JPS63221177A - Positive type photosensitive anionic electrodeposition paint composition - Google Patents
Positive type photosensitive anionic electrodeposition paint compositionInfo
- Publication number
- JPS63221177A JPS63221177A JP5414287A JP5414287A JPS63221177A JP S63221177 A JPS63221177 A JP S63221177A JP 5414287 A JP5414287 A JP 5414287A JP 5414287 A JP5414287 A JP 5414287A JP S63221177 A JPS63221177 A JP S63221177A
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- unsaturated
- unsaturated monomer
- compsn
- 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
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 29
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 15
- 239000003973 paint Substances 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 39
- -1 azidosulfonic acid halide Chemical class 0.000 claims abstract description 16
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 239000008199 coating composition Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 25
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 16
- 239000004925 Acrylic resin Substances 0.000 abstract description 10
- 229920000178 Acrylic resin Polymers 0.000 abstract description 10
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 230000036211 photosensitivity Effects 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FBYUNLMTXMFAQK-UHFFFAOYSA-N butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC.CCCCCCCCCCCC(=O)OCCCC FBYUNLMTXMFAQK-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はポジ型感光性アニオン電着塗料組成物に関し、
さらに詳しくは銅張積層板に電着塗装して粘着性のない
平滑な塗膜を形成し、且つポジを通して紫外線、で容易
に感光するプリント配線フォトレジスト形成に好適なア
ニオン電着塗料組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive photosensitive anionic electrodeposition coating composition,
More specifically, it relates to an anionic electrodeposition coating composition suitable for forming a printed wiring photoresist, which can be electrodeposited on a copper-clad laminate to form a smooth, non-adhesive coating film, and which is easily exposed to ultraviolet light through a positive. It is something.
従来、集Ｗｔ回路用などのプリント配線板は、一般に、
絶縁体に銅箔を張った積層板上に銅めっきを施し、その
上に感光性フィルムがラミネートされ、さらに写真ネガ
を重ねて露光および現像をしたのち、回路パターン以外
の不要の銅箔をエツチング処理し、しかる後感光性フィ
ルムを脱膜することによって形成されている。しかし、
この感光性フィルムは一般に５０μ麹と厚いなめに露光
、現像して形成される回路パターンがシャープでなく、
しかも銅箔面に均一にラミネートするのが困難であり、
特にスルーホール部分を被覆することは殆ど不可能であ
る。Conventionally, printed wiring boards for integrated Wt circuits are generally
Copper plating is applied to a laminated board with copper foil on an insulator, a photosensitive film is laminated on top of it, a photographic negative is layered, exposed and developed, and unnecessary copper foil other than the circuit pattern is etched. It is formed by processing and then removing the photosensitive film. but,
This photosensitive film is generally formed by exposing and developing a thick layer of 50μ koji, and the circuit pattern is not sharp.
Moreover, it is difficult to laminate uniformly on the copper foil surface.
In particular, it is almost impossible to cover the through-hole portions.
一方、プリント配線板の作成方式にネガ型フォトレジス
トとポジ型フォトレジストがある。すなわち、前者は光
照射により硬化する組成物を用い、未露光部分を溶解除
去せしめて現像する方法であり、後者はオルトキノンジ
アジド化合物などのごとく露光するとアルカリ水溶液な
どへの溶解性が増す化合物を用い、露光部分を溶解除去
して現像する方法である。この両方式において、前者は
露光量の弱い部分は硬化しに＜＜、特に、スルーホール
部にレジスト膜を設けるには強い光で長時間照射しなけ
ればならないので効率が悪く、スルホールの径が小さい
と硬化させることが困難である。On the other hand, methods for producing printed wiring boards include negative photoresist and positive photoresist. That is, the former method uses a composition that hardens upon light irradiation and develops by dissolving and removing the unexposed areas, while the latter method uses a compound such as an orthoquinone diazide compound that increases its solubility in an alkaline aqueous solution when exposed to light. , a method of developing by dissolving and removing the exposed area. In both of these methods, the former does not harden the areas where the exposure amount is weak, especially in order to form a resist film on the through-hole area, it must be irradiated with strong light for a long time, which is inefficient, and the diameter of the through-hole is If it is small, it is difficult to harden it.
一方、後者では未露光部がレジスト膜として残るので前
者に比ベスルーホール部へのレジスト膜の形成が容易で
あるが実用的にはまだ十分でなく、しかも画像の解像性
も十分とは言えず、しかも製造コストも高いなどの問題
点を有している。On the other hand, in the latter case, the unexposed area remains as a resist film, so it is easier to form a resist film on the through-hole area compared to the former, but it is still not sufficient for practical use, and the image resolution is not sufficient. Moreover, the manufacturing cost is high.
本発明は、プリント配線板を作成する際における前記し
た問題点を解消することを目的になされたものであり、
その結果、紫外線感光性に優れ、しかも鋼張積層板の表
面やスルーホール部に、現像可能な塗膜を均一に形成す
ることができるプリント配線ポジ型フォトレジスト形成
用アニオン電着塗料組成物を提供するものである。The present invention was made for the purpose of solving the above-mentioned problems when creating a printed wiring board,
As a result, we developed an anionic electrodeposition coating composition for forming a positive photoresist for printed circuits that has excellent ultraviolet sensitivity and is capable of uniformly forming a developable coating film on the surface of steel-clad laminates and through holes. This is what we provide.
而して、本発明に従えば
（ａ）１分子中に１個の重合性不飽和基と１個以上のウ
レタン結合を有する不飽和単量体に、オルトキノンジア
ジドスルホン酸及び／又はオルトナフトキノンジアジド
スルホン酸のハロゲン化物を反応せしめてなる不飽和単
量体
（ｂ）カルボキシル基含有不飽和単量体、リン酸基含有
不飽和単址体及びスルボン酸基含有不飽和嗅量体から選
ばれる１Ｆ！１または２種以上の不飽和単量体及び
（Ｃ）必要に応じて、モノエチレン性不飽和単量体
を共重合して得られるアクリル系アニオン樹脂を主成分
として含有することを特徴とするポジ型感光性アニオン
電着塗料組成物が提供される。According to the present invention, (a) orthoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide is added to the unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule. Unsaturated monomer formed by reacting a halide of sulfonic acid (b) 1F selected from carboxyl group-containing unsaturated monomers, phosphoric acid group-containing unsaturated monomers, and sulfonic acid group-containing unsaturated olfactory substances ! It is characterized by containing as a main component an acrylic anion resin obtained by copolymerizing one or more unsaturated monomers and (C) optionally a monoethylenically unsaturated monomer. A positive-working photosensitive anionic electrodeposition coating composition is provided.
