,
Preferably, it is contained in the electrodeposition coating composition in an amount of 1.0 to 5.0 parts by weight. When the content of the ultraviolet absorber is less than 0.5 part by weight, the weather resistance of the coating film is deteriorated, and when the content is more than 10 parts by weight, improvement of the weather resistance cannot be obtained.
【００５７】次いで、得られた樹脂混合物を水性媒体中
に分散させるが、水性媒体中には水の他に種々の有機溶
剤を樹脂の溶解、粘度などの調整のために用いてもよ
い。使用しうる溶剤の例としては炭化水素類（例えば、
キシレンまたはトルエン）、アルコール類（例えば、メ
チルアルコール、ｎ−ブチルアルコール、イソプロピル
アルコール、２−エチルヘキシルアルコール、エチレン
グリコール、プロピレングリコール）、エーテル類（例
えば、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、エチレングリコール
モノヘキシルエーテル、プロピレングリコールモノエチ
ルエーテル、３−メチル−３−メトキシブタノール、ジ
エチレングリコールモノエチルエーテル、ジエチレング
リコールモノブチルエーテル）、ケトン類（例えば、メ
チルイソブチルケトン、シクロヘキサノン、イソホロ
ン、アセチルアセトン）、エステル類（例えば、エチレ
ングリコールモノエチルエーテルアセテート、エチレン
グリコールモノブチルエーテルアセテート）あとはそれ
らの混合物が挙げられる。これらの溶剤の使用量は塗料
全体に対して約０.０１〜２５重量％、好ましくは０.０
５〜１５重量％である。Next, the obtained resin mixture is dispersed in an aqueous medium. In the aqueous medium, various organic solvents other than water may be used for adjusting the dissolution, viscosity and the like of the resin. Examples of solvents that can be used include hydrocarbons (eg,
Xylene or toluene), alcohols (eg, methyl alcohol, n-butyl alcohol, isopropyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol), ethers (eg, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene) Glycol monohexyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), ketones (eg, methyl isobutyl ketone, cyclohexanone, isophorone, acetylacetone), esters (eg, , Ethylene glycol monoethyl ether acetate, ethylene glycol monobuty Ether acetate) After the mixtures thereof. The amount of these solvents to be used is about 0.01 to 25% by weight, preferably 0.0 to 25% by weight, based on the whole paint.
5 to 15% by weight.
【００５８】このようにして得られた本発明の電着塗料
組成物はそのままクリヤー塗料組成物として用いること
ができる。また、必要に応じてさらに顔料ペーストと混
合してもよい。これらは、通常用いられる条件及び方法
で塗装できる。塗装条件としては、例えば、塗料温度２
０〜４０℃、印加電圧５０〜５００Ｖ、通電時間３０秒
〜１０分が挙げられる。また、電着された塗膜は、一般
に約１００〜２００℃、好ましくは１３０〜１６０℃に
５〜５０分間保つことにより硬化させる。The electrodeposition coating composition of the present invention thus obtained can be used as it is as a clear coating composition. Moreover, you may mix further with a pigment paste as needed. These can be applied under conditions and methods commonly used. The coating conditions include, for example, coating temperature 2
0 to 40 ° C., an applied voltage of 50 to 500 V, and a conduction time of 30 seconds to 10 minutes. The electrodeposited coating is generally cured by keeping it at about 100-200 ° C., preferably 130-160 ° C. for 5-50 minutes.
【００５９】被塗物には、従来から電着塗装されてきた
もの全てが挙げられる。例えば、鉄、銅、亜鉛メッキ
材、アルミニウム及びこれらの合金のような金属材料で
ある。Examples of the object to be coated include all materials which have been conventionally subjected to electrodeposition coating. For example, metal materials such as iron, copper, galvanized materials, aluminum and alloys thereof.
【００６０】[0060]
【実施例】以下、実施例及び比較例を挙げて更に具体的
に説明するが、本発明は、これらの実施例に何ら制約さ
れるものではない。The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００６１】製造例１ ４級化剤の調製 Production Example 1 Preparation of quaternizing agent
【００６２】[0062]
【表１】 反応物 重量部 固形分 ２−エチルヘキサノールハーフブロック化ＩＰＤＩ のメチルイソブチルケトン溶液 370.8 352.3 ジメチルエタノールアミン 87.2 87.2 乳酸水溶液 117.6 88.2ブチルセロソルブa) 45.2 − a) エチレングリコールモノブチルエーテル[Table 1] Reactant parts by weight Solid content 2-ethylhexanol half-blocked IPDI solution in methyl isobutyl ketone 370.8 352.3 Dimethylethanolamine 87.2 87.2 Aqueous lactic acid solution 117.6 88.2 Butyl cellosolve a) 45.2- a) Ethylene glycol monobutyl ether
【００６３】表１に示す組成に従って、還流冷却器、撹
拌機を取り付けた４口フラスコ中に反応物を混合し、乾
燥窒素雰囲気下、室温で撹拌した。混合物の発熱が収ま
った後、８０℃で１時間、ついで６５℃で約０.５時間
撹拌しながら加熱保持し、４級化剤を得た。According to the composition shown in Table 1, the reactants were mixed in a four-necked flask equipped with a reflux condenser and a stirrer, and stirred at room temperature under a dry nitrogen atmosphere. After the exotherm of the mixture had subsided, the mixture was heated and maintained at 80 ° C. for 1 hour and then at 65 ° C. for about 0.5 hour while stirring to obtain a quaternizing agent.
【００６４】製造例２ 樹脂ビヒクルの調製 Production Example 2 Preparation of resin vehicle
【００６５】[0065]
【表２】 反応物 重量部 固形分 エポン８２９a) 710.0 681.2 ビスフェノールＡ 289.6 289.6 ２−エチルヘキサノールハーフブロック化ＩＰＤＩ のメチルイソブチルケトン溶液 470.9 447.4 製造例１の４級化剤 546.4 464.4 脱イオン水 75.0 −ブチルセロソルブ 597.6 − a) シェル・ケミカル社製のビスフェノールＡ型エポキシ樹脂（エポキシ当量１９ ３〜２０３）[Table 2] Reactant parts by weight Solid Epon 829 a) 710.0 681.2 Bisphenol A 289.6 289.6 Methyl isobutyl ketone solution of 2-ethylhexanol half-blocked IPDI 470.9 447.4 Quaternizing agent of Production Example 1 546.4 464.4 Deionized water 75.0- Butyl cellosolve 597.6- a) Bisphenol A type epoxy resin manufactured by Shell Chemical Company (epoxy equivalent: 193-203)
【００６６】表２に示す組成に従って、還流冷却器、撹
拌機を取り付けた４口フラスコ中にエポン８２９及びビ
スフェノールＡを混合し、乾燥窒素雰囲気下、室温で撹
拌した。混合物の発熱が収まった後、１５０〜１６０℃
で１時間撹拌し、１２０℃に冷却した。その後、２−エ
チルヘキサノールハーフブロック化イソホロンジイソシ
アネート(ＩＰＤＩ)のメチルイソブチルケトン溶液を添
加し、混合物を撹拌しながら１１０〜１２０℃で約１時
間加熱保持した。According to the composition shown in Table 2, Epon 829 and bisphenol A were mixed in a four-necked flask equipped with a reflux condenser and a stirrer, and stirred at room temperature under a dry nitrogen atmosphere. After the exotherm of the mixture has subsided,
For 1 hour and cooled to 120 ° C. Thereafter, a solution of 2-ethylhexanol half-blocked isophorone diisocyanate (IPDI) in methyl isobutyl ketone was added, and the mixture was heated and maintained at 110 to 120 ° C. for about 1 hour while stirring.
