JPS63221178A - Positive type photosensitive cationic electrodeposition paint composition - Google Patents
Positive type photosensitive cationic electrodeposition paint compositionInfo
- Publication number
- JPS63221178A JPS63221178A JP5414387A JP5414387A JPS63221178A JP S63221178 A JPS63221178 A JP S63221178A JP 5414387 A JP5414387 A JP 5414387A JP 5414387 A JP5414387 A JP 5414387A JP S63221178 A JPS63221178 A JP S63221178A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated monomer
- parts
- group
- sulfonic acid
- 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 37
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 20
- 239000003973 paint Substances 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000008199 coating composition Substances 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 claims 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 28
- 238000000576 coating method Methods 0.000 abstract description 28
- -1 sulfonic acid halide Chemical class 0.000 abstract description 18
- 239000004925 Acrylic resin Substances 0.000 abstract description 11
- 229920000178 Acrylic resin Polymers 0.000 abstract description 11
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 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
- 230000036211 photosensitivity Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 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
- 150000007522 mineralic acids Chemical class 0.000 description 2
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-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
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GVCPFNMXSFHJQQ-UHFFFAOYSA-N C(C)Cl.C(CO)O Chemical compound C(C)Cl.C(CO)O GVCPFNMXSFHJQQ-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
- 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 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
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009343 monoculture Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920003986 novolac Polymers 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
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003208 petroleum 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 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
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-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カチ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カチ
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 cationic electrodeposition coating composition,
More specifically, it relates to a cationic electrodeposition coating composition suitable for forming a printed wiring photoresist that can be electrocoated onto copper-clad laminates to form a smooth, non-adhesive coating and is easily exposed to ultraviolet light through a positive. It is.
従来、集積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つきを施し、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−と厚いために露光、
現像して形成される回路パターンがシャープでなく、し
かも鋼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 circuits and the like are generally made by applying copper plating to a laminate of insulators covered with copper foil, on top of which a photosensitive film is laminated, and then a photographic negative is layered and exposed to light. After development, unnecessary copper foil other than the circuit pattern is etched, and then the photosensitive film is removed. However, since this photosensitive film is generally as thick as 50 μ-
The circuit pattern formed by development is not sharp, and it is difficult to laminate the steel foil uniformly on the surface of the steel foil. 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ｌ−配線板を作成する際における６７
１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、しかも銅張積層
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
ト形成用カチオン電着塗料組成物を提供するものである
。The present invention provides a method for producing a pudding l-wiring board.
This was developed with the aim of solving the problems mentioned in 1. As a result, it has excellent ultraviolet sensitivity and forms a uniform developable coating film on the surface and through-hole areas of copper-clad laminates. The present invention provides a cationic electrodeposition coating composition for forming a positive photoresist for printed wiring.
即ち、本発明は、
（ａ）１分子中に１個の重合性不飽和基と１個以上のウ
レタン結合と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）アシン基含有不飽和単量体
（’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ビニル系カチ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カチオン電
着塗料組成物及び（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と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
反応せしめでなる不飽和単量体
（ｄ）グリシジル基含有不飽和単量体
（ｅ）必要に応じて、モノエチレン性不飽和単量体を共
重合して得られる共重合体にアシン化合物を反応せしめ
てなるビニル系カチ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カチオン電着塗料組成物に
関する。That is, the present invention provides: (a) an unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule; Unsaturated monomer obtained by reacting an acid halide (b) Unsaturated monomer containing an acine group ('c) Vinyl obtained by copolymerizing a monoethylenically unsaturated monomer as necessary A positive photosensitive cationic electrodeposition coating composition characterized by containing a cationic resin as a main component, and (a) having one polymerizable unsaturated group and one or more urethane bonds in one molecule. An unsaturated monomer obtained by reacting an unsaturated monomer with a halide of orthobenzoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide sulfonic acid (d) An unsaturated monomer containing a glycidyl group (e) If necessary Positive photosensitive cationic electrodeposition characterized by containing as a main component a vinyl cationic resin obtained by reacting an acine compound with a copolymer obtained by copolymerizing a monoethylenically unsaturated monomer. The present invention relates to coating compositions.
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）〜（ＩＩ）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 (II).
Ｒ。R.