本発明で用いられる（ａ）成分の不飽和単量体としては
、下記一般式（１）〜（ＩＩＩ）で表わされるものを挙
げることができる。Examples of the unsaturated monomer of component (a) used in the present invention include those represented by the following general formulas (1) to (III).
［式中、Ｒ３は水素原子またはメチル基を表わし、Ｒ７
は炭素数１〜２４個の直鎖または分岐鎖状のアルキレン
基もしくはアルキレンエーテル基を表わし、Ｒ１はジイ
ソシアネート化合物残基を表−Ｏ−Ｃ−Ｎ −Ｒ３−Ｎ
−Ｃ−ＯＲｓ又は−０−Ｃ−Ｎ−Ｒ，ＳをＩＩＩ
Ｉｌｌ ｌ１１ＯＲ，、Ｒ，ＯＯＲ
１
表わしくＲｉは炭素数１〜２０個のアルキル基、置換も
しくは未置換のフェニル基、シクロアルキル基、または
アラルキル基を表わす）、ｍは０〜５の整数を表わすコ
Ｉ
（式中、Ｒ，、Ｒ，、Ｒ８及びＲ４は前記の意味を表わ
し、Ｂは−Ｎ−Ｃ−ＯＲ５または
Ｒ，Ｏ
Ｎ Ｃ０−Ｆｔ２−０−Ｃ−Ｎ−Ｒｓを表わし、＋
１ ＩＩ ＋Ｒ４００Ｒ。[In the formula, R3 represents a hydrogen atom or a methyl group, and R7
represents a linear or branched alkylene group or alkylene ether group having 1 to 24 carbon atoms, and R1 represents a diisocyanate compound residue -O-C-N-R3-N
-C-ORs or -0-C-N-R,S III
Ill l11OR,,R,OOR
1 Ri typically represents an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a cycloalkyl group, or an aralkyl group), and m represents an integer of 0 to 5. ,, R,, R8 and R4 represent the above meanings, B represents -N-C-OR5 or R,O N C0-Ft2-0-C-N-Rs, +
1 II +R400R.
ｍは前記の意味を表わす） 青 。m represents the above meaning) Blue.
（式中、Ｒ＋ 、 Ｒ２、Ｒ４及びＲ５は前記の意味を
表わす）
前記（１）、（Ｉ［）及び（ＩＩＩ）式で表されるオル
トキノンジアジド基含有不飽和単量体（ａ）は、１分子
中に１個の重合性不飽和基と１個以上のウレタン結合を
有する不飽和単量体にオルトベンゾキノンジアジドスル
ホン酸及び／又はオルトナフトキノンジアジドスルホン
酸のハロゲン化物（好ましくは塩化物）を縮合付加反応
することにより得ることができる。(In the formula, R+, R2, R4 and R5 have the above meanings) The orthoquinonediazide group-containing unsaturated monomer (a) represented by the formulas (1), (I[) and (III) above, A halide (preferably a chloride) of orthobenzoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide sulfonic acid is added to an unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule. It can be obtained by a condensation addition reaction.
重合性不飽和基とウレタン結合を有する不飽和単量体は
、前記一般式（Ｉ）、（ＩＩ ）及び（ＩＩ）式におけ
るＲ４が水素原子である化合物である。The unsaturated monomer having a polymerizable unsaturated group and a urethane bond is a compound in which R4 in the general formulas (I), (II) and (II) is a hydrogen atom.
前記式におけるＲ２は具体的には一〇 Ｈｔ ＣＨ２−
１ＣＨ２ＣＨ２ＣＨ２−１−ＣＨ，ＣＨ−１Ｈｊ
−ＣＨｚ ＣＨ２ＣＨ２ＣＨ２−１−ＣＨＣＨ２ＣＨｔ
−１ＣＨｓ
−ＣＨｔｃ ＨＣＲ２−１−ＣＨ２ＣＨ２ＣＨ２ＣＨ２
ＣＲ２−１ＣＨ，Ｉ
ＣＨ２ＣＨｚ ＣＨ２ＣＨ−ＣＨｔ ＣＨ２−１ＣＨ２
ＣＨ２０ＣＨｔＣＨｚ−１
ＣＨ２ＣＨ２ＣＲ２０ＣＨ２ＣＨ２ＣＲ２−１−ＣＨ２
ＣＨ−〇−ＣＨ，ＣＨ−１
Ｉ
ＣＨ，ＣＨ５
などを挙げることができこれらのうち、Ｒ２として特に
好適なものは−ＣＨ，ＣＨ，−１−ｃＨ。Specifically, R2 in the above formula is 10 Ht CH2-
1CH2CH2CH2-1-CH, CH-1Hj -CHz CH2CH2CH2-1-CHCH2CHt
-1CHs -CHtc HCR2-1-CH2CH2CH2CH2
CR2-1CH,I CH2CHz CH2CH-CHt CH2-1CH2
CH20CHtCHz-1 CH2CH2CR20CH2CH2CR2-1-CH2
Examples include CH-〇-CH, CH-1 I CH, CH5, etc. Among these, those particularly preferred as R2 are -CH, CH, -1-cH.
ＣＨ，ＣＨ２−１−ＣＨ２ＣＨ，ＣＨ２ＣＨ７−１また
、Ｒ１はジイソシアネート化合物の残基を表わし、ジイ
ソシアネート化合物としては、例えばヘキサメチレンジ
イソシアネート、リジンジイソシアネート、イソホロン
ジイソシアネート、１−リレンジイソシアネート、キシ
リレンジイソシアネート、ジフェニルメタンジイソシア
ネート、メチレンビスシクロヘキシルジイソシアネート
などの脂肪族系、芳香族系及び脂環族系ジイソシアネー
１〜を挙げることができ、これらのうち、リジンジイン
シアネート、イソホロンジイソシアネート、トリレイジ
イソシアネートが好適である。CH, CH2-1-CH2CH, CH2CH7-1 In addition, R1 represents a residue of a diisocyanate compound, and examples of the diisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1-lylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate. , methylene biscyclohexyl diisocyanate, and other aliphatic, aromatic and alicyclic diisocyanates 1 to 1. Among these, lysine diisocyanate, isophorone diisocyanate and tolyl diisocyanate are preferred.