【００６７】ブチルセロソルブを添加後、反応混合物を
８５〜９５℃に冷却し、均一撹拌した。次いで、脱イオ
ン水及び製造例１の４級化剤を添加し、反応混合物を撹
拌しながら酸価が１に低下するまで８０〜８５℃に加熱
保持し、固形分濃度約７０％の樹脂ビヒクルを得た。After the addition of butyl cellosolve, the reaction mixture was cooled to 85-95 ° C. and stirred uniformly. Next, deionized water and the quaternizing agent of Production Example 1 are added, and the reaction mixture is stirred and heated at 80 to 85 ° C. until the acid value decreases to 1, and a resin vehicle having a solid content of about 70% is added. I got
【００６８】製造例３ 顔料ペーストの調製 Production Example 3 Preparation of Pigment Paste
【００６９】[0069]
【表３】 反応物 重量部 固形分 製造例２の樹脂ビヒクル 357.1 250.0 ブチルセロソルブ 84.2 − 脱イオン水(1) 391.6 − カーボンブラック 23.0 23.0 二酸化チタン 917.0 917.0 塩基性ケイ酸鉛 60.0 60.0脱イオン水(2) 667.1 − [Table 3] Reactant parts by weight Solids Resin vehicle of Preparation Example 2 357.1 250.0 Butyl cellosolve 84.2-Deionized water (1) 391.6-Carbon black 23.0 23.0 Titanium dioxide 917.0 917.0 Basic lead silicate 60.0 60.0 Deionized water (2) 667.1 −
【００７０】表３に示す組成に従って、ステンレスベッ
セルの中に、製造例２の樹脂ビヒクル、ブチルセロソル
ブ及び脱イオン水(1)を混合し、均一に撹拌した。次い
で、カーボンブラック、二酸化チタン及び塩基性ケイ酸
鉛を添加し、サンドグラインドミルで分散し、粒度１０
μm以下、総固形分５０.０％、樹脂固形分１０％及び顔
料固形分４０％の顔料ペーストを得た。According to the composition shown in Table 3, the resin vehicle of Production Example 2, butyl cellosolve, and deionized water (1) were mixed in a stainless steel vessel and uniformly stirred. Next, carbon black, titanium dioxide and basic lead silicate were added, and the mixture was dispersed with a sand grind mill.
A pigment paste having a solid content of 50.0% or less, a total solid content of 50.0%, a resin solid content of 10% and a pigment solid content of 40% was obtained.
【００７１】製造例４ ポリウレタン架橋剤の調製 Production Example 4 Preparation of polyurethane crosslinking agent
【００７２】[0072]
【表４】反応物 重量部 固形分 ＩＰＤＩa) 371.4 371.4 ２−エチルヘキサノール 218.0 218.0 トリメチロールプロパン 75.0 75.0 ジブチル錫ジラウレート 0.08 −ブチルセロソルブ 284.7 − a) イソホロンジイソシアネートTable 4 Reactant parts by weight Solid content IPDI a) 371.4 371.4 2-ethylhexanol 218.0 218.0 Trimethylolpropane 75.0 75.0 Dibutyltin dilaurate 0.08- Butyl cellosolve 284.7- a) Isophorone diisocyanate
【００７３】表４に示す組成に従って、冷却器、撹拌機
を取り付けた４口フラスコ中に、ＩＰＤＩを入れ、乾燥
窒素雰囲気下、室温で撹拌しながら２−エチルヘキサノ
ールを添加した。反応混合物を冷却し、３８℃に保持し
た。According to the composition shown in Table 4, IPDI was placed in a four-necked flask equipped with a condenser and a stirrer, and 2-ethylhexanol was added with stirring at room temperature under a dry nitrogen atmosphere. The reaction mixture was cooled and kept at 38 ° C.
【００７４】同温度で30分保持した後60℃に昇温した。
ジブチル錫ジラウレートを添加後、撹拌しながらトリメ
チロールプロパンを添加し、昇温して反応混合物を１２
０℃で約１.５時間加熱保持した。赤外吸収スペクトル
によりイソシアネート基の吸収の消失を確認した後、エ
チルセロソルブで希釈し、ポリウレタン架橋剤を得た。After maintaining at the same temperature for 30 minutes, the temperature was raised to 60 ° C.
After adding dibutyltin dilaurate, trimethylolpropane was added with stirring, and the temperature was raised to 12
It was heated and held at 0 ° C. for about 1.5 hours. After confirming disappearance of isocyanate group absorption by infrared absorption spectrum, the mixture was diluted with ethyl cellosolve to obtain a polyurethane crosslinking agent.
【００７５】製造例５ 低分子量ポリオールの調製 Production Example 5 Preparation of low molecular weight polyol
【００７６】[0076]
【表５】反応物 重量部 固形分 ＳＴ−３０００a) 921.6 921.6 ビスフェノールＡ 228.0 228.0 ブチルセロソルブ(1) 284.4 − ジメチルベンジルアミン(1) 3.0 − 安息香酸 237.9 237.9 ブチルセロソルブ(2) 52.5 − ジメチルベンジルアミン(2) 7.0 − ε−カプロラクトン 399.0 399.0 ブチルセロソルブ(3) 239.6 −ジブチル錫オキサイド 9.0 − a) 東都化成社製の水添ビスフェノールＡ型エポキシ樹脂
(分子量４００、エポキシ当量２３０.４)[Table 5] Reactant parts by weight Solid content ST-3000 a) 921.6 921.6 Bisphenol A 228.0 228.0 Butyl cellosolve (1) 284.4-Dimethylbenzylamine (1) 3.0-Benzoic acid 237.9 237.9 Butyl cellosolve (2) 52.5-Dimethylbenzylamine (2 ) 7.0-ε-caprolactone 399.0 399.0 butyl cellosolve (3) 239.6- dibutyltin oxide 9.0- a) Hydrogenated bisphenol A type epoxy resin manufactured by Toto Kasei
(Molecular weight 400, Epoxy equivalent 230.4)
【００７７】表５に示す組成に従って、環流冷却器、攪
拌機を取り付けた４口フラスコ中に、ＳＴ−３０００、
ビスフェノールＡ及びブチルセロソルブ(１)を混合し、
窒素気流下、攪拌しながら１２０℃に加熱保持した。ジ
メチルベンジルアミン(１)(以下「ＤＭＢＡ」と略す)を添
加後、さらに攪拌しながら１８０℃で３時間加熱保持し
た。１４０℃に冷却後、安息香酸とブチルセロソルブ
(２)とを添加し、同温度で攪拌しながら加熱保持した。
ＤＭＢＡ(２)を添加後、更に同温度で攪拌しながら酸価
が０.５以下になるまで加熱保持した。１３０℃に冷却
後、ε−カプロラクトン、ブチルセロソルブ(３)及びジ
ブチル錫オキサイドを添加し、同温度で３時間、攪拌し
ながら加熱保持して、固形分濃度７５％の低分子量ポリ
オール溶液を得た。According to the composition shown in Table 5, ST-3000 was placed in a four-necked flask equipped with a reflux condenser and a stirrer.