１、式中、Ｒ１は水素原子またはメチル基を表わし、Ｒ
２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 −Ｒ、−
Ｎ −Ｃ−ＯＲ、又は−〇 −Ｃ−Ｎ −ＲｓをＩＩＩ
Ｉｌｌ ｌ１ｌＯＲ，Ｒ４００
Ｒ１
表わしくＲＳ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Ｏ〜５の整数を表わす］
（式中、Ｒ３、Ｒ２、Ｒ１及びＲ１は前記の意味を表わ
し、Ｂは−Ｎ−Ｃ−ＯＲ５または
ｌ ＩＩ
Ｒ，Ｏ
Ｎ ＣＯＲ２０ＣＮ−Ｒ３を表わし、ｌ ＩＩ
ＩＩ １Ｒ４０ＯＲ４
ｍは前記の意味を表わす）
Ｒ。1, where R1 represents a hydrogen atom or a methyl group, and R
2 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-R, -
N -C-OR, or -〇 -C-N -Rs as III
Ill l1lOR, R400
R1 represents an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a cycloalkyl group, or an aralkyl group), m represents an integer of O to 5] (wherein R3, R2, R1 and R1 have the above-mentioned meanings, B represents -N-C-OR5 or l II R, O N COR20CN-R3, l II
II 1R40OR4 m has the above meaning) R.
（式中、Ｒ１、Ｒ２、Ｒ４及びＲ２は前記の意味を表わ
す）
前記（１）、（ＩＩ）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址体（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ボン
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, R1, R2, R4 and R2 represent the above meanings) The orthoquinone diazide group-containing unsaturated monomer (a) represented by the formulas (1), (II) and (III) is 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 the 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（１）、（Ｉｆ＞及び（Ｉ［［）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 (1), (If> and (I[[)) is a hydrogen atom.
前記式におけるＲ３は具体的には−ＣＨ２ＣＨｔ−１Ｃ
ｆ（２ＣＨ２ＣＨ２−ｌ−ＣＨ２ＣＨ−１■
ＣＨ。R3 in the above formula is specifically -CH2CHt-1C
f(2CH2CH2-l-CH2CH-1■ CH.
ＣＨ２ＣＨ２ＣＨ２ＣＨｚ−５ＣＨＣＨｔ ＣＨ２−１
ＣＨ。CH2CH2CH2CHz-5CHCHt CH2-1
CH.
−ＣＨｔＣＨＣＨｔ−５−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｃ
Ｈｔ−５Ｈ３
−ＣＨ２ＣＨ２ＣＨ２ＣＨ，ＣＨ２ＣＨ２−１ＣＨ２Ｃ
Ｈｔ ０ ＣＨ２ＣＨｔ−１ＣＨｚＣＨｚＣＨｚ
ＯＣＨ２ＣＨ２ＣＨｘ−１ＣＨｚＣＨＯ−ＣＨ２Ｃ
Ｈ−１
ｌ
ＣＨ３ＣＨ。-CHtCHCHt-5-CH2CH2CH2CH2C
Ht-5H3 -CH2CH2CH2CH, CH2CH2-1CH2C
Ht 0 CH2CHt-1CHzCHzCHz
OCH2CH2CHx-1CHzCHO-CH2C
H-1 l CH3CH.
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−ＣＨ２ＣＨｔ−１−ＣＨ。Among these, -CH2CHt-1-CH is particularly preferred as R2.
ＣＨ２ＣＨ，−１ＣＨ２ＣＨ２ＣＨ２ＣＨ２−１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、インホロンジ
インシアネート、トリレンジイソシアネート、キシリレ
ンジイソシアネート、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トを
挙げることができ、これらのうち、リジンジイソシアネ
ート、イン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。CH2CH, -1CH2CH2CH2CH2-1 Also,
R1 represents a residue of a diisocyanate compound, and examples of the diisocyanate compound include aliphatic and aromatic compounds such as hexamethylene diisocyanate, lysine diisocyanate, inphorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and methylenebiscyclohexyl diisocyanate. Among them, lysine diisocyanate, inphorone diisocyanate, and trilay diisocyanate are preferred.
また、Ｒｓはメチル基、エチル基、プロピル基、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。Also, Rs is a methyl group, ethyl group, propyl group, butyl group, octyl group, stearyl group, cyclohexyl group, 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
単量体の好適な具体例としては、例えばＨ（ＣＨｊ）
ＩＩ
Ｈ（ＣＨ３）
Ｈ（ｃＨ，）
ＩＩ ＩＨ
ＨＯ０
＋ｔ（ＣＨ３）
■
Ｈ（ＣＨ，）
１１（ＣＩ＋、）
■
０ Ｈｌ
Ｈｓ
ｌ Ｈ１１
ＣＨ３０
Ｈ（ＣＨ３）
■
ｃＨ２＝Ｃ−Ｃ−０−ＣＨｚＣＨｉ−０−Ｃ−Ｎ−ＣＨ
ｚＣＨｚＣＨ，ＣＨ＋ＩＩ ＩＩ
１Ｈ（Ｃ１ｈ）
ＣＨ３＝ＣＣＯＣＨｚＣＨＣＨｓ
０ ０−Ｃ−Ｎ−ＣＨ２ＣＨ２ＣＨ２ＣＨ３
Ｈ
）１ （ＣＨ３）
Ｑ ＯＨＨ（ＣＨ，）
０ ０ Ｈなどを挙げ
ることができる。Preferred specific examples of unsaturated monomers having a polymerizable unsaturated group and a urethane bond include, for example, H(CHj) II H(CH3) H(cH,) II IH HO0 +t(CH3) ■ H(CH,) 11(CI+,) ■ 0 Hl Hs l H11 CH30 H(CH3) ■ cH2=C-C-0-CHzCHi-0-C-N-CH
zCHzCH,CH+II II
1H (C1h) CH3=CCOCHzCHCHs 0 0-C-N-CH2CH2CH2CH3
Examples include H )1 (CH3) Q OHH(CH,) 0 0 H.