また、Ｒ９はメチル基、エチル基、１０ビル基、ブチル
基、オクチル基、ステアリル基、シクロへキシル基、ｔ
ｅｒｔ−ブチルフェニル基、ベンジル基などを表わし、
好適にはメチル基、エチル基、プロピル基、ブチル基で
ある。In addition, R9 is a methyl group, an ethyl group, a 10-biru group, a butyl group, an octyl group, a stearyl group, a cyclohexyl group, a t
Represents ert-butylphenyl group, benzyl group, etc.
Preferred are methyl group, ethyl group, propyl group, and butyl group.
而して、重合性不飽和基とウレタン結合を有する不飽和
ｖ樋体の好適な具体例としては、例えば［４（ＣＨｚ）
Ｈ（ＣＨｓ）
ＨＩＩ
Ｈ（ＣＨｓ）
嘔
ＩＩ ＩＨ
ＨＯ０
Ｈ（ＣＨ，）
著
）（（ＣＨｊ）
ＣＨ２”Ｃ−Ｃ−０−ＣＨ２ＣＨ２Ｎ−Ｃ−〇−ＣＨ２
ＣＨ２ＣＨ２ＣＨｚ＋１’Ｈ１ｌ
Ｏ０
Ｈ（Ｃｌ（、）
■
Ｏ１
ＣＨ３
ＣＨ２Ｃ−Ｎ−Ｃ−０−ＣＨ２ＣＨ２ＣＨ２ＣＨ３Ｉ
Ｈｌｌ
ＣＨ３０
Ｈ（ＣＨ３）
Ｃｌ４２−Ｃ−Ｃ−０−ＣＨ２ＣＨ２−０−Ｃ−Ｎ−Ｃ
Ｈ２ＣＨ２ＣＨ２ＣＨ３ＩＩ １
１ １
０ ０Ｈ
Ｈ（ＣＨｓ）
ＣＨ３＝ＣＣＯＣＨ２ＣＨＣＨ３
００−Ｃ−Ｎ Ｃ）（２ＣＨｘＣＨ２ＣＨｚ Ｈ
Ｈ（ＣＨ，）
Ｏ０Ｈ
Ｈ（Ｃ１，）
ＯＯＨ
などを挙げることができる。Preferred specific examples of unsaturated v-shaped bodies having a polymerizable unsaturated group and a urethane bond include, for example, [4(CHz) H(CHs) HII H(CHs) 小II IH HO0 H(CH, ) ((CHj) CH2”C-C-0-CH2CH2N-C-〇-CH2
CH2CH2CHz+1'H1l O0 H(Cl(,) ■ O1 CH3 CH2C-N-C-0-CH2CH2CH2CH3I
Hll CH30 H(CH3) Cl42-C-C-0-CH2CH2-0-C-N-C
H2CH2CH2CH3II 1
Examples include 1 1 0 0H H(CHs) CH3=CCOCH2CHCH3 00-C-N C) (2CHxCH2CHz H H(CH,) OOH H(C1,) OOH.
前記した重合性不飽和基とウレタン結合を有する不飽和
単量体は、オルトベンゾキノンジアジドスルホン酸及び
／又はオルトナフトキノンジアジドスルホン酸のハロゲ
ンロ化物と縮合付加反応されて本発明で用いる不飽和単
量体（ａ＞を生成する０反応条件はジアゾ基の分解を防
ぐため６０℃以下及びアルコールや水分等が存在しない
状態で行なうのが好ましい。The unsaturated monomer having a polymerizable unsaturated group and a urethane bond as described above is subjected to a condensation addition reaction with a halide of orthobenzoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide sulfonic acid to obtain the unsaturated monomer used in the present invention. The reaction conditions for producing (a>) are preferably 60° C. or lower and in the absence of alcohol, water, etc. in order to prevent decomposition of the diazo group.
つぎに、不飽和単量体（Ｂ）として用いられるカルボン
酸基含有不飽和単量体、リン酸基含有不飽和ＩＩＬ量体
及びスルホン酸基含有不飽和単量体としては、（メタ）
アクリル酸、２−（メタ）アクリロイルオキシエチルコ
ハク酸、２−（メタ）アクリロイルオキシエチルマレイ
ン酸、２−（メタ）アクロイルオキシエチルフタル酸、
２−（メタ）アクリロイルオキシエチルへキサヒドロフ
タル酸、β−カルボキシエチル（メタ）アクリレート、
２−（メタ）アクリロイルオキシエチルアシッドホスフ
ェート、２−（メタ）アクロイルオキシプロピルアシッ
ドホスフェート、（メタ）アクリロイルオキシプロパン
スルホン酸、ｔｅｒｔ−ブチルアクリルアミドスルホン
酸等があげられる。Next, the carboxylic acid group-containing unsaturated monomer, phosphoric acid group-containing unsaturated IIL polymer, and sulfonic acid group-containing unsaturated monomer used as the unsaturated monomer (B) are (meth)
Acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxyethyl phthalic acid,
2-(meth)acryloyloxyethyl hexahydrophthalic acid, β-carboxyethyl (meth)acrylate,
Examples include 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxypropanesulfonic acid, and tert-butylacrylamide sulfonic acid.
これらの中で、好適に用いられるものは、（メタ）アク
リル酸、２−〈メタ）アクリロイルオキシエチルアシッ
ドホスフェートである。Among these, (meth)acrylic acid and 2-(meth)acryloyloxyethyl acid phosphate are preferably used.
また、必要に応じて使用されるモノエチレン性不飽和啄
量体（Ｃ）としてはスチレン、メチル（メタ）アクリレ
ート、エチル（メタ）アクリレート、ブチル（メタ）ア
クリレート、２−エチルヘキシル（メタ）アクリレート
、ラウリル（メタ）アクリレート、ヒドロキシエチル（
メタ）アクリレート、ヒドロキシプロピル（メタ）アク
リレート、ウレタン結合含有（メタ）アクリレート等が
あげられる。Further, monoethylenically unsaturated polymers (C) used as necessary include styrene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, hydroxyethyl (
Examples include meth)acrylate, hydroxypropyl (meth)acrylate, and urethane bond-containing (meth)acrylate.
本発明のポジ型感光性アニオン電着資料組成物は前記し
た（ａ）〜（ｃ）の不飽和単量体を共重合して得られる
アクリル系アニオン樹脂を主成分とするものであるが、
このアクリル系樹脂は前記（ａ）〜（Ｃ）の不飽和単量
体を下記の割合で重合して得られるものである。（）内
は好適な範囲を示す。The positive photosensitive anionic electrodeposited material composition of the present invention is mainly composed of an acrylic anionic resin obtained by copolymerizing the unsaturated monomers (a) to (c) described above.