Mix bisphenol A and butyl cellosolve (1),
The mixture was heated and maintained at 120 ° C. while stirring under a nitrogen stream. After adding dimethylbenzylamine (1) (hereinafter abbreviated as “DMBA”), the mixture was heated and maintained at 180 ° C. for 3 hours with further stirring. After cooling to 140 ° C, benzoic acid and butyl cellosolve
(2) was added, and the mixture was heated and maintained at the same temperature with stirring.
After the addition of DMBA (2), the mixture was further heated and stirred at the same temperature until the acid value became 0.5 or less. After cooling to 130 ° C., ε-caprolactone, butyl cellosolve (3) and dibutyltin oxide were added, and the mixture was heated and maintained at the same temperature for 3 hours with stirring to obtain a low molecular weight polyol solution having a solid content of 75%.
【００７８】製造例６〜８及び比較製造例１〜４ 低分子量ポリオールの調製 Preparation Examples 6 to 8 and Comparative Preparation Examples 1 to 4 Preparation of Low Molecular Weight Polyol
【００７９】エポキシ樹脂、ビスフェノールＡ、モノカ
ルボン酸、ε−カプロラクトンを以下の表６及び７に示
す組成で配合すること以外は製造例５と同様にして、低
分子量ポリオール溶液を得た。A low-molecular-weight polyol solution was obtained in the same manner as in Production Example 5, except that the epoxy resin, bisphenol A, monocarboxylic acid, and ε-caprolactone were blended in the compositions shown in Tables 6 and 7 below.
【００８０】[0080]
【表６】 製造例 ５ ６ ７ ８ ＳＴ−３０００a) 921.6 921.6 1382.4 − ＳＴ−５１００b) − − − 1821.8 ビスフェノールＡ 228.0 228.0 456.0 − ブチルセロソルブc)(1) 284.4 284.4 453.6 − ＤＭＢＡd)(1) 3.0 3.0 6.0 − 安息香酸 237.9 − 237.9 237.9 ＤＭＰＡe) − 254.6 − − ブチルセロソルブ(2) 52.5 56.7 49.0 504.4 ＤＭＢＡ(2) 7.0 7.0 10.5 10.5 ε-カプロラクトン 399.0 399.0 513.0 399.0 ブチルセロソルブ(3) 239.6 241.0 331.0 292.4ジブチル錫オキサイド 9.0 9.0 13.0 12.3 固形分（％） 75 75 75 75 Table 6 Production Example 5 67 8 ST-3000 a) 921.6 921.6 1382.4-ST-5100 b) ---1821.8 Bisphenol A 228.0 228.0 456.0-Butyl cellosolve c) (1) 284.4 284.4 453.6-DMBA d) (1) 3.0 3.0 6.0 − Benzoic acid 237.9 − 237.9 237.9 DMPA e) − 254.6 − − Butyl cellosolve (2) 52.5 56.7 49.0 504.4 DMBA (2) 7.0 7.0 10.5 10.5 ε-Caprolactone 399.0 399.0 513.0 399.0 Butyl cellosolve (3) 239.6 241.0 331.0 292.4 Dibutyltin Oxide 9.0 9.0 13.0 12.3 Solids (%) 75 75 75 75
【００８１】[0081]
【表７】 比較製造例 １ ２ ３ ４ ＳＴ−３０００ 460.8 921.6 921.6 − ＹＤ−０１４f) − − − 1900.0 ビスフェノールＡ − 228.0 228.0 − ブチルセロソルブ(1) − 284.4 284.4 − DMBA(1) − 3.0 3.0 − 安息香酸 237.9 237.9 183.0 237.9 ブチルセロソルブ(2) 171.2 52.5 38.8 523.8 ＤＭＢＡ(2) 3.5 7.0 7.0 10.7 ε-カプロラクトン 171.0 171.0 342.0 627.0 ブチルセロソルブ(3) 110.7 164.8 216.7 373.4ジブチル錫オキサイド 4.5 7.8 8.4 13.8 固形分（％） 75 75 75 75 a) 東都化成社製の水添ビスフェノールＡ型エポキシ樹脂(分子量４００、エポキ シ当量２３０.４)b) 東都化成社製の環状脂肪族系エポキシ樹脂(分子量１８００、エポキシ当量９ １０.９)c) エチレングリコールモノブチルエーテルd) ジメチルベンジルアミンe) ジメチロールプロピオン酸[２,２−ビス(ヒドロキシメチル)プロピオン酸]f) 東都化成社製のビスフェノールＡ型エポキシ樹脂(分子量１９００、エポキシ 当量９５０)Table 7 Comparative Production Example 1 2 3 4 ST-3000 460.8 921.6 921.6-YD-014 f) ---1900.0 Bisphenol A-228.0 228.0-Butyl cellosolve (1)-284.4 284.4-DMBA (1)-3.0 3.0-Benzo Acid 237.9 237.9 183.0 237.9 Butyl cellosolve (2) 171.2 52.5 38.8 523.8 DMBA (2) 3.5 7.0 7.0 10.7 ε-caprolactone 171.0 171.0 342.0 627.0 Butyl cellosolve (3) 110.7 164.8 216.7 373.4 Dibutyltin oxide 4.5 7.8 8.4 13.8 Solids (%) 75 75 75 75 a) Hydrogenated bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd. (molecular weight: 400, epoxy equivalent: 230.4) b) Cyclic aliphatic epoxy resin manufactured by Toto Kasei Co., Ltd. (molecular weight: 1800, epoxy equivalent: 910.9 ) ) c) ethylene glycol monobutyl ether d) dimethylbenzylamine e) dimethylol propionic acid [2,2-bis (hydroxymethyl) propionic acid] f) Tohto Kasei Manufactured bisphenol A type epoxy resin (molecular weight 1900, epoxy equivalent 950)
【００８２】製造例９ カチオン性高分子量ポリオールの調製 Production Example 9 Preparation of cationic high molecular weight polyol
【００８３】[0083]
【表８】 反応物 重量部 固形分 キシレン 465.0 − グリシジルメタクリレート 170.0 170.0 ２−ヒドロキシエチルメタクリレート 90.0 90.0 エチルメタクリレート 317.0 317.0 スチレン 250.0 250.0 n−ブチルアクリレート 136.0 136.0 n−ブチルメタクリレート 37.0 37.0 α,α'−アゾビスイソブチロニトリル(1) 40.0 40.0 ３−メトキシ−n−ブタノール 5.0 − α,α'−アゾビスイソブチロニトリル(2) 5.0 5.0Ｎ−メチルエタノールアミン 92.6 92.6 Table 8 Reactant parts by weight Solids xylene 465.0-Glycidyl methacrylate 170.0 170.0 2-hydroxyethyl methacrylate 90.0 90.0 Ethyl methacrylate 317.0 317.0 Styrene 250.0 250.0 n-Butyl acrylate 136.0 136.0 n-Butyl methacrylate 37.0 37.0 α, α'-azobis Isobutyronitrile (1) 40.0 40.0 3-Methoxy-n-butanol 5.0-α, α'-azobisisobutyronitrile (2) 5.0 5.0 N-methylethanolamine 92.6 92.6
【００８４】表８に示す組成に従って、滴下ロート、環
流冷却器、攪拌機を取り付けた５口フラスコ中にキシレ
ンを入れ、窒素気流下１２０℃に加熱保持した。グリシ
ジルメタクリレート、２−ヒドロキシエチルメタクリレ
ート、エチルメタクリレート、スチレン、n−ブチルア
クリレート、n−ブチルメタクリレート及びα,α'−ア
ゾビスイソブチロニトリル(以下ＡＩＢＮと略す)(１)の
混合物を４時間かけてフラスコに撹拌しながら滴下し
た。According to the composition shown in Table 8, xylene was charged into a five-necked flask equipped with a dropping funnel, a reflux condenser and a stirrer, and heated and maintained at 120 ° C. under a nitrogen stream. A mixture of glycidyl methacrylate, 2-hydroxyethyl methacrylate, ethyl methacrylate, styrene, n-butyl acrylate, n-butyl methacrylate and α, α′-azobisisobutyronitrile (hereinafter abbreviated as AIBN) (1) over 4 hours The mixture was dropped into the flask with stirring.