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。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. Generate (a).
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。In order to prevent decomposition of the diazo group, the reaction conditions are preferably 60° C. or lower and in the absence of alcohol, moisture, etc.
本発明で用いられる（ｂ）成分の不飽和単量体としては
、下記した一般式（■）で表わされるものが挙げられる
。Examples of the unsaturated monomer of component (b) used in the present invention include those represented by the following general formula (■).
（式中、ｎは１〜６の整数、Ｒ２は水素原子又はメチル
基、Ｒ６及びＲ２は各々水素原子又は０１〜。(In the formula, n is an integer of 1 to 6, R2 is a hydrogen atom or a methyl group, and R6 and R2 are each a hydrogen atom or 01 to 6.
のアルキル基を表わす）で示される単量体であり、例え
ば、アミノエチル（メタ）アクリレート、Ｎ−ｔｅｒｔ
ブチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ
−ジメチルアミンエチル（メタ）アクリレート、Ｎ、Ｎ
−ジエチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ
−ジメチルアミノプロピル（メタ）アクリレート、Ｎ、
Ｎ−ジメチルアミノブチル（メタ）アクリレート等が挙
げられる。(representing an alkyl group), for example, aminoethyl (meth)acrylate, N-tert
Butylaminoethyl (meth)acrylate, N, N
-dimethylamine ethyl (meth)acrylate, N, N
-diethylaminoethyl (meth)acrylate, N, N
-dimethylaminopropyl (meth)acrylate, N,
Examples include N-dimethylaminobutyl (meth)acrylate.
中でも好ましくはＮ、Ｎ−ジメチルアミノエチル（メタ
）アクリレート、Ｎ、Ｎ−ジエチルアミノエチル（メタ
）アクリレート、Ｎ、Ｎ−ジメチルアミンプロピル（メ
タ）アクリレート、Ｎ、Ｎ−ジメチルアミノブチル（メ
タ）アクリレートである。Among them, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminepropyl (meth)acrylate, and N,N-dimethylaminobutyl (meth)acrylate are preferred. be.
また、必要に応じて使用されるモノエチレン性不飽和単
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−Ｉ・、
アクリルアシド、（メタ）アクリロニトリル、ビニルビ
ロリド、ビニルピリジン、ビニルピペリジン、ビニルキ
ノリン、ビニルイミダゾール等が挙げられる。In addition, as the monoethylenically unsaturated monomer (C) used as necessary, styrene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, hydroxyethyl (
meth)acrylate, hydroxypropyl (meth)acrylate, urethane bond-containing (meth)acrylate-I,
Acrylic acid, (meth)acrylonitrile, vinyl birolide, vinylpyridine, vinylpiperidine, vinylquinoline, vinylimidazole, and the like.
本発明のポジ型感光性カチオン電着塗料組成物で用いる
共重合体は不飽和単量体（ａ）、アミノ基合有不飽和単
蓋体（ｂ）及び必要に応じてモノエチレン性不飽和単殖
体（ｃ）を共重合反応させることにより製造することが
できる。The copolymer used in the positive photosensitive cationic electrodeposition coating composition of the present invention includes an unsaturated monomer (a), an unsaturated monocapsule (b) having an amino group, and, if necessary, a monoethylenically unsaturated monomer. It can be produced by copolymerizing monocultures (c).
本発明のポジ型感光性カチオン電着望料組成物は前記し
た（ａ）〜（ｃ）の不飽和単量体を共重合して得られる
アクリル系カチ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。０内は
好適な範囲を示す。The positive photosensitive cationic electrodeposition composition of the present invention is mainly composed of an acrylic cationic 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. Values within 0 indicate a suitable range.
