JP4302178B1 - Positive photosensitive anionic electrodeposition coating composition - Google Patents
Positive photosensitive anionic electrodeposition coating composition Download PDFInfo
- Publication number
- JP4302178B1 JP4302178B1 JP2008286540A JP2008286540A JP4302178B1 JP 4302178 B1 JP4302178 B1 JP 4302178B1 JP 2008286540 A JP2008286540 A JP 2008286540A JP 2008286540 A JP2008286540 A JP 2008286540A JP 4302178 B1 JP4302178 B1 JP 4302178B1
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- parts
- weight
- carboxyl group
- electrodeposition coating
- positive photosensitive
- Prior art date
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 75
- 239000008199 coating composition Substances 0.000 title claims abstract description 20
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 46
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- -1 polyphenol compound Chemical class 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 238000011161 development Methods 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 19
- 230000032683 aging Effects 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
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- 238000003756 stirring Methods 0.000 description 19
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- 238000004519 manufacturing process Methods 0.000 description 16
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 229960002887 deanol Drugs 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
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- 150000001450 anions Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 1
- WFNXYMSIAASORV-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)cyclohexyl]phenol Chemical compound OC1=CC=CC=C1C1(C=2C(=CC=CC=2)O)CCCCC1 WFNXYMSIAASORV-UHFFFAOYSA-N 0.000 description 1
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- 229960003280 cupric chloride Drugs 0.000 description 1
- CQAZHDHHROTUHL-UHFFFAOYSA-N cyclohexane;methanol;prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.C1CCCCC1 CQAZHDHHROTUHL-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-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
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000012972 dimethylethanolamine Substances 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
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- YGRMNBNGHHDGCX-UHFFFAOYSA-N n-(ethoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCNC(=O)C(C)=C YGRMNBNGHHDGCX-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/164—Coating processes; Apparatus therefor using electric, electrostatic or magnetic means; powder coating
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
【課題】液経時安定性が良好であり、且つ現像性、耐エッチング性等の回路形成能が良好なポジ型感光性アニオン電着塗料用組成物を提供すること。
【解決手段】（Ａ） 以下の（ａ）〜（ｃ）成分を用いて共重合することにより得られる、主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体 ６０〜９５重量部、
（ａ）置換基としてカルボキシル基を有する共重合性ビニル系単量体 ２〜１５重量部
（ｂ）（ａ）以外の共重合性ビニル系単量体 ８５〜９８重量部
（ｃ）カルボキシル基を有する連鎖移動剤 共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、０．０５〜１０重量部
（Ｂ） １分子につき、平均１から２個の感光性基を有する低分子感光剤 ５〜４０重量部
（Ｃ） 中和剤としての３級アミン （Ａ）成分のカルボキシル基１モルに対し、０．２〜０．９モルを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用組成物。
【選択図】なしDisclosed is a positive photosensitive anionic electrodeposition coating composition having good liquid aging stability and good circuit forming ability such as developability and etching resistance.
(A) A water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the end of the main chain, obtained by copolymerization using the following components (a) to (c): 60 to 95 Parts by weight,
(A) 2-15 parts by weight of a copolymerizable vinyl monomer having a carboxyl group as a substituent (b) 85-98 parts by weight of a copolymerizable vinyl monomer other than (a) (c) a carboxyl group Chain transfer agent having 0.05 to 10 parts by weight (B) of 1 to 2 photosensitive groups per molecule on the basis of a total of 100 parts by weight of the copolymerizable vinyl monomers (a) and (b) 5 to 40 parts by weight of a low molecular weight photosensitizer (C) A tertiary amine as a neutralizing agent (A) 0.2 to 0.9 moles per mole of carboxyl group of component (A) A composition for positive photosensitive anionic electrodeposition coating.
[Selection figure] None
Description
本発明は、液安定性、現像性、耐エッチング性に優れ、回路形成能が良好なポジ型感光性アニオン電着塗料用組成物、該ポジ型感光性アニオン電着塗料用組成物を電着塗装したリジット及びフレキシブルプリント基板及び該プリント基板から露光工程、現像工程等の所定の工程を経て得られるプリント配線板に関するものである。 The present invention relates to a composition for positive photosensitive anionic electrodeposition coating composition having excellent liquid stability, developability and etching resistance and good circuit forming ability, and electrodeposition of the positive photosensitive anionic electrodeposition coating composition. The present invention relates to a coated rigid and flexible printed circuit board and a printed wiring board obtained from the printed circuit board through predetermined processes such as an exposure process and a development process.
電子機器等に利用されるプリント基板は、レジスト材料によって回路パターンが形成されるが、近年、電子機器の小型化に対応して高密度・高精度が求められており、回路パターンの微細化が進んでいる。微細化への対応手法として、以前よりポジ型感光性電着レジストが提案されている。 Printed circuit boards used in electronic devices and the like have a circuit pattern formed of a resist material. Recently, high-density and high-accuracy have been demanded in response to downsizing of electronic devices. Progressing. As a countermeasure for miniaturization, a positive photosensitive electrodeposition resist has been proposed.