【００８５】滴下終了後、さらに同温度で１時間、攪拌
しながら加熱保持した。次いで３−メトキシ−n−ブタ
ノールとＡＩＢＮ(２)の混合物を５分間かけて滴下し、
さらに同温度で１時間加熱保持して、グリシジル基含有
アクリルポリオール溶液を得た。このアクリルポリオー
ルは、Ｔg ５０℃、数平均分子量８０００、水酸基価３
９であった。得られたポリオール溶液を９０℃に冷却
後、Ｎ−メチルアミノエタノールを配合し、窒素気流
下、１３０℃で２時間反応を行って、固形分濃度７０.
７％のアミン付加アクリルポリオール溶液を得た。After completion of the dropwise addition, the mixture was heated and maintained at the same temperature for 1 hour while stirring. Then, a mixture of 3-methoxy-n-butanol and AIBN (2) was added dropwise over 5 minutes,
Further, the mixture was heated and maintained at the same temperature for 1 hour to obtain a glycidyl group-containing acrylic polyol solution. This acrylic polyol has a Tg of 50 ° C., a number average molecular weight of 8,000 and a hydroxyl value of 3
Nine. After cooling the obtained polyol solution to 90 ° C., N-methylaminoethanol was added, and the mixture was reacted at 130 ° C. for 2 hours under a nitrogen stream to obtain a solid content of 70.
A 7% amine-added acrylic polyol solution was obtained.
【００８６】製造例１０及び比較製造例５ カチオン性高分子量ポリオールの調製 Production Example 10 and Comparative Production Example 5 Preparation of cationic high molecular weight polyol
【００８７】アクリルモノマー及びカチオン性付与剤を
以下の表９に示す組成で配合すること以外は製造例９と
同様にして、アミン付加アクリルポリオール溶液を得
た。An amine-added acrylic polyol solution was obtained in the same manner as in Production Example 9 except that the acrylic monomer and the cationicity-imparting agent were blended in the composition shown in Table 9 below.
【００８８】[0088]
【表９】 製造例 比較製造例 ９ １０ ５ モノマー配合 グリシジルメタクリレート 170.0 100.0 85.0 2-ヒドロキシエチルメタクリレート 90.0 90.0 90.0 ＦＭ−１a) − 150.0 − スチレン 250.0 250.0 250.0 エチルメタクリレート 317.0 − − n-ブチルアクリレート 37.0 105.0 333.0 n-ブチルメタクリレート 136.0 140.0 − メチルメタクリレート − 165.0 157.0 カチオン性付与剤 Ｎ−メチルエタノールアミン 92.6 54.5 46.3 特性値 Ｔg(℃) 50 35 16 水酸基価 38.8 73.0 38.8 Ｍn 8000 8000 8000 固形分（％） 70.7 70.0 69.8 a) ダイセル化学社製のε−カプロラクトン変性メタアクリレートTable 9 Production Example Comparative Production Example 9 10 5 Monomer blended glycidyl methacrylate 170.0 100.0 85.0 2-hydroxyethyl methacrylate 90.0 90.0 90.0 FM-1 a) -150.0-Styrene 250.0 250.0 250.0 Ethyl methacrylate 317.0--n-butyl acrylate 37.0 105.0 333.0 n-butyl methacrylate 136.0 140.0-Methyl methacrylate-165.0 157.0 Cation imparting agent N-methylethanolamine 92.6 54.5 46.3 Characteristic value Tg (° C) 50 35 16 Hydroxyl value 38.8 73.0 38.8 Mn 8000 8000 8000 8000 Solids (%) 70.7 70.0 69.8 a) ε-caprolactone-modified methacrylate manufactured by Daicel Chemical Industries , Ltd.
【００８９】製造例１１ アニオン性高分子量ポリオールの調製 Production Example 11 Preparation of an anionic high molecular weight polyol
【００９０】[0090]
【表１０】 反応物 重量部 固形分 キシレン 447.9 − メタクリル酸 56.8 56.8 2-ヒドロキシエチルメタクリレート 90.0 90.0 2-ヒドロキシプロピルメタクリレート 123.0 123.0 スチレン 250.0 250.0 n-ブチルアクリレート 111.3 111.3 n-ブチルメタクリレート 368.9 368.9 ＡＩＢＮ(1) 40.0 40.0 ３−メトキシ−n−ブタノール 5.0 −ＡＩＢＮ(2) 5.0 5.0 Table 10 Reactant parts by weight Solids xylene 447.9-Methacrylic acid 56.8 56.8 2-Hydroxyethyl methacrylate 90.0 90.0 2-Hydroxypropyl methacrylate 123.0 123.0 Styrene 250.0 250.0 n-Butyl acrylate 111.3 111.3 n-Butyl methacrylate 368.9 368.9 AIBN (1) 40.0 40.0 3-methoxy-n-butanol 5.0- AIBN (2) 5.0 5.0
【００９１】表１０に示す組成に従って、滴下ロート、
環流冷却器、攪拌機を取り付けた５口フラスコ中にキシ
レンを入れ、窒素気流下１２０℃に加熱保持した。キシ
レン、メタクリル酸、２−ヒドロキシエチルメタクリレ
ート、２−ヒドロキシプロピルメタクリレート、スチレ
ン、n−ブチルアクリレート、n−ブチルメタクリレート
及びＡＩＢＮ(１)の混合物を４時間かけて撹拌しながら
滴下した。According to the composition shown in Table 10, a dropping funnel,
Xylene was charged into a 5-neck flask equipped with a reflux condenser and a stirrer, and heated and maintained at 120 ° C. under a nitrogen stream. A mixture of xylene, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, n-butyl acrylate, n-butyl methacrylate and AIBN (1) was added dropwise with stirring over 4 hours.
【００９２】滴下終了後、さらに１２０℃で１時間、攪
拌しながら加熱保持した。次いで３−メトキシ−n−ブ
タノールとＡＩＢＮ(２)の混合物を５分間かけて滴下
し、さらに同温度で１時間加熱保持して、固形分濃度約
７０％のアクリルポリオール溶液を得た。このアクリル
ポリオールは、Ｔg ３５℃、数平均分子量８０００、酸
価３７、水酸基価８６.７であった。After completion of the dropwise addition, the mixture was heated and maintained at 120 ° C. for 1 hour with stirring. Next, a mixture of 3-methoxy-n-butanol and AIBN (2) was added dropwise over 5 minutes, and the mixture was further heated and maintained at the same temperature for 1 hour to obtain an acrylic polyol solution having a solid concentration of about 70%. This acrylic polyol had a Tg of 35 ° C., a number average molecular weight of 8,000, an acid value of 37, and a hydroxyl value of 86.7.