不飽和単量体（ａ）：５〜９８重量％
（２０〜７０重量％）
不飽和単量体（ｂ）：２〜６０重量％
（３〜４０重量％）
不飽和単量体（ｃ）：０〜９０重量％
（１０〜７０重量％）
また、本発明のポジ型感光性カチオン電着塗料組成物で
用いる共重合体は前記したもの以外に前記した不飽和単
量体（ａ）、グリシジル基含有不飽和単量体（ｄ）及び
必要に応じてモノエチレン性不飽和単量体（Ｃ）を共重
合反応させてグリシジル基含有共重合体を得たのち、該
共重合体と第２級アミン化合物を反応させることによっ
ても製造することができる。Unsaturated monomer (a): 5-98% by weight (20-70% by weight) Unsaturated monomer (b): 2-60% by weight (3-40% by weight) Unsaturated monomer (c) :0 to 90% by weight (10 to 70% by weight) In addition to the above-described copolymers, the copolymers used in the positive-type photosensitive cationic electrodeposition coating composition of the present invention include the above-mentioned unsaturated monomers (a), After copolymerizing the glycidyl group-containing unsaturated monomer (d) and, if necessary, the monoethylenically unsaturated monomer (C) to obtain a glycidyl group-containing copolymer, the copolymer and It can also be produced by reacting a secondary amine compound.
グリシジル基含有不飽和単呈体（ｄ）としては、例えば
グリシジジル（メタ）アクリレート、グリシジジル（メ
タ）アクリルアミド、アリルグリシジルエーテル等が挙
げられる。Examples of the glycidyl group-containing unsaturated monomer (d) include glycidyl (meth)acrylate, glycidyl (meth)acrylamide, allyl glycidyl ether, and the like.
また、モノエチレン性不飽和単量体（ｃ）としては、グ
リシジル基と反応する基を有さないＡラジカル重合性の
単量体であれば特に制限されることなく使用できる６
更に、第２級アミン化合物としては、例えば、ジメチル
アミン、ジエチルアミン、ジ−Ｎ−プロピルアミン等の
低級ジアルキルアミン、ジェタノールアミン、ジイソプ
ロパツールアミン、Ｎ−メチルエタノールアミン等のジ
アルカノールアミンあるいはＮ−アルキルアルカノール
アミン、ピペリジン、モルホリン、Ｎ−メチルビペラジ
ン等のような環状アミンなどが挙げられる。In addition, as the monoethylenically unsaturated monomer (c), any A radical polymerizable monomer that does not have a group that reacts with a glycidyl group can be used without any particular restrictions6. Examples of the lower amine compounds include lower dialkylamines such as dimethylamine, diethylamine, and di-N-propylamine, dialkanolamines such as jetanolamine, diisopropanolamine, and N-methylethanolamine, or N-alkyl alkanols. Examples include cyclic amines such as amines, piperidine, morpholine, N-methylbiperazine, and the like.
本発明のポジ型感光性カチオン電着塗料組成物は前記し
た（ａ）、（ｄ＞及び（ｃ）の不飽和単量体を共重合し
て得られるアクリル系カチ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）、（ｄ）及
び（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。The positive photosensitive cationic electrodeposition coating composition of the present invention has as its main component an acrylic cationic resin obtained by copolymerizing the unsaturated monomers (a), (d>, and (c)) described above. However, this acrylic resin is obtained by polymerizing the unsaturated monomers (a), (d), and (C) in the following proportions.
０内は好適な範囲を示す。Values within 0 indicate a suitable range.
不飽和単量体（ａ）：５〜９８重量％
（２０〜７０重及％）
不飽和単量体（ｄ）：２〜６０重量％
（３〜４０重景％重
量飽和単量体＜Ｃ＞：Ｏ〜９０重量％
（１０〜７０重景％重
量くして得られるアクリル系樹脂は、数平均分子策１，
０００〜１００，０００、好ましくは３．０００〜３０
，０００、アミン価３０〜２５０、好適には４０〜１５
０、オルトキノンジアジド基の含有量、分子量１００当
り０．０４〜０゜２０個、好ましくは０．０６〜０．１
５個有するものである。Unsaturated monomer (a): 5-98% by weight (20-70% by weight) Unsaturated monomer (d): 2-60% by weight (3-40% by weight saturated monomer <C >:O to 90% by weight (10 to 70% by weight) The resulting acrylic resin has a number average molecular weight of 1,
000-100,000, preferably 3.000-30
,000, amine value 30-250, preferably 40-15
0, content of orthoquinonediazide groups, 0.04 to 0.20 per 100 molecular weight, preferably 0.06 to 0.1
It has 5 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＠膜が破壊されやずく、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１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 coated film will be destroyed during electrodeposition, making it impossible to obtain a uniform coating. On the other hand, if it is 10,000 or more, the smoothness of the electrodeposition coating film is poor and the coating surface is uneven, resulting in poor resolution of one image line.