This acrylic resin is obtained by polymerizing the unsaturated monomers (a) to (C) described above in the proportions shown below. The numbers in parentheses indicate suitable ranges.
不飽和単量体（ａ）：５〜９８重量％
（２０〜７０重景％）
重量和単量体（ｂ）：２〜６０重皿％
（３〜４０重量％）
不飽和単量体（ｃ）：０〜９０重量％
（１０〜７０重量％）
かくして得られるアクリル系樹脂は、数平均分子量１，
０００〜１００，０００、好ましくは３．０００〜３０
，０００．酸価１０〜２５０、好適には２０〜６０、オ
ルトキノンジアジド基の含有量分子量１００当り０．０
４〜０．２０個、好ましくは０，０６〜０，１５個有す
るものである。Unsaturated monomer (a): 5-98% by weight (20-70% by weight) Weight sum monomer (b): 2-60% by weight (3-40% by weight) Unsaturated monomer ( c): 0 to 90% by weight (10 to 70% by weight) The acrylic resin thus obtained has a number average molecular weight of 1,
000-100,000, preferably 3.000-30
,000. Acid value 10-250, preferably 20-60, orthoquinonediazide group content 0.0 per 100 molecular weight
It has 4 to 0.20 pieces, preferably 0.06 to 0.15 pieces.
アクリル系樹脂の数平均分子量が１．０００以下の場合
電着塗装時に塗装された塗膜が破壊されやすく、均一な
塗膜が得られない、他方１０．０００以上の場合、電着
塗膜の平滑性が悪く凹凸の塗面となるため、画線の解像
性が劣る。If the number average molecular weight of the acrylic resin is less than 1.000, the paint film applied during electrodeposition will be easily destroyed and a uniform coating cannot be obtained. The painting surface has poor smoothness and is uneven, resulting in poor image resolution.
また酸価が１０未満の場合、水溶性もしくは水分散性に
することができず電着塗料組成物にならない、ｆｌ！！
方２５０を超えると電着塗料が基板に塗装され難くなり
、塗布址を多くするためには大きな電力を要する。If the acid value is less than 10, the electrodeposition coating composition cannot be made water-soluble or water-dispersible, and fl! !
If it exceeds 250, it becomes difficult for the electrodeposition paint to be applied to the substrate, and a large amount of electric power is required to increase the coating area.
また、オルトキノンジアジド基の含有呈が０゜０４個未
満であると光照射後の露光部のケテン鼠が少なく、依っ
てカルボン酸の量が少ないため、弱アルカリによる現像
が困難になる。他方０．２０個を超えると樹脂のガラス
転移温度（’Ｔ’ｇ）が高くなり、形成される電着塗膜
が硬くなるためヒビ割れをおこす。Furthermore, if the content of orthoquinonediazide groups is less than 0.04, there will be less ketene in the exposed area after irradiation with light, and therefore the amount of carboxylic acid will be less, making development with a weak alkali difficult. On the other hand, if the number exceeds 0.20, the glass transition temperature ('T'g) of the resin becomes high, and the electrodeposited coating film formed becomes hard and cracks occur.
本発明のポジ型アニオン電着塗料はオルトキノンジアジ
ド基及び酸基を含有する上記アクリル系樹脂をアミンも
しくはアルカリ化合物で中和し、水に分散もしくは溶解
することによって得られる。The positive-type anionic electrodeposition paint of the present invention can be obtained by neutralizing the above-mentioned acrylic resin containing an orthoquinone diazide group and an acid group with an amine or an alkali compound, and dispersing or dissolving it in water.
中和剤としては、たとえばモノエタノールアミン、ジェ
タノールアミン、トリエタノールアミン等のアルカノー
ルアミン類、トリエチルアミン、ジエチルアミン、モノ
エチルアミン、ジイソプロピルアミン、トリメチルアミ
ン、ジイソブチルアミン等のアルキルアミン類、ジメチ
ルアミノエタノール等のアルキルアルカノールアミン類
、ミクロヘキシルアミンなどの脂環族アミン類、カセイ
ソーダ、カセイカリ等のアルカリ金属水酸化物、アンモ
ニア等があり、これらは単独または混合物として使用で
きる。Examples of neutralizing agents include alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; and alkyl amines such as dimethylaminoethanol. Examples include alkanolamines, alicyclic amines such as microhexylamine, alkali metal hydroxides such as caustic soda and caustic potash, and ammonia, and these can be used alone or as a mixture.
本発明において、水溶化または水分散化した電着塗料の
流動性をさらに向上させるために親水性溶剤（たとえば
イソプロパツール、ｎ−ブタノール、ｔ−ブタノール、
メトキシエタノール、エトキシエタノール、ブトキシェ
タノール、ジエチレングリコール、メチルエーテル、ジ
オキサン、テトラヒドロフランなど）を加えることがで
きる。In the present invention, hydrophilic solvents (such as isopropanol, n-butanol, t-butanol,
methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane, tetrahydrofuran, etc.).
親水性溶剤の使用量はアクリル系樹脂１００重量部に対
し３００重量部以下の範囲が望ましい。The amount of the hydrophilic solvent used is preferably 300 parts by weight or less per 100 parts by weight of the acrylic resin.
また、被塗物への塗布象を多くするため、疎水性溶剤（
たとえばｌ−ルエン、キシレン等の石油系溶剤、メチル
エチルケトン、メチルイソブチルケトン等のケトン類、
酢酸エチル、酢酸ブチル等のエステル類、２−エチルヘ
キシルアルコール等アルコール類など）も加えることが
できる。疎水性溶剤の使用蓋はアクリル系樹脂１００重
重部に対し２００重量部以下の範囲が望ましい。In addition, in order to increase the coating effect on the object to be coated, a hydrophobic solvent (
For example, petroleum solvents such as l-luene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone,
Esters such as ethyl acetate and butyl acetate, alcohols such as 2-ethylhexyl alcohol, etc.) can also be added. The amount of hydrophobic solvent used is preferably 200 parts by weight or less per 100 parts by weight of the acrylic resin.