【００９３】製造例１２及び比較製造例６ アニオン性高分子量ポリオールの調製 Production Example 12 and Comparative Production Example 6 Preparation of Anionic High Molecular Weight Polyol
【００９４】アクリルモノマーを以下の表１１に示す組
成で配合すること以外は製造例９と同様にして、アクリ
ルポリオール溶液を得た。An acrylic polyol solution was obtained in the same manner as in Production Example 9 except that the acrylic monomer was blended in the composition shown in Table 11 below.
【００９５】[0095]
【表１１】 製造例 比較製造例 １１ １２ ６ モノマー配合 メタクリル酸 56.8 − 30.0 アクリル酸 − 45.0 − 2-ヒドロキシエチルメタクリレート 90.0 90.0 90.0 2-ヒドロキシプロピルメタクリレート 123.0 − − スチレン 250.0 250.0 250.0 n-ブチルアクリレート 111.3 100.0 125.0 n-ブチルメタクリレート 368.9 290.0 265.0 エチルメタクリレート − 200.0 240.0 アクリルアミド − 25.0 − 特性値 Ｔg 35.0 42.8 40.0 水酸基価 86.7 38.8 38.8 酸価 37.0 35.0 19.5 Ｍn 8000 8000 8000 固形分（％） 70 70 70 [Table 11] Production Example Comparative Production Example 11 126 Monomer blended methacrylic acid 56.8-30.0 Acrylic acid-45.0-2-hydroxyethyl methacrylate 90.0 90.0 90.0 2-hydroxypropyl methacrylate 123.0--Styrene 250.0 250.0 250.0 n-butyl acrylate 111.3 100.0 125.0 n-butyl methacrylate 368.9 290.0 265.0 ethyl methacrylate-200.0 240.0 acrylamide-25.0- characteristic value Tg 35.0 42.8 40.0 hydroxyl value 86.7 38.8 38.8 acid value 37.0 35.0 19.5 Mn 8000 8000 8000 8000 solids (%) 70 70 70
【００９６】実施例１ カチオン電着塗料組成物の調製 Example 1 Preparation of cationic electrodeposition coating composition
【００９７】[0097]
【表１２】 成分 重量部 固形分 製造例５の低分子量ポリオール 207.1 145.0 製造例９のカチオン性高分子量ポリオール 820.4 580.0 製造例４のポリウレタン架橋剤 392.9 275.0 チヌビン１１３０a) 20.0 20.0 アデカスタブＬＡ−６２b) 10.0 10.0 氷酢酸 19.1 − 脱イオン水(1) 1391.6 − 製造例３の顔料ペースト 130.4 65.2脱イオン水(2) 2484.5 − a) チバガイギー社製の紫外線吸収剤b) 旭電化工業社製の光安定剤 Ingredients : parts by weight Solids Low molecular weight polyol of Preparation Example 5 207.1 145.0 Cationic high molecular weight polyol of Preparation Example 820.4 580.0 Polyurethane crosslinker of Preparation Example 392.9 275.0 Tinuvin 1130 a) 20.0 20.0 ADK STAB LA-62 b) 10.0 10.0 Glacial acetic acid 19.1-Deionized water (1) 1391.6-Pigment paste of Production Example 3 130.4 65.2 Deionized water (2) 2484.5- a) UV absorber manufactured by Ciba-Geigy b) Light stabilizer manufactured by Asahi Denka Kogyo
【００９８】上記配合に従い、製造例５で得られた低分
子量ポリオール、製造例９で得られたカチオン性高分子
量ポリオール、製造例４で得られたポリウレタン架橋
剤、チヌビン１１３０及びアデカスタブＬＡ−６２を均
一混合し、氷酢酸で中和した後、脱イオン水(１)でゆっ
くり希釈した。次いで、製造例３で得られた顔料ペース
トを添加して均一混合し、さらに脱イオン水(２)を加え
て均一攪拌し、固形分濃度約２０％のカチオン電着塗料
組成物を得た。According to the above formulation, the low molecular weight polyol obtained in Production Example 5, the cationic high molecular weight polyol obtained in Production Example 9, the polyurethane crosslinker obtained in Production Example 4, Tinuvin 1130 and Adekastab LA-62 were used. After homogeneously mixing and neutralizing with glacial acetic acid, the mixture was slowly diluted with deionized water (1). Next, the pigment paste obtained in Production Example 3 was added and mixed homogeneously. Further, deionized water (2) was added and the mixture was stirred uniformly to obtain a cationic electrodeposition coating composition having a solid content of about 20%.
【００９９】実施例２〜５及び比較例１〜４ カチオン電着塗料組成物の調製 Examples 2-5 and Comparative Examples 1-4 Preparation of cationic electrodeposition coating compositions
【０１００】低分子量ポリオール、高分子量ポリオー
ル、架橋剤、紫外線吸収剤、中和剤及び脱イオン水(1)
を以下の表１３及び１４に示す組成で配合すること以外
は実施例１と同様にして、カチオン電着塗料組成物を得
た。Low molecular weight polyol, high molecular weight polyol, crosslinking agent, ultraviolet absorber, neutralizing agent and deionized water (1)
Was prepared in the same manner as in Example 1 except that it was blended in the composition shown in Tables 13 and 14 below to obtain a cationic electrodeposition coating composition.
【０１０１】[0101]
【表１３】 実施例 １ ２ ３ ４ ５ 低分子量ポリオール 製造例５ 193.3 193.3 − − − 製造例６ − − 193.3 − − 製造例７ − − − 193.3 − 製造例８ − − − − 193.3 高分子量ポリオール 製造例９ 820.4 − 820.4 820.4 820.4 製造例１０ − 828.6 − − − 架橋剤 製造例４ 392.9 392.9 392.9 392.9 392.9 中和剤 氷酢酸 19.1 11.7 19.1 19.1 19.1脱イオン水(1) 1435.4 1434.6 1435.4 1435.4 1435.4 Table 13 Example 1 2 3 4 5 Low molecular weight polyol Production Example 5 193.3 193.3---Production Example 6--193.3--Production Example 7---193.3-Production Example 8----193.3 Production of high molecular weight polyol Example 9 820.4-820.4 820.4 820.4 Preparation 10-828.6---Crosslinker Preparation 4 392.9 392.9 392.9 392.9 392.9 Neutralizer Glacial acetic acid 19.1 11.7 19.1 19.1 19.1 Deionized water (1) 1435.4 1434.6 1435.4 1435.4 1435.4
【０１０２】[0102]
【表１４】 比較例 １ ２ ３ ４ 低分子量ポリオール 比較製造例１ 193.3 − − 830.9 比較製造例２ − 193.3 − − 比較製造例３ − − 193.3 − 製造例５ − − − 193.3 高分子量ポリオール 製造例９ 820.4 820.4 820.4 − 架橋剤 製造例４ 392.9 392.9 392.9 392.9 中和剤 氷酢酸 19.1 19.1 19.1 9.6脱イオン水(1) 1435.4 1435.4 1435.4 1434.4 Table 14 Comparative Example 1 2 3 4 Low molecular weight polyol Comparative production example 1 193.3--830.9 Comparative production example 2-193.3--Comparative production example 3--193.3-Production example 5---193.3 High molecular weight polyol Production example 9 820.4 820.4 820.4-Crosslinking agent Production Example 4 392.9 392.9 392.9 392.9 Neutralizing agent Glacial acetic acid 19.1 19.1 19.1 9.6 Deionized water (1) 1435.4 1435.4 1435.4 1434.4
【０１０３】実施例６ カチオン電着塗料組成物の調製 Example 6 Preparation of cationic electrodeposition coating composition
【０１０４】[0104]
【表１５】 成分 重量部 固形分 製造例５の低分子量ポリオール 207.1 145.0 製造例９のカチオン性高分子量ポリオール 820.4 580.0 製造例４のポリウレタン架橋剤 392.9 275.0 チヌビン１１３０ 20.0 20.0 アデカスタブＬＡ−６２ 10.0 10.0 氷酢酸 19.1 −脱イオン水 3680.5 − Component 15 parts by weight Solid content Low molecular weight polyol of Production Example 5 207.1 145.0 Cationic high molecular weight polyol of Production Example 82 0.4580.0 Polyurethane crosslinker of Production Example 392.9 275.0 Tinuvin 1130 20.0 20.0 ADK STAB LA-62 10.0 10.0 Glacial acetic acid 19.1 − Deionized water 3680.5 −
【０１０５】上記配合に従い、製造例５で得られた低分
子量ポリオール、製造例９で得られたカチオン性高分子
量ポリオール、製造例４で得られたポリウレタン架橋
剤、チヌビン１１３０及びアデカスタブＬＡ−６２を均
一混合し、氷酢酸で中和した後、脱イオン水でゆっくり
希釈することにより、固形分濃度約２０％のカチオン電
着塗料組成物を得た。According to the above composition, the low molecular weight polyol obtained in Production Example 5, the cationic high molecular weight polyol obtained in Production Example 9, the polyurethane crosslinking agent obtained in Production Example 4, Tinuvin 1130 and ADK STAB LA-62 were used. After uniform mixing and neutralization with glacial acetic acid, the mixture was slowly diluted with deionized water to obtain a cationic electrodeposition coating composition having a solid content of about 20%.