またアミン価が３０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、他方
２５０を超えると電着塗料が基板に塗装され難くなり、
塗布量を多くするためには大きな電力を要する。If the amine value is less than 30, the electrodeposition coating composition cannot be made water-soluble or water-dispersible, and on the other hand, if it exceeds 250, the electrodeposition coating composition becomes difficult to coat on the substrate.
In order to increase the amount of coating, a large amount of electric power is required.
また、オルトキノンジアジド基の含有量が０゜０４個未
満であると光照射後の露光部のケテン量が少なく、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（Ｔｇ）が高くなり、形成される電＠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, the amount of ketene in the exposed area after irradiation with light is small, and therefore the amount of carboxylic acid is small, making development with a weak alkali difficult. On the other hand, if the number exceeds 0.20, the glass transition temperature (Tg) of the resin becomes high, and the formed coating film becomes hard and cracks occur.
本発明のポジ型カチオン電着塗料は上記アクリル系樹脂
中のアミノ基を有機酸もしくは無機酸で中和し、水に分
散もしくは溶解せしめることによって得られる。The positive cationic electrodeposition paint of the present invention can be obtained by neutralizing the amino groups in the acrylic resin with an organic or inorganic acid and dispersing or dissolving it in water.
中和に用いる有ｍ酸としては酢酸、乳酸、無機酸として
はリン酸などがあげられ、中和は０．１〜１．０当址の
範囲が好ましく、０．１当量より少なくなると水分散性
が低下した電着塗装が困難となり、１．０当量より多く
なると貯蔵安定性が劣るおそれがある。Examples of organic acids used for neutralization include acetic acid and lactic acid, and examples of inorganic acids include phosphoric acid. Neutralization is preferably in the range of 0.1 to 1.0 equivalents, and when it is less than 0.1 equivalents, water dispersion is performed. Electrodeposition coating with reduced properties becomes difficult, and if the amount exceeds 1.0 equivalent, storage stability may be poor.
本発明において、水溶化または水分散化した塗料の流動
性をさらに向上させるために親水性溶剤（たとえばイン
プロパツール、Ｔ１−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。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。In the present invention, in order to further improve the fluidity of the water-solubilized or water-dispersed paint, hydrophilic solvents (e.g., impropatol, T1-butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane, tetrahydrofuran, etc.). The amount of the hydrophilic solvent used is preferably 300 parts by weight or less per 100 parts by weight of the acrylic resin.
被塗物への塗布量を多くするため、疎水性溶剤（たとえ
ばトルエン、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
。疎水性溶剤の使用量はアクリル系樹脂１００重量部に
対し２００重叛部以Ｆの範囲が望ましい。In order to increase the amount of coating on the object, hydrophobic solvents (for example, petroleum solvents such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, 2-ethyl, Alcohols such as hexyl alcohol) can also be added. The amount of the hydrophobic solvent used is preferably in the range of 200 parts by weight or more per 100 parts by weight of the acrylic resin.
本発明のポジ型感光性カチオン電着塗料組成物には、必
要に応じて、例えばアクリル樹脂、フェノール樹脂、ポ
リウレタン樹脂などを配合して電着塗膜の性能を適宜調
整することもで！５゜本発明のポジ型感光性カチオン電
着塗料組成物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。If necessary, the positive photosensitive cationic electrodeposition coating composition of the present invention may contain, for example, an acrylic resin, phenol resin, polyurethane resin, etc. to adjust the performance of the electrodeposition coating film as appropriate! 5. A printed wiring board using the positive photosensitive cationic electrodeposition coating composition of the present invention is produced as follows.
上記アクリル系樹脂の中和物を主成分とするカチオン電
着塗料浴をｐＨ３〜９、浴濃度（固形分濃度）３〜３０
重厘％、好ましくは５〜１５重景％重量温度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
るプリント配線基板を陰極として浸漬し、２０〜４００
ｖ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、Ｊ１！厚は乾燥膜厚
で２〜１００μｍ、好適には３〜２０μｒｎであること
が望ましい。A cationic electrodeposition paint bath containing a neutralized product of the above acrylic resin as a main component has a pH of 3 to 9 and a bath concentration (solid content concentration) of 3 to 30.
Heavy weight %, preferably 5-15 heavy weight % weight temperature 15-40
The temperature is preferably controlled at 15-30°C. Next, a printed wiring board made of a copper-plated insulating board covered with copper foil was immersed in this electrodeposition paint bath as a cathode, and
This is done by passing a direct current of v. The appropriate energization time is 30 seconds to 5 minutes, and J1! The dry film thickness is preferably 2 to 100 μm, preferably 3 to 20 μrn.
電着塗装後、電着浴から被塗物を引き上げ水洗いしたの
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 with 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、高解像
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 aqueous alkaline solution, and high resolution can be achieved.