ポジ型電着レジスト組成物としては、種々提案されているが、非化学増幅型ポジ型電着レジスト組成物では、大きく分けて、(1)カルボキシル基含有樹脂に感光性官能基を導入
する方法（例えば、特許文献１）、(2)カルボキシル基を持たない樹脂と感光性官能基を
もつハロゲン化物を反応させた高分子感光剤とカルボキシル基含有樹脂をブレンドする方法（例えば、特許文献２）、(3)感光性官能基を持つハロゲン化物と不飽和基を持つ化合
物の反応により合成した感光性を有する不飽和モノマーとカルボキシル基含有不飽和モノマーを共重合する方法（例えば、特許文献３）、(4)カルボキシル基含有樹脂と感光剤を
ブレンドする方法（例えば、特許文献４）の４種類に、その技術内容から分類することができる。
Various positive electrodeposition resist compositions have been proposed, but non-chemically amplified positive electrodeposition resist compositions can be broadly divided into (1) a method of introducing a photosensitive functional group into a carboxyl group-containing resin. (For example, Patent Document 1), (2) A method of blending a carboxyl group-containing resin with a polymer photosensitive agent obtained by reacting a resin having no carboxyl group with a halide having a photosensitive functional group (for example, Patent Document 2) (3) A method of copolymerizing a photosensitive unsaturated monomer and a carboxyl group-containing unsaturated monomer synthesized by reacting a halide having a photosensitive functional group with a compound having an unsaturated group (for example, Patent Document 3) (4) A method of blending a carboxyl group-containing resin and a photosensitizer (for example, Patent Document 4) can be classified from the technical contents.
方法(1)、及び、(2)では、高分子と低分子の反応で反応効率が悪く、工程が煩雑であるだけでなくカルボキシル基を持つ樹脂では、副反応で樹脂がゲル化するため、使用は難しく、方法(3)では、感光性を有する不飽和モノマーの合成が煩雑であるだけでなく、コス
トアップになるので好ましくはない。このような背景から、方法(4)でポジ型電着レジス
ト組成物を作製する方法が技術的に有望である。
In the methods (1) and (2), the reaction efficiency is poor due to the reaction between the polymer and the low molecule, the process is complicated, and the resin having a carboxyl group is gelled by a side reaction. It is difficult to use, and the method (3) is not preferable because not only the synthesis of the unsaturated monomer having photosensitivity is complicated but also the cost is increased. From such a background, a method of producing a positive electrodeposition resist composition by the method (4) is technically promising.
しかしながら、方法(4)においても、カルボキシル基含有樹脂と感光剤の相溶性があま
りよくないために、感光剤が分離沈降し、感度を上げるために感光剤を増量することがこれまで困難であった。
この点を改良するため、アクリル樹脂等の改善が種々提案されているが（例えば、特許文献５）、アクリル樹脂製造工程が複雑になる問題があった。このように複雑な製造工程を用いず、液安定性が良好で、且つ現像性、耐エッチング性等の回路形成能が良好なポジ型感光性アニオン電着塗料用組成物は未だ見出せていなかった。
However, in the method (4), since the compatibility between the carboxyl group-containing resin and the photosensitizer is not so good, the photosensitizer is separated and settled, and it has been difficult to increase the photosensitizer in order to increase sensitivity. It was.
In order to improve this point, various improvements of acrylic resin and the like have been proposed (for example, Patent Document 5), but there has been a problem that the acrylic resin manufacturing process becomes complicated. There has not yet been found a composition for positive photosensitive anion electrodeposition coating composition that does not use such a complicated manufacturing process, has good liquid stability, and has good circuit forming ability such as developability and etching resistance. .
本発明は、前記したような従来技術における問題を解決し、複雑なアクリル樹脂製造工程を用いず、液経時安定性が良好であり、且つ現像性、耐エッチング性等の回路形成能が良好なポジ型感光性アニオン電着塗料用組成物を提供することを目的とする。 The present invention solves the problems in the prior art as described above, does not use a complicated acrylic resin production process, has good liquid aging stability, and good circuit forming ability such as developability and etching resistance. An object of the present invention is to provide a composition for positive photosensitive anionic electrodeposition coating.
本願発明者らは、主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体、１分子につき、平均１から２個の感光性基を有する低分子感光剤を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用組成物を用いて電着塗装を行なうことにより、上記課題を克服できることを見出し、本願発明にいたった。
すなわち本発明は、
（Ａ） 以下の（ａ）〜（ｃ）成分を用いて共重合することにより得られる、主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体 ６０〜９５重量部、
（ａ）置換基としてカルボキシル基を有する共重合性ビニル系単量体２〜１５重量部
（ｂ）（ａ）以外の共重合性ビニル系単量体８５〜９８重量部
（ｃ）カルボキシル基を有する連鎖移動剤 共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、０．０５〜１０重量部
（Ｂ） １分子につき、平均１から２個の感光性基を有する低分子感光剤 ５〜４０重量部
（Ｃ） 中和剤として（Ａ）成分のカルボキシル基１モルに対し、３級アミンを０．２〜０．９モルを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用組成物、を要旨とするものである。
The inventors of the present invention contain a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the end of the main chain, and a low-molecular photosensitizer having an average of 1 to 2 photosensitive groups per molecule. The inventors have found that the above-mentioned problems can be overcome by performing electrodeposition coating using the characteristic positive-type photosensitive anion electrodeposition coating composition, and have arrived at the present invention.