【０１０６】実施例７ アニオン電着塗料組成物の調製 Example 7 Preparation of an anionic electrodeposition coating composition
【０１０７】[0107]
【表１６】 成分 重量部 固形分 製造例５の低分子量ポリオール 213.3 160.0 製造例１１のアニオン性高分子量ポリオール 914.3 640.0 サイメル２３５a) 204.1 200.0 チヌビン１１３０ 20.0 20.0 アデカスタブＬＡ−６２ 10.0 10.0 トリエチルアミン 25.0 −脱イオン水 3763.3 − a) 三井サイテック社製のアルキル化メラミン樹脂 Component 16 parts by weight Solid content Low molecular weight polyol of Production Example 5 213.3 160.0 Anionic high molecular weight polyol of Production Example 91 914.3 640.0 Cymel 235 a) 204.1 200.0 Tinuvin 1130 20.0 20.0 ADK STAB LA-62 10.0 10.0 Triethylamine 25.0- Deionized Water 3763.3- a) Alkylated melamine resin manufactured by Mitsui Cytec
【０１０８】上記配合に従い、製造例５で得られた低分
子量ポリオール、製造例１１で得られたアニオン性高分
子量ポリオール、サイメル２３５、チヌビン１１３０及
びアデカスタブＬＡ−６２を均一混合し、トリエチルア
ミンで中和した後、脱イオン水でゆっくり希釈すること
により、固形分濃度約２０％のアニオン電着塗料組成物
を得た。According to the above composition, the low molecular weight polyol obtained in Production Example 5, the anionic high molecular weight polyol obtained in Production Example 11, Cymel 235, Tinuvin 1130 and ADK STAB LA-62 were uniformly mixed and neutralized with triethylamine. After that, the mixture was slowly diluted with deionized water to obtain an anionic electrodeposition coating composition having a solid content of about 20%.
【０１０９】実施例８〜１２及び比較例５〜８ アニオン電着塗料組成物の調製 Examples 8 to 12 and Comparative Examples 5 to 8 Preparation of anionic electrodeposition coating compositions
【０１１０】低分子量ポリオール、高分子量ポリオー
ル、架橋剤、紫外線吸収剤、中和剤及び脱イオン水を以
下の表１７及び１８に示す組成で配合すること以外は実
施例７と同様にして、アニオン電着塗料組成物を得た。Anion was conducted in the same manner as in Example 7 except that a low molecular weight polyol, a high molecular weight polyol, a crosslinking agent, an ultraviolet absorber, a neutralizing agent and deionized water were blended in the compositions shown in Tables 17 and 18 below. An electrodeposition coating composition was obtained.
【０１１１】[0111]
【表１７】 実施例 ７ ８ ９ １０ １１ １２ 低分子量ポリオール 製造例５ 213.3 213.3 213.3 − − − 製造例６ − − − 213.3 − − 製造例７ − − − − 213.3 − 製造例８ − − − − − 213.3 高分子量ポリオール 製造例１１ 914.3 − − 914.3 914.3 914.3 製造例１２ − 914.3 − − − − ＷＥ−８０４a) − − 1066.7 − − − 架橋剤 サイメル２３５b) 204.1 204.1 204.1 204.1 204.1 204.1 中和剤 トリエチルアミン 25.0 23.6 25.5 25.0 25.0 25.0脱イオン水 3763.3 3764.7 3762.8 3763.3 3763.3 3763.3 a) 東レ社製の水溶性アニオン性アクリル樹脂「コータックスＷＥ−８０４」(固形 分５５％、Ｔｇ４３℃、水酸基価４３、酸価３７．７、数平均分子量７０００)b) 三井サイテック社製のアルキル化メラミン樹脂Table 17 Example 7 8 9 10 11 12 Low molecular weight polyol Production Example 5 213.3 213.3 213.3---Production Example 6---213.3--Production Example 7----213.3-Production Example 8----- 213.3 High molecular weight polyol Production Example 11 914.3--914.3 914.3 914.3 Production Example 12-914.3----WE-804 a) --1066.7---Crosslinking agent Cymel 235 b) 204.1 204.1 204.1 204.1 204.1 204.1 Neutralizing agent triethylamine 25.0 23.6 25.5 25.0 25.0 25.0 Deionized water 3763.3 3764.7 3762.8 3763.3 3763.3 3763.3 a) Water-soluble anionic acrylic resin “Kotax WE-804” manufactured by Toray (solid content 55%, Tg 43 ° C, hydroxyl value 43, acid value 37. 7, number average molecular weight 7000) b) Alkylated melamine resin manufactured by Mitsui Cytec
【０１１２】[0112]
【表１８】 比較例 ５ ６ ７ ８ 低分子量ポリオール 比較製造例１ 213.3 − − − 比較製造例２ − 213.3 − − 比較製造例３ − − 213.3 − 製造例５ − − − 213.3 高分子量ポリオール 製造例１１ 914.3 914.3 914.3 − 比較製造例６ − − − 914.3 架橋剤 サイメル２３５ 204.1 204.1 204.1 204.1 中和剤 トリエチルアミン 25.0 25.0 25.0 13.2脱イオン水 3763.3 3763.3 3763.3 3775.1 Table 18 Comparative Example 5 6 7 8 Low molecular weight polyol Comparative production example 1 213.3---Comparative production example 2-213.3--Comparative production example 3--213.3-Production example 5---213.3 High molecular weight polyol Production example 11 914.3 914.3 914.3-Comparative Production Example 6---914.3 Crosslinker Cymel 235 204.1 204.1 204.1 204.1 Neutralizer Triethylamine 25.0 25.0 25.0 13.2 Deionized water 3763.3 3763.3 3763.3 3775.1
【０１１３】実施例１３ アニオン電着塗料組成物の調製 Example 13 Preparation of an anionic electrodeposition coating composition
【０１１４】[0114]
【表１９】 成分 重量部 固形分 製造例５の低分子量ポリオール 213.3 160.0 製造例１１のアニオン性高分子量ポリオール 914.3 640.0 サイメル２３５ 204.1 200.0 チヌビン１１３０ 20.0 20.0 アデカスタブＬＡ−６２ 10.0 10.0 トリエチルアミン 25.0 − 脱イオン水(1) 1474.4 − カーボンブラック 1.2 1.2 二酸化チタン 47.1 47.1 ケイ酸アルミ 3.1 3.1脱イオン水(2) 2495.0 − Component 19 parts by weight Solid content Low molecular weight polyol of Production Example 5 213.3 160.0 Anionic high molecular weight polyol of Production Example 91 914.3 640.0 Cymel 235 204.1 200.0 Tinuvin 1130 20.0 20.0 ADK STAB LA-62 10.0 10.0 Triethylamine 25.0-Deionized water ( 1) 1474.4 − Carbon black 1.2 1.2 Titanium dioxide 47.1 47.1 Aluminum silicate 3.1 3.1 Deionized water (2) 2495.0 −