さらに必要に応じて、上記アクリル系樹脂以外の樹脂を
配合して電着塗膜の性能を適宜調整することもでき、さ
らに染料や顔料なども添加することができる。Furthermore, if necessary, resins other than the above-mentioned acrylic resins can be blended to adjust the performance of the electrodeposition coating film, and dyes, pigments, etc. can also be added.
本発明のアニオン電着塗料を用いたプリント配線基板の
製造は次のようにして行なわれる。A printed wiring board using the anionic electrodeposition paint of the present invention is produced as follows.
上記オルトキノンジアジド基含有アニオン性アクリル樹
脂の中和物を主成分とするアニオン電着塗料浴をｐＨ５
〜１０、浴濃度（固形分濃度）３〜３０重藍％、好まし
くは５・〜１５重量％、浴温度１５〜４０℃、好適には
１５〜３０℃に管理する。ついで、この電着塗料浴に、
銅箔を張った絶縁板に銅めっきを施してなる１リント配
線基板を陽極として浸漬し、２０〜４００Ｖの直流電流
を通電することによって行なわれる。通電時間は３０秒
〜５分が適当であり、膜厚は乾燥膜厚で２〜１００μｍ
、好適には３〜２０μｍであることが望ましい。An anionic electrodeposition paint bath containing a neutralized product of the above-mentioned orthoquinone diazide group-containing anionic acrylic resin as a main component was prepared at a pH of 5.
-10, bath concentration (solid content concentration) 3-30% by weight, preferably 5-15% by weight, bath temperature 15-40°C, preferably 15-30°C. Then, in this electrodeposition paint bath,
A one-lint wiring board made of an insulating board covered with copper foil and plated with copper is immersed as an anode, and a DC current of 20 to 400 V is applied. Appropriate current application time is 30 seconds to 5 minutes, and the dry film thickness is 2 to 100 μm.
, preferably 3 to 20 μm.
電着塗装後、電着浴から被塗物を引き上げ水洗機したの
ち、電着塗膜中に含まれる水分が熱風などで除去される
。After electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed in water, and then the moisture contained in the electrodeposition coating is removed with hot air or the like.
ついで、このように形成された感光性電着塗膜面にパタ
ーンマスク（写真ポジ）を重ねてから導体回路（回路パ
ターン）以外の不要部分のみに紫外線などの活性光線を
照射露光する。この露光部分中オルトキノンジアジド化
合物がケテンを経てカルボン酸となるため、アルカリ水
溶液などの現像液の現像処理によって除去され、貰解像
度を実現できる。Next, a pattern mask (photographic positive) is placed on the surface of the photosensitive electrodeposition coating film thus formed, and only unnecessary parts other than the conductor circuit (circuit pattern) are exposed to active light such as ultraviolet rays. Since the orthoquinone diazide compound in this exposed area becomes a carboxylic acid via ketene, it is removed by a developing process using a developer such as an alkaline aqueous solution, thereby realizing an image resolution.
本発明において露光に使用する活性光線は３０００〜４
５００人の波長を有する光線がよい、これらの光源とし
て太陽光、水銀灯、クセノンランプ、アーク灯などがあ
る。活性光線の照射は通常、１秒〜２０分の範囲で行な
われる。In the present invention, the active light rays used for exposure are 3000 to 4
Light having a wavelength of about 500 nm is preferred; these light sources include sunlight, mercury vapor lamps, xenon lamps, arc lamps, etc. Irradiation with actinic rays is usually carried out for a period of 1 second to 20 minutes.
また、現懺処理は塗膜面上に弱アルカリ水を吹きつける
ことによって塗膜の感光部分を洗い流すことによって行
なわれる０弱アルカリ水は通常ｐ Ｈ８〜１０のカセイ
ソーダ、炭酸ソーダ、カセイカリ、アンモニア水など塗
膜中に有する遊離のカルボン酸と中和して水溶性な与え
ることのできるものが使用可能である。In addition, the present printing process is carried out by spraying weakly alkaline water onto the coating surface to wash away the photosensitive areas of the coating.The weakly alkaline water is usually made of caustic soda, soda carbonate, caustic potash, or ammonia water with a pH of 8 to 10. It is possible to use compounds that can neutralize the free carboxylic acid present in the coating film to make it water-soluble.
ついで、現像処理によって基板上に露出しな銅箔部分（
非回路部分）は例えば、塩化第２鉄溶液等を用いた通常
のエツチング処理によって除去される。しかる後、回路
パターン上の未露光塗膜もエチルセロソルブ、エチルセ
ロソルブアセテートなどのセロソルブ系溶剤、トルエン
、キシレンなどの芳香族炭化水素系溶剤、メチルエチル
ケトン、メチルイソブチルケトンなどのケトン系溶剤、
酢酸エチル、酢酸ブチルなどの酢酸エステル系溶剤、ト
リクロルエチレンなどのクロル系溶剤またはｐ Ｈ１２
以上のカセイソーダ、カセイカリなどによって溶解除去
されて基板上にプリント回路が形成される。Next, the exposed copper foil portion (
The non-circuit portions) are removed by a conventional etching process using, for example, a ferric chloride solution. After that, the unexposed coating film on the circuit pattern is also treated with cellosolve solvents such as ethyl cellosolve and ethyl cellosolve acetate, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone,
Acetate ester solvents such as ethyl acetate and butyl acetate, chlorine solvents such as trichlorethylene, or pH 12
The above-mentioned caustic soda, caustic potash, and the like are dissolved and removed to form a printed circuit on the substrate.
［作 用］
本発明のポジ型感光性アニオン電着塗料は鋼箔上に容易
にアニオン電着塗装でき、析出した塗膜４乾燥されて均
一な感光膜を形成する。この感光膜に弘ポジフィルムを
通して光照射すると、露光部は前記のごとく変化して弱
アルカリ水によって現像され、また未露光部も溶剤また
は強アルカリによって溶解除去することができるので、
従来の感光性フィルムと置き換えることができる。[Function] The positive-type photosensitive anionic electrodeposition paint of the present invention can be easily anionically electrodeposited onto steel foil, and the deposited coating film 4 is dried to form a uniform photoresist film. When this photosensitive film is irradiated with light through a positive film, the exposed areas change as described above and are developed with weak alkaline water, and the unexposed areas can also be dissolved and removed with a solvent or strong alkali.
Can replace traditional photosensitive film.