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にれらの光源として
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６
また、現像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。弱アルカリ水は通常カセイソーダ、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を与えることめできるも
のが使用可能である。In the present invention, the active light rays used for exposure are 3000 to 4
Light sources that emit light with a wavelength of about 500 people include sunlight, mercury lamps, xenon lamps, and arc lamps. Irradiation with actinic rays is usually carried out for a period of 1 second to 20 minutes.6 Development treatment is also carried out by spraying weak alkaline water onto the surface of the coating film to wash away the exposed areas of the coating film. The weak alkaline water that can be used is usually caustic soda, soda carbonate, caustic potash, or aqueous ammonia, which can neutralize free carboxylic acid present in the coating film and make it water-soluble.
ついで、現像処理によって基板上に露出しな鋼箔部分（
非回路部分）は例えば、水酸化アンモニウムと塩化アン
モニウムとの混合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 steel foil portion (
The non-circuit portions) are removed by a conventional etching process using, for example, a mixed solution of ammonium hydroxide and ammonium chloride. Thereafter, the unexposed coating film on the circuit pattern is 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, ethyl acetate, A printed circuit is formed on the board by dissolving and removing it with an acetate-based solvent such as butyl acetate or a chloro-based solvent such as trichloroethylene.
し作 用］
本発明のポジ型感光性アニオン電着塗料は銅箔上に容易
にカチオン電着塗装でき、析出した塗膜に乾燥されて均
一な感光膜を形成する。この感光膜にはポジフィルムを
通して光照射すると、露光部は前記のごと（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。Effect] The positive photosensitive anionic electrodeposition coating material of the present invention can be easily cationically electrodeposited onto copper foil, and the deposited coating film 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. Can be replaced.
特に、本発明の電着塗料はスルーポールを有するプリン
ト基板の製造にｆ＆速であり、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 f& speed for manufacturing printed circuit boards with through poles, and when a photosensitive dry film is used, there is no need for a solder plating process, etc.
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％はそれぞれ重呈部及び重量％である
。Parts and percentages in the examples are weight percentages and weight percentages, respectively.
■胞則浬ＪＪすＪす１１
４つ１コフラスコに２−ヒドロキシエチルアクリレート
１１６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、インシアネート価が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。116 parts of 2-hydroxyethyl acrylate and 99 parts of butyl isocyanate were placed in 4 flasks, heated to 70°C and kept under stirring for 5 hours until the incyanate value reached 0.
After confirming that the temperature was 40°C, the temperature was lowered to 40°C. Next, 100 parts of dioxane and 101 parts of triethylamine were added, and then 1 part of a solution of 269 parts of orthonaphthoquinonediazide sulfonic acid chloride dissolved in 800 parts of dioxane was added.
After dropping over a period of time, the solution was kept 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重電体を得た。This solution was placed in deionized water to precipitate the reactants. The precipitate was placed in a vacuum dryer to remove the solvent, thereby obtaining an unsaturated heavy electric material containing an orthoquinone diazide group.
徂用体」ゴ矢反カー
４つロフラスコにイン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２一ヒドロギシエ
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０次にｎ−ブチルアルコール７４
部、ジブチルチンジラウレート０．０４部を入れ、３時
間保ちイソシアネート価が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２２４８部中に溶かした溶液を２時間かけて滴下した
後４０℃で３時間保った。222 parts of inphorone diisocyanate was placed in a 4-car flask, heated to 80°C, and 116 parts of 2-hydroxyethyl acrylate was added dropwise over 2 hours without stirring.
Zero-order n-butyl alcohol 74 kept at 80°C for 5 hours
After adding 0.04 parts of dibutyltin dilaurate and keeping it for 3 hours to confirm that the isocyanate value became 0, 200 parts of dioxane was added and the temperature was lowered to 40°C. Next, 101 parts of triethylamine was added, and a solution of 404 parts of orthonaphthoquinonediazide sulfonic acid chloride dissolved in 2,248 parts of dioxane was added dropwise over 2 hours, and the mixture was kept 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。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ｌ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、
不飽和単景体１を３８０部、メチルメタクリレート２５
０部、ｎ−ブチルアクリレート２５０部、
、Ｎ、Ｎ−ジメチルアミノエチル
アクリレート１２０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エチルエーテル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（
アミン価４７）を得な。Example 1 600 parts of ethylene glycol monoethyl ether was placed in a fourth flask 1, and the temperature was raised to 60°C while stirring.
380 parts of unsaturated monomer 1, 25 parts of methyl methacrylate
0 parts, 250 parts of n-butyl acrylate,
A mixed solution of 120 parts of N,N-dimethylaminoethyl acrylate and 50 parts of azobisdimethylvaleronitrile was added dropwise over 3 hours and kept for 1 hour, followed by 70 parts of ethylene glycol monoethyl ether.