【０１１５】上記配合に従い、製造例５で得られた低分
子量ポリオール、製造例１１で得られたアニオン性高分
子量ポリオール、サイメル２３５、チヌビン１１３０及
びアデカスタブＬＡ−６２を均一混合し、トリエチルア
ミンで中和した後、脱イオン水(１)でゆっくり希釈し
た。さらに、カーボンブラック、二酸化チタン及びケイ
酸アルミを添加し均一混合した後、脱イオン水(２)でゆ
っくり希釈して、固形分濃度約２０％のアニオン電着塗
料組成物を得た。According to the above composition, the low molecular weight polyol obtained in Production Example 5, the anionic high molecular weight polyol obtained in Production Example 11, Cymel 235, Tinuvin 1130 and ADK STAB LA-62 were uniformly mixed and neutralized with triethylamine. After that, it was slowly diluted with deionized water (1). Further, after adding and uniformly mixing carbon black, titanium dioxide and aluminum silicate, the mixture was slowly diluted with deionized water (2) to obtain an anionic electrodeposition coating composition having a solid content of about 20%.
【０１１６】[0116]
【電着塗料組成物の評価】以下の方法により、実施例及
び比較例で調整した電着塗料組成物の安定性、耐温水性
及び耐候性を評価した。結果を表１７に示す。[Evaluation of electrodeposition coating composition] The stability, warm water resistance and weather resistance of the electrodeposition coating compositions prepared in Examples and Comparative Examples were evaluated by the following methods. Table 17 shows the results.
【０１１７】塗料安定性 得られた電着塗料組成物４０００ｇを容器に密封して４
０℃の環境下で２週間保存した。保存後の塗料組成物を
４００メッシュのナイロン製フィルタでろ過し、残渣の
多少により以下の基準で塗料の安定性を評価した。 ろ過残渣無し ○ ろ過残渣有り △ ろ過残渣顕著 × Coating stability 4000 g of the obtained electrodeposition coating composition was sealed in a container and dried.
It was stored for 2 weeks in an environment of 0 ° C. The coating composition after storage was filtered through a 400-mesh nylon filter, and the stability of the coating was evaluated according to the following criteria depending on the amount of residue. No filtration residue ○ Filtration residue present △ Filtration residue outstanding ×
【０１１８】耐温水性 得られた電着塗料組成物に厚さ０.７mmのＳＰＣＣ鋼板
を浸漬し、３０μ膜厚になる様、電圧／時間を制御し
た。次いで、この鋼板を１７０℃で２０分間保持するこ
とにより塗膜を硬化させた。 Warm water resistance A 0.7 mm thick SPCC steel plate was immersed in the obtained electrodeposition coating composition, and the voltage / time was controlled so as to obtain a film thickness of 30 μm. Next, the steel sheet was kept at 170 ° C. for 20 minutes to cure the coating film.
【０１１９】電着塗装された鋼板の塗装面にカッターを
用いて、鋼板の表面に達する深さの直線状の切り込み
を、２mm間隔で縦横それぞれ１０本づつ入れ、１００個
のマス目を形成した。Using a cutter on the coated surface of the electrodeposited steel sheet, ten linear cuts each having a depth reaching the surface of the steel sheet were formed at intervals of 2 mm each in the vertical and horizontal directions to form 100 squares. .
【０１２０】切り込みを入れた塗装鋼板を６０℃のイオ
ン交換水に１２０時間浸漬し、その後室温で２４時間保
つことにより乾燥させた。The cut steel sheet was immersed in ion-exchanged water at 60 ° C. for 120 hours and then dried at room temperature for 24 hours.
【０１２１】塗膜表面のマス目を形成した部分にニチバ
ン社製の粘着テープ「セロテープ」を乗せ、指で充分に圧
迫して接着させた。次いで、このセロテープの端部を持
ち、垂直方向に一気に剥離した。粘着テープと共に剥離
せず残存した塗膜の面積の多少により耐温水性を評価し
た。残存した塗膜の面積はマス目の数で示す。An adhesive tape “Cellotape” manufactured by Nichiban Co., Ltd. was placed on the portion of the coating film surface where the grids were formed, and was sufficiently pressed with a finger to adhere. Next, the end of the cellophane tape was held and peeled off at once in the vertical direction. Warm water resistance was evaluated based on the area of the remaining coating film without peeling off with the adhesive tape. The area of the remaining coating film is indicated by the number of squares.
【０１２２】耐候性 耐温水性評価と同様にして、塗装表面に切り込みのマス
目が形成された塗装鋼板を調製した。この塗装鋼板をサ
ンシャインウェザオメーターにて６００時間放置した。
次いで、塗装鋼板を温度５０℃及び湿度９５％以上の環
境に２４０時間放置し、その後室温で２４時間保つこと
により乾燥させた。In the same manner as in the evaluation of weather resistance and warm water resistance, a coated steel sheet having cut squares formed on the coating surface was prepared. The coated steel sheet was left for 600 hours with a sunshine weatherometer.
Next, the coated steel sheet was allowed to stand in an environment at a temperature of 50 ° C. and a humidity of 95% or higher for 240 hours, and then dried at room temperature for 24 hours.