特に、本発明の電着塗料はスルーホールを有するプリン
ト基板の製造に最適であり、感光性ドライフィルムを使
用した場合に比ベハンダメッキ工程などがなくなり、プ
リント基板製造工程を短縮することができる。また光硬
化型電着塗料では小さな径のスルーホールに硬化膜を形
成するのは困難であるが、本発明では未露光部がレジス
ト膜として残るので小さな径を有するプリント基板の製
造にも適している。In particular, the electrodeposition paint of the present invention is optimal for manufacturing printed circuit boards having through-holes, and when a photosensitive dry film is used, there is no need for a solder plating process, and the printed circuit board manufacturing process can be shortened. In addition, it is difficult to form a cured film on small-diameter through-holes with photocurable electrodeposition paint, but with the present invention, the unexposed areas remain as a resist film, making it suitable for manufacturing printed circuit boards with small diameters. There is.
次に、本発明に関する実施例について説明する。Next, examples related to the present invention will be described.
実施例中の部及び％はそれぞれ重量部及び重量％である
。Parts and percentages in the examples are parts by weight and percentages by weight, respectively.
） 量 １の ゝ
４つロフラスコに２−ヒドロキシエチルアクリレート１
１６部、ブチルイソシアネート９９部を入れ７０℃に昇
温し５時間撹拌しながら保ち、イソシアネート価が０に
なるのを確認した後、温度を４０℃に下げた。ついで、
ジオキサン１００部、トリエチルアミン１０１部を入れ
た後、オルトナフトキノンジアジドスルホン酸クロライ
ド２６９部をジオキサン８００部に溶かした溶液を１時
間かけて滴下したのち、４０℃で３時間保った。) Amount: 1 2-Hydroxyethyl acrylate in a 4-hole flask
16 parts of butyl isocyanate and 99 parts of butyl isocyanate were added thereto, the temperature was raised to 70°C, and the temperature was maintained with stirring for 5 hours. After confirming that the isocyanate value became 0, the temperature was lowered to 40°C. Then,
After adding 100 parts of dioxane and 101 parts of triethylamine, a solution of 269 parts of orthonaphthoquinonediazide sulfonic acid chloride dissolved in 800 parts of dioxane was added dropwise over 1 hour, and then maintained at 40°C for 3 hours.
この溶液を脱イオン水中に入れ反応物を沈殿させた。沈
殿物を減圧乾燥器に入れ溶媒を除去し、オルトキノンジ
アジド基含有不飽和単量体を得た。This solution was placed in deionized water to precipitate the reactants. The precipitate was placed in a vacuum dryer and the solvent was removed to obtain an unsaturated monomer containing an orthoquinonediazide group.
玉熟：ｌ（］ ［Ｃ２Ｏ繁漢２
４つ目フラスコにイソホロンジイソシアネート２２２部
を入れ、８０℃昇温し、撹拌しなから２−ヒドロキシエ
チルアクリレート１１６部を２時間かけて滴下した後、
８０℃で５時間保った。次にｎ−ブチルアルコール７４
部、ジブチルジラウレート０．０４部を入れ、３時間保
ちインシアネート価が０になるのを確認した後、ジオキ
サン２００部を入れ温度を４０℃に下げた。ついでトリ
エチルアミン１０１部を入れた後、オルトナフトキノン
ジアジドスルホン酸クロライド４０４部をジオキサン２
２４８部中に溶かした溶液を２時間かけて滴下した後４
０℃で３時間保った。Yushu: l(] [C2O Flowing Han 2 Put 222 parts of isophorone diisocyanate into the fourth flask, raise the temperature to 80°C, and dropwise add 116 parts of 2-hydroxyethyl acrylate over 2 hours without stirring.
It was kept at 80°C for 5 hours. Next, n-butyl alcohol 74
After adding 0.04 parts of dibutyl dilaurate and keeping it for 3 hours to confirm that the incyanate value became 0, 200 parts of dioxane was added and the temperature was lowered to 40°C. Then, after adding 101 parts of triethylamine, 404 parts of orthonaphthoquinonediazide sulfonic acid chloride was added to 2 parts of dioxane.
After dropping the solution dissolved in 248 parts over 2 hours, 4
It was kept at 0°C for 3 hours.
この溶液を脱イオン水中に入れ反応物を沈殿させた。こ
の沈殿物を減圧乾燥器に入れ溶媒を除去し、オルトキノ
ンジアジド基含有不飽和単址体を得た。This solution was placed in deionized water to precipitate the reactants. This precipitate was placed in a vacuum dryer to remove the solvent to obtain an unsaturated monomer containing an orthoquinonediazide group.
実施例 １
４つ目フラスコにエチレングリコールモノエチルエーテ
ル６００部を入れ撹拌しながら６０℃に昇温した後、不
飽和単量体１を３８０部、メチルメタクリレート３００
部、ｎ−ブチルアクリレート２６０部、アクリル酸６０
部、アゾビスジメチルバレロニトリル５０部の混合溶液
を３時間がけて滴下し、１時間保った後、エチレングリ
コールモノメチルエーテル７０部、アゾビスジメチルバ
レロニトリル部の混合溶液を１時間かけて滴下し、さら
に２時間保ちポジ型感光性樹脂（酸価４５）を得た。Example 1 After putting 600 parts of ethylene glycol monoethyl ether into a fourth flask and raising the temperature to 60°C with stirring, 380 parts of unsaturated monomer 1 and 300 parts of methyl methacrylate were added.
parts, n-butyl acrylate 260 parts, acrylic acid 60 parts
A mixed solution of 70 parts of ethylene glycol monomethyl ether and 50 parts of azobisdimethylvaleronitrile was added dropwise over a period of 3 hours. The mixture was further kept for 2 hours to obtain a positive photosensitive resin (acid value: 45).
次で、この感光性樹脂溶液にトリエチルアミン４０部を
加えて十分に中和した後固形分が１５％になるように脱
イオン水を加えて電着塗装浴（ｐＨ７，２）とした。Next, 40 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 15% to prepare an electrodeposition coating bath (pH 7.2).
実施例 ２
４つ目フラスコにエチレングリコールモノエチルエーテ
ル６００部を入れ撹拌しながら６０℃に昇温した後、不
飽和単量体１を３８０部、メチルメタクリレート２００
、ｎ−ブチルアクリレート２４０．２−メタロロイルオ
キシエチルアシッドホスフェート１６０部、アゾビスジ
メチルバレロニトリル５０部の混合溶液を３時間かけて
滴下し、１時間保った後、エチレングリコールモノメチ
ルエーテル７０部、アゾビスジメチルバレロニトリル５
部の混合溶液を１時間かけて滴下し、さらに２時間保ち
ポジ型感光性樹脂（酸価４４）を得た。Example 2 600 parts of ethylene glycol monoethyl ether was placed in a fourth flask and the temperature was raised to 60°C with stirring, followed by 380 parts of unsaturated monomer 1 and 200 parts of methyl methacrylate.