A mixed solution of 5 parts of azobisdimethylvaleronitrile was added dropwise over 1 hour, and the mixture was kept for an additional 2 hours.
Obtain an amine value of 47).
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（ｐＨ６，３）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 6.3).
実施例 ２
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６０℃に昇温した後、不
飽和単量体１を４００部、メチルアクリレート３８０部
、グリシジルメタクリレート１４５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エチルエ
ーテル７０部、アゾビスジメチルバレロニＩ・ツル５部
の混合溶液を１時間かけて滴下し、さらに２時間保った
後、ジエチルアミン７５部を加えて３時間保つことによ
り、ポジ型感光性樹脂（アミン価５７）を得た。Example 2 600 parts of ethylene glycol monoethyl ether was placed in a four-bottle flask and heated to 60°C with stirring, followed by 400 parts of unsaturated monomer 1, 380 parts of methyl acrylate, 145 parts of glycidyl methacrylate, and azobisdimethyl. A mixed solution of 50 parts of valeronitrile was added dropwise over 3 hours, kept for 1 hour, and then a mixed solution of 70 parts of ethylene glycol monoethyl ether and 5 parts of azobisdimethylvaleronitrile I was added dropwise over 1 hour. After keeping the mixture for another 2 hours, 75 parts of diethylamine was added and the mixture was kept for 3 hours to obtain a positive photosensitive resin (amine value: 57).
次で、この感光性樹脂溶液に酢酸３０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ｊｆｔ塗装浴（ｐＨ６，５）とした。Next, 30 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 electric JFT coating bath (pH 6.5).
実施例 ３
４つロ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Ｒ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、Ｎ、Ｎ−ジメチルアミノエチルメタ
アクリレート１４０部、ブチルアクリレ−１・３１０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、オルトナフトキノンジアジ
ドスルホン酸クロライド２７０部、ジオキサン６３０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（アミン価５０）を得た。Example 3 400 parts of methyl isobutyl ketone was placed in a four-bottle flask and heated 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, N,N-dimethylaminoethyl A mixed solution of 140 parts of methacrylate, 1.310 parts of butyl acrylate, and 35 parts of azobisisobutylnitrile was added dropwise over 3 hours, kept for 1 hour, and then mixed with 80 parts of methyl isobutyl ketone and 10 parts of azobisdimethylvaleronitrile. The solution was added dropwise over 1 hour and kept for 2 hours, then 40
Lower the temperature to ℃. Furthermore, a mixed solution of 270 parts of orthonaphthoquinonediazide sulfonic acid chloride and 630 parts of dioxane was added dropwise over 2 hours, and kept for 2 hours to obtain a positive photosensitive resin (amine value: 50).
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１５％になるように脱イオン水を
加えて電着塗装浴（ｐＨ６，２）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 15% to prepare an electrodeposition coating bath (pH 6.2).
実施例 ４
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５０℃に昇温した後、不
飽和単量体２を４４０部、ｎ−ブチルアクリレート４４
０部、Ｎ、Ｎ−ジメチルアミノエチルアクリレート１２
０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７０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時間保ちポジ型感光性樹脂（
アミン価４７）を得た。Example 4 After putting 600 parts of ethylene glycol monoethyl ether into a fourth flask and raising the temperature to 50°C with stirring, 440 parts of unsaturated monomer 2 and 44 parts of n-butyl acrylate were added.
0 parts, N,N-dimethylaminoethyl acrylate 12
A mixed solution of 0 parts of ethylene glycol monoethyl ether and 50 parts of azobismethoxydimethylvaleronitrile was added dropwise over 3 hours and kept for 1 hour. Add drops and keep for another 2 hours until positive photosensitive resin (
An amine value of 47) was obtained.
次で、この感光性樹脂溶液に酢酸２５部を力Ｕ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（ｐＨ６，３）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 6.3).
実施例 ５
エピコート１００１
（シェル化学製ビスフェ
ノールタイプエポキシ樹脂） ９５０重足部１″Ｉ
エチレングリコール
モノエチルエーテル ７００部エピコート１
００１のエチレングリコールモノエチルエーテル溶液を
５０℃に加熱し、同温度に保ちながら上記オルトキノン
ジアジド化合物を徐々に加えた後、１時間反応させてポ
ジ型感光性樹脂（アミン価６９）を得た。Example 5 Epicoat 1001 (Bisphenol type epoxy resin manufactured by Shell Chemical Co., Ltd.) 950 heavy foot portion 1″I Ethylene glycol monoethyl ether 700 parts Epicoat 1
The ethylene glycol monoethyl ether solution of No. 001 was heated to 50° C., and the above-mentioned orthoquinone diazide compound was gradually added while maintaining the same temperature, followed by reaction for 1 hour to obtain a positive photosensitive resin (amine value: 69).