【０１２３】塗膜表面のマス目を形成した部分にニチバ
ン社製の粘着テープ「セロテープ」を乗せ、指で充分に圧
迫して接着させた。次いで、このセロテープの端部を持
ち、垂直方向に一気に剥離した。粘着テープと共に剥離
せず残存した塗膜の面積の多少により耐候性を評価し
た。残存した塗膜の面積はマス目の数で、以下の基準に
より示す。 ８０個以上 ○ ８０個未満 ×An adhesive tape “Cellotape” manufactured by Nichiban Co., Ltd. was placed on the portion of the coating film surface where the grids were formed, and was sufficiently pressed with a finger to adhere. Next, the end of the cellophane tape was held and peeled off at once in the vertical direction. The weather resistance was evaluated based on the area of the remaining coating film without peeling off with the adhesive tape. The area of the remaining coating film is the number of squares, and is indicated by the following criteria. 80 or more ○ Less than 80 ×
【０１２４】[0124]
【表２０】 [Table 20]
【０１２５】[0125]
【表２１】 [Table 21]
【０１２６】[0126]
【発明の効果】耐食性、耐候性及び耐温水性に優れた塗
膜を形成しうる電着塗料組成物が提供された。The present invention provides an electrodeposition coating composition capable of forming a coating film having excellent corrosion resistance, weather resistance and hot water resistance.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｄ 133/06 Ｃ０９Ｄ 133/06 167/04 167/04 175/04 175/04 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C09D 133/06 C09D 133/06 167/04 167/04 175/04 175/04
Claims (8)
シ当量２００〜１５００の環状脂肪族部分を有するエポ
キシ樹脂をモノカルボン酸と反応させ、ついで、残存す
る水酸基をε−カプロラクトンと反応させることにより
得られる、１級水酸基を有する低分子量ポリオール；及
び（ｃ）架橋剤；を含有する電着塗料組成物。1. An epoxy resin having a cyclic aliphatic moiety having a molecular weight of 400 to 3000 and an epoxy equivalent of 200 to 1500 is reacted with a monocarboxylic acid, and then the remaining hydroxyl group is reacted with ε-caprolactone. An electrodeposition coating composition comprising: a low molecular weight polyol having a primary hydroxyl group; and (c) a crosslinking agent.
シ当量２００〜１５００の環状脂肪族部分を有するエポ
キシ樹脂をモノカルボン酸と反応させ、ついで、残存す
る水酸基をε−カプロラクトンと反応させることにより
得られる、１級水酸基を有する低分子量ポリオール； （ｂ）分子量３０００〜２０００００及び水酸基価１５
〜１２０のイオン性高分子量ポリオール；及び （ｃ）架橋剤；を含有する電着塗料組成物。(A) reacting an epoxy resin having a cyclic aliphatic moiety having a molecular weight of 400 to 3000 and an epoxy equivalent of 200 to 1500 with a monocarboxylic acid, and then reacting the remaining hydroxyl group with ε-caprolactone. (B) a molecular weight of 3000 to 200,000 and a hydroxyl value of 15
And (c) a crosslinking agent.
シ当量２００〜１５００の環状脂肪族部分を有するエポ
キシ樹脂をモノカルボン酸と反応させ、ついで、残存す
る水酸基をε−カプロラクトンと反応させることにより
得られる、１級水酸基を有する低分子量ポリオール５〜
３５重量％； （ｂ）分子量３０００〜２０００００及び水酸基価１５
〜１２０のイオン性高分子量ポリオール９５〜６５重量
％；及び （ｃ）該ポリオール成分(ａ)及び(ｂ)の合計１００重量
部に対して２０〜１００重量部の架橋剤；を含有する電
着塗料組成物。3. An epoxy resin having a cycloaliphatic moiety having a molecular weight of 400 to 3000 and an epoxy equivalent of 200 to 1500 is reacted with a monocarboxylic acid, and then the remaining hydroxyl groups are reacted with ε-caprolactone. Low molecular weight polyol having a primary hydroxyl group
(B) molecular weight 3000 to 200,000 and hydroxyl value 15
And (c) 20 to 100 parts by weight of a crosslinking agent based on 100 parts by weight of the total of the polyol components (a) and (b). Paint composition.
び(ｂ)の合計１００重量部に対して０．５〜１０重量部
の紫外線吸収剤；を含有する請求項３記載の電着塗料組
成物。4. The electrodeposition according to claim 3, further comprising (d) an ultraviolet absorber in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the total of the polyol components (a) and (b). Paint composition.
フェノールＡ型エポキシ樹脂である請求項１〜４のいず
れか記載の電着塗料組成物。5. The electrodeposition coating composition according to claim 1, wherein said epoxy resin is a hydrogenated bisphenol A type epoxy resin.
チロールプロピオン酸、ジメチロールブタン酸、グリコ
ール酸からなる群から選択される請求項１〜４のいずれ
か記載の電着塗料組成物。6. The electrodeposition coating composition according to claim 1, wherein the monocarboxylic acid is selected from the group consisting of benzoic acid, dimethylolpropionic acid, dimethylolbutanoic acid, and glycolic acid.
基の量と用いられるε−カプロラクトンの量とのモル比
が１／０．５〜１／１である請求項１〜４のいずれか記
載の電着塗料組成物。7. The battery according to claim 1, wherein the molar ratio of the amount of hydroxyl group contained in the low molecular weight polyol to the amount of ε-caprolactone used is 1 / 0.5 to 1/1. Coating composition.
含有量０〜２５重量％である請求項１〜４のいずれか記
載の電着塗料組成物。8. The electrodeposition coating composition according to claim 1, wherein the low molecular weight polyol has a phenyl moiety content of 0 to 25% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30666596A JPH10147734A (en) | 1996-11-18 | 1996-11-18 | Electrodepositon coating material composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30666596A JPH10147734A (en) | 1996-11-18 | 1996-11-18 | Electrodepositon coating material composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10147734A true JPH10147734A (en) | 1998-06-02 |
Family
ID=17959851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30666596A Pending JPH10147734A (en) | 1996-11-18 | 1996-11-18 | Electrodepositon coating material composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10147734A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000290584A (en) * | 1999-02-05 | 2000-10-17 | Kansai Paint Co Ltd | Resin composition for coating |
| JP2006291111A (en) * | 2005-04-13 | 2006-10-26 | Basf Coatings Japan Ltd | Coating composition, coating finishing method, and coated article |
| JP2007112996A (en) * | 2005-09-22 | 2007-05-10 | Kansai Paint Co Ltd | Anion electrodeposition paint |
| CN104877407A (en) * | 2015-05-20 | 2015-09-02 | 苏州市贝克生物科技有限公司 | Anti-radiation wear-proof paint and preparation method thereof |
| KR20220043188A (en) * | 2019-08-08 | 2022-04-05 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Polyol polymers, methods for making such polymers, and coating compositions comprising the same |
-
1996
- 1996-11-18 JP JP30666596A patent/JPH10147734A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000290584A (en) * | 1999-02-05 | 2000-10-17 | Kansai Paint Co Ltd | Resin composition for coating |
| JP2006291111A (en) * | 2005-04-13 | 2006-10-26 | Basf Coatings Japan Ltd | Coating composition, coating finishing method, and coated article |
| JP2007112996A (en) * | 2005-09-22 | 2007-05-10 | Kansai Paint Co Ltd | Anion electrodeposition paint |
| CN104877407A (en) * | 2015-05-20 | 2015-09-02 | 苏州市贝克生物科技有限公司 | Anti-radiation wear-proof paint and preparation method thereof |
| KR20220043188A (en) * | 2019-08-08 | 2022-04-05 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Polyol polymers, methods for making such polymers, and coating compositions comprising the same |
| CN114502614A (en) * | 2019-08-08 | 2022-05-13 | Ppg工业俄亥俄公司 | Polyol polymers, process for preparing such polymers and coating compositions containing polyol polymers |
| JP2022543466A (en) * | 2019-08-08 | 2022-10-12 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Polyol polymers, methods of preparing such polymers, and coating compositions containing same |
| CN114502614B (en) * | 2019-08-08 | 2024-03-08 | Ppg工业俄亥俄公司 | Polyol polymers, methods of making such polymers, and coating compositions containing polyol polymers |
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