A mixed solution of 240 parts of n-butyl acrylate, 160 parts of 2-metalloloyloxyethyl acid phosphate, and 50 parts of azobisdimethylvaleronitrile was added dropwise over 3 hours, and after keeping for 1 hour, 70 parts of ethylene glycol monomethyl ether and 160 parts of azobisdimethylvaleronitrile were added dropwise. Bisdimethylvaleronitrile 5
A mixed solution of 50% was added dropwise over 1 hour, and the mixture was kept for an additional 2 hours to obtain a positive photosensitive resin (acid value: 44).
次で、この感光性樹脂溶液にトリエチルアミン４０部を
加えて十分に中和した後、固形分が１５％になるように
脱イオン水を加えて電着塗装浴（ｐＨ７，３）とした。Next, 40 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 15% to prepare an electrodeposition coating bath (pH 7.3).
実施例 ３
４つ目フラスコにメチルイソブチルケトン４００部を入
れ撹拌しながら８０℃に昇温した後、２−ヒドロキシエ
チルアクリレート１モルとブチルイソシアネート１モル
の付加物２８０部、メチルアクリレート４００部、アク
リル酸５０部、アゾビスイソブチルニトリル３５部の混
合溶液を３時間かけて滴下し、１時間保った後、メチル
イソブチルケトン８０部、アゾビスジメチルバレロニト
リル１０部の混合溶液を１時間かけて滴下し、２時間保
った後、４０℃に温度を下げる。さらに、オルトキノン
ジアジドスルホン酸クロライド２７０部、ジオキサン６
３０部の混合溶液を２時間かけて滴下し、２時間保ちポ
ジ型感光性樹脂（酸価３８）を得た。Example 3 400 parts of methyl isobutyl ketone was placed in a fourth flask and the temperature was raised to 80°C with stirring, followed by 280 parts of an adduct of 1 mole of 2-hydroxyethyl acrylate and 1 mole of butyl isocyanate, 400 parts of methyl acrylate, and acrylic. A mixed solution of 50 parts of acid and 35 parts of azobisisobutylnitrile was added dropwise over 3 hours, kept for 1 hour, and then a mixed solution of 80 parts of methyl isobutyl ketone and 10 parts of azobisdimethylvaleronitrile was added dropwise over 1 hour. After holding for 2 hours, lower the temperature to 40°C. Furthermore, 270 parts of orthoquinonediazide sulfonic acid chloride, 6 parts of dioxane
30 parts of the mixed solution was added dropwise over 2 hours and kept for 2 hours to obtain a positive photosensitive resin (acid value: 38).
次で、この感光性樹脂溶液にエチレングリコールモノメ
チルエーテル２００部、ジメチル゛エタノールアミン６
０部を加えて十分に中和した後、固形分が１５％になる
ように脱イオン水を加えて電着塗装浴（ｐＨ７，５）と
しな。Next, 200 parts of ethylene glycol monomethyl ether and 6 parts of dimethyl ethanolamine were added to this photosensitive resin solution.
After sufficiently neutralizing by adding 0 parts, deionized water was added so that the solid content was 15% to form an electrodeposition coating bath (pH 7.5).
実施例 ４
４つロフラスコにエチレングリコールモノエチルエーテ
ル６００部を入れ撹拌しながら５０℃に昇温した後、不
飽和単量体２を４４０部、エチルアクリレート５００部
、アクリル酸６０部、アゾビスメトキシジメチルバレロ
ニトリル５０部の混合溶液を３時間かけて滴下し、１時
間保った後、エチレングリコールモノエチルエーテル７
０部、アゾビスメトキシジメチルバレロニトリル５部の
混合溶液を１時間かけて滴下し、さらに２時間保ぢポジ
型感光性樹脂（酸価４５）を得た。Example 4 600 parts of ethylene glycol monoethyl ether was placed in a four-bottle flask and the temperature was raised to 50°C with stirring, followed by 440 parts of unsaturated monomer 2, 500 parts of ethyl acrylate, 60 parts of acrylic acid, and azobismethoxy. A mixed solution of 50 parts of dimethylvaleronitrile was added dropwise over 3 hours, and after keeping for 1 hour, ethylene glycol monoethyl ether 7
A mixed solution of 0 parts of azobismethoxydimethylvaleronitrile and 5 parts of azobismethoxydimethylvaleronitrile was added dropwise over 1 hour, and maintained for another 2 hours to obtain a positive type photosensitive resin (acid value: 45).
次で、この感光性樹脂溶液に酢酸２５部を加えて十分に
中和した後、固形分が１０％になるように脱イオン水を
加えて電着塗装浴（ｐＨ７，２）とした。Next, 25 parts of acetic acid was added to this photosensitive resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 10% to prepare an electrodeposition coating bath (pH 7.2).
実施例 ５
オルトナフトキノンジアジドスルホン酸クロライド８１
部、ノボラック樹脂３３部、ジオキサン６５０部、トリ
エチルアミン３２部の混合液を撹拌しながら４０℃に昇
温し、５時間保つ、次にこの溶液を脱イオン水中に入れ
反応物を沈殿させた。Example 5 Orthonaphthoquinonediazide sulfonic acid chloride 81
A mixed solution of 33 parts of novolak resin, 650 parts of dioxane, and 32 parts of triethylamine was heated to 40° C. with stirring and maintained for 5 hours, and then the solution was poured into deionized water to precipitate the reactants.
沈殿物を減圧乾燥器に入れ溶媒を除去し、オルトキノン
ジアジド基含有ノボラック樹脂を得た。The precipitate was placed in a vacuum dryer to remove the solvent to obtain an orthoquinonediazide group-containing novolac resin.
このノボラック樹脂１００部を実施例１の感光性樹脂溶
液１７００部に混合した。100 parts of this novolak resin was mixed with 1700 parts of the photosensitive resin solution of Example 1.
次でこの感光性樹脂にトリエチルアミン４０部を加えて
十分に中和した後、固形分が１５％になるように説イオ
ン水を加えて電着塗装浴（ＰＨ７゜１）とした。Next, 40 parts of triethylamine was added to this photosensitive resin to sufficiently neutralize it, and then ionized water was added so that the solid content was 15% to prepare an electrodeposition coating bath (PH7.1).