この感光性樹脂溶液１４０部と実施例１の感光性樹脂溶
液１７００部を混合した。140 parts of this photosensitive resin solution and 1700 parts of the photosensitive resin solution of Example 1 were mixed.
次で、この感光性樹脂溶液に酢酸３０部を加えて十分に
中和した後、メチルイソブチルケトン５００部を加え、
固形分が１０％になるように脱イオン水を加えて電＠塗
装浴（ｐＨ６−１）とした。Next, 30 parts of acetic acid was added to this photosensitive resin solution to sufficiently neutralize it, and then 500 parts of methyl isobutyl ketone was added.
Deionized water was added so that the solid content was 10% to prepare an electrocoating bath (pH 6-1).
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酢酸２５部を加えて１−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（ｐＨ６，７）とした。Next, 25 parts of acetic acid was added to this photosensitive resin solution to neutralize it for 1 minute, and then deionized water was added so that the solid content was 10% to prepare an electrodeposition coating bath (pH 6, 7). .
応用例
実施例１〜６で得た各々の電着塗装浴にスルーポールの
あるプリント配線用銅張積層板（２４０Ｘ１７０ｘｌ、
５ｆｉ＋＋＋）を陰極として浸漬し、浴温２５°Ｃで１
００■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１５０ ｍ、Ｊ ／ ０ｍ２ず
つ照射した０次に露光部を１％炭酸ソーダ水溶液で洗い
出し現像を行ない、水洗後（水酸化アンモニウムと塩化
アンモニウムとの混合液）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
Ｉしμエーテル溶剤で取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 (240x170xl,
5fi+++) was immersed as a cathode, and the bath temperature was 25°C.
Electrodeposition coating was performed by applying a DC current of 0.00 mm for 3 minutes. 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. Next, a positive film was brought into close contact with the electrodeposited surface using a vacuum device, and both sides were irradiated with 150 m and J/0 m2 using a 3KW ultra-high pressure mercury lamp.The zero-order exposed area was washed out with a 1% aqueous solution of sodium carbonate. After developing and washing with water, the copper foil is removed by etching with a mixture of ammonium hydroxide and ammonium chloride, and the unexposed areas are removed with ethylene glycol monoethyl chloride and μ ether solvent to form through-holes. A printed circuit board with a clean sharp pattern was obtained, with copper foil also attached to the parts.
Claims (1)
のウレタン結合と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）アシノ基含有不飽和単量体 （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カチオン樹脂を主成分
として含有することを特徴とするポジ型感光性カチオン
電着塗料組成物。 ２、（ａ）１分子中に１個の重合性不飽和基と１個以上
のウレタン結合と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 （ｄ）グリシジル基含有不飽和単量体 （ｅ）必要に応じて、モノエチレン性不飽和単量体を共
重合して得られる共重合体にアシン化合物を反応せしめ
てなるアクリル系カチ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カチオン電着塗料組成物
。[Scope of Claims] 1. (a) An unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule, orthobenzoquinone diazide sulfonic acid and/or orthonaphtho Unsaturated monomer obtained by reacting a halide of quinonediazide sulfonic acid (b) Unsaturated monomer containing an acyno group (c) Obtained by copolymerizing a monoethylenically unsaturated monomer as necessary A positive photosensitive cationic electrodeposition coating composition containing an acrylic cationic resin as a main component. 2. (a) A halide of orthobenzoquinonediazide sulfonic acid and/or orthonaphthoquinonediazide sulfonic acid in an unsaturated monomer having one polymerizable unsaturated group and one or more urethane bonds in one molecule. (d) An unsaturated monomer containing a glycidyl group (e) If necessary, an acine compound is added to the copolymer obtained by copolymerizing a monoethylenically unsaturated monomer. 1. A positive photosensitive cationic electrodeposition coating composition containing as a main component an acrylic cationic resin obtained by reacting the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5414387A JPS63221178A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive cationic electrodeposition paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5414387A JPS63221178A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive cationic electrodeposition paint composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63221178A true JPS63221178A (en) | 1988-09-14 |
Family
ID=12962334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5414387A Pending JPS63221178A (en) | 1987-03-11 | 1987-03-11 | Positive type photosensitive cationic electrodeposition paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63221178A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709314A (en) * | 2013-12-25 | 2014-04-09 | 齐鲁工业大学 | Cationic acrylic resin for cathode electrophoretic coating, and preparation method of cationic acrylic resin |
-
1987
- 1987-03-11 JP JP5414387A patent/JPS63221178A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709314A (en) * | 2013-12-25 | 2014-04-09 | 齐鲁工业大学 | Cationic acrylic resin for cathode electrophoretic coating, and preparation method of cationic acrylic resin |
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