実施例 ６
実施例１の感光性樹脂溶液１７００部にノボラックフェ
ノール樹脂１００部を溶解混合した。Example 6 100 parts of novolak phenol resin was dissolved and mixed in 1700 parts of the photosensitive resin solution of Example 1.
次で、この感光性樹脂溶液にジメチルエタノールアミン
５５部を加えて十分に中和した後、固形分が１０％にな
るように脱イオン水を加えて電着塗装浴（ｐＨ７，２）
とした。Next, 55 parts of dimethylethanolamine was added to this photosensitive resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 10% to create an electrodeposition coating bath (pH 7.2).
And so.
応用例
実施例１〜６で得た各々の電着塗装浴にスルーホールの
あるプリント配線用銅張積層板（２４０ｘ１７Ｑｘ１．
５ｍ＋）を陽極として浸漬し、浴温２５℃で１００Ｖの
直流電流を３分間通電して電着塗装した。塗膜を水洗し
、５０℃で５分間乾燥して厚さ５μの粘着性のない平滑
な感光膜を形成した。ついで、ポジフィルムを真空装置
でこの電着塗面に密着させ、３ＫＷの超高圧水銀灯を用
いて、両面とも１５０１１Ｊ／ｃＩ１１２ずつ照射した
。次に露光部を０．１％炭酸ソーダ水溶液で洗い出し現
像を行ない、水洗後（塩化第２鉄溶液）で銅箔をエツチ
ング処理して除去し、ついで未露光部をエチレングリコ
ールモノエチレンエーテル溶剤で収り除くことによって
、スルーホール部にも銅箔がついているきれいなシャー
プなパターンのプリント回路板が得られた。Application Examples Copper-clad laminates for printed wiring (240x17Qx1.
5m+) was immersed as an anode, and a 100V DC current was applied for 3 minutes at a bath temperature of 25°C for electrodeposition coating. The coating film was washed with water and dried at 50° C. for 5 minutes to form a smooth, non-adhesive photosensitive film with a thickness of 5 μm. Then, a positive film was brought into close contact with the electrodeposited surface using a vacuum device, and both surfaces were irradiated with 15011 J/cI112 using a 3 KW ultra-high pressure mercury lamp. Next, the exposed areas were washed with a 0.1% sodium carbonate aqueous solution and developed. After washing with water (ferric chloride solution), the copper foil was etched and removed, and the unexposed areas were etched with ethylene glycol monoethylene ether solvent. By removing the copper foil, a printed circuit board with a clean, sharp pattern was obtained, with copper foil also attached to the through holes.
Claims (1)
のウレタン結合を有する不飽和単量体に、オルトベンゾ
キノンジアジドスルホン酸及び／又はオルトナフトキノ
ンジアジドスルホン酸のハロゲン化物を反応せしめてな
る不飽和単量体 （ｂ）カルボキシル基含有不飽和単量体、リン酸基含有
不飽和単量体及びスルホン酸基含有不飽和単量体から選
ばれる１種または２種以上の不飽和単量体及び （ｃ）必要に応じて、モノエチレン性不飽和単量体 を共重合して得られるアクリル系アニオン樹脂を主成分
として含有することを特徴とするポジ型感光性アニオン
電着塗料組成物。[Claims] 1. (a) An unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule, orthobenzoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide Unsaturated monomer obtained by reacting a halide of sulfonic acid (b) 1 selected from carboxyl group-containing unsaturated monomers, phosphoric acid group-containing unsaturated monomers, and sulfonic acid group-containing unsaturated monomers It is characterized by containing as a main component an acrylic anion resin obtained by copolymerizing a species or two or more unsaturated monomers and (c) optionally a monoethylenically unsaturated monomer. Positive type photosensitive anionic electrodeposition coating composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5414287A JPS63221177A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive anionic electrodeposition paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5414287A JPS63221177A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive anionic electrodeposition paint composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63221177A true JPS63221177A (en) | 1988-09-14 |
Family
ID=12962308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5414287A Pending JPS63221177A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive anionic electrodeposition paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63221177A (en) |
-
1987
- 1987-03-11 JP JP5414287A patent/JPS63221177A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2585070B2 (en) | Image forming method | |
| JPS62262856A (en) | Electrodeposition paint composition for photoresist of printed circuit | |
| JPH01121375A (en) | Positive-type photo-sensitive cationic electro-deposition paint composition | |
| AU613463B2 (en) | Electrodeposition coating process of photoresist for printed circuit board | |
| JP2749646B2 (en) | Positive photosensitive electrodeposition coating composition and method for producing circuit board using the same | |
| JP2804579B2 (en) | Positive photosensitive electrodeposition coating composition and method for producing circuit board using the same | |
| JPH0389353A (en) | Positive type photosensitive resin composition | |
| CA1334897C (en) | Electrodeposition coating composition and image-forming method using the same | |
| JP2847321B2 (en) | Positive photoresist composition | |
| JPS62262855A (en) | Electrodeposition paint composition for photoresist of printed circuit | |
| JPS63221177A (en) | Positive type photosensitive anionic electrodeposition paint composition | |
| JP4116342B2 (en) | Positive photosensitive coating composition, method for producing positive photosensitive resin, and pattern forming method | |
| JPH0473763A (en) | Photosetting composition for electrodeposition coating | |
| JPH0453877A (en) | Positive photosensitive electrodeposition coating composition | |
| JPS636070A (en) | Positive photosensitive electrodeposition coating | |
| JPS63221178A (en) | Positive type photosensitive cationic electrodeposition paint composition | |
| JPH07119375B2 (en) | Positive photosensitive anion electrodeposition coating composition | |
| JPH0643644A (en) | Negative photosensitive electrodeposition coating resin composition and production of electrodeposition bath and resist pattern using the composition | |
| JPH01122189A (en) | Electrodeposition paint composition for printed wiring board photo-resist | |
| JPH04198372A (en) | Positive type photosensitive anion electrodeposition coating composition | |
| JPH07278471A (en) | Positive photosensitive anionic electrodeposition coating composition and pattern formation by using the same | |
| JP2911958B2 (en) | UV curable electrodeposition coating composition | |
| JPH04198370A (en) | Positive type photosensitive cation electrodeposition coating composition | |
| JPH0659453A (en) | Positive photosensitive resin composition | |
| JPH03100073A (en) | Positive photosensitive electrodeposition coating resin composition |