That is, the present invention
(A) 60-95 parts by weight of a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the end of the main chain, obtained by copolymerization using the following components (a) to (c):
(A) 2-15 parts by weight of a copolymerizable vinyl monomer having a carboxyl group as a substituent (b) 85-98 parts by weight of a copolymerizable vinyl monomer other than (a) (c) a carboxyl group Chain transfer agent having 0.05 to 10 parts by weight (B) of 1 to 2 photosensitive groups per molecule on the basis of a total of 100 parts by weight of the copolymerizable vinyl monomers (a) and (b) 5 to 40 parts by weight of a low molecular weight photosensitizer (C) The neutralizing agent contains 0.2 to 0.9 mol of a tertiary amine with respect to 1 mol of the carboxyl group of the component (A). The gist of the composition is a positive photosensitive anionic electrodeposition coating composition.
本発明のポジ型感光性アニオン電着塗料用組成物は上記したような構成であり、本発明のポジ型感光性アニオン電着塗料用組成物を使用することで、電着塗料液安定性と併せて、現像性、解像度が良好な感光性電着塗膜を得ることができ、産業上極めて有用である。 The composition for positive photosensitive anionic electrodeposition coating composition of the present invention has the above-described configuration, and by using the composition for positive photosensitive anionic electrodeposition coating composition of the present invention, In addition, a photosensitive electrodeposition coating film having good developability and resolution can be obtained, which is extremely useful industrially.
本発明の構成と作用を説明する。本発明においては、主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）、１分子につき、平均１から２個の感光性基を有する低分子感光剤（Ｂ）、中和剤としての３級アミン（Ｃ）の各成分は、ポジ型感光性アニオン電着塗料用組成物を得るための必須構成成分である。 The configuration and operation of the present invention will be described. In the present invention, a water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the end of the main chain (A), a low molecular weight photosensitizer (B) having an average of 1 to 2 photosensitive groups per molecule. Each component of the tertiary amine (C) as a neutralizing agent is an essential component for obtaining a positive photosensitive anionic electrodeposition coating composition.
（Ａ）成分の主鎖末端にカルボキシル基を有する水溶性又は水分散性のビニル系共重合体を構成する、置換基としてカルボキシル基を有する共重合性ビニル系単量体（ａ）としては、アクリル酸、メタクリル酸、アクリル酸ダイマー、イタコン酸、無水マレイン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸、メサコン酸等のアクリル系アニオン電着塗料に一般的に使用されるものを用いられるがこれらに限定されない。これらの中では、アクリル酸、メタクリル酸を用いるのが望ましい。 As the copolymerizable vinyl monomer (a) having a carboxyl group as a substituent, constituting a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the main chain terminal of the component (A), Acrylic acid, methacrylic acid, acrylic acid dimer, itaconic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, etc. However, it is not limited to these. In these, it is desirable to use acrylic acid and methacrylic acid.
（Ａ）成分の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体を構成する、その他のビニル系単量体（ｂ）としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ−プロピルアクリレート、ｎ−プロピルメタクリレート、イソプロピルアクリレート、イソプロピルメタクリレート、ノルマルブチルアクリレート、ノルマルブチルメタクリレート、ノルマルヘキシルアクリレート、ノルマルヘキシルメタクリレート、ノルマルヘプチルアクリレート、ノルマルヘプチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレート、ノルマルラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート等の炭素数約２０までのアルキル基を有する同様な共重合性ビニルエステルやシクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレートなどの側鎖に脂環式炭化水素基を有する共重合性ビニルエステル系単量体、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシ
プロピルメタクリレート、３−ヒドロキシプロピルアクリレート、３−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルアクリレート、４−ヒドロキシブチルメタクリレート、ジエチレングリコールモノアクリレート、シクロヘキサンジメタノールモノアクリレート等の水酸基含有単量体、及び、スチレン、α−メチルスチレン、α−クロロスチレン、ビニルトルエン等の芳香族基を有するビニル系単量体が使用できる。さらにアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−エトキシメチルアクリルアミド、Ｎ−イソブトキシメチルアクリルアミド、Ｎ−ブトキシメチルアクリルアミド、メタクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−メトキシメチルメタクリルアミド、Ｎ−エトキシメチルメタクリルアミド、Ｎ−イソブトキシメチルメタクリルアミド、Ｎ−ブトキシメチルメタクリルアミド等の（メタ）アクリルアミド類やアクリロニトリル、酢酸ビニル等を使用することも出来る。
The other vinyl monomer (b) constituting the water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the main chain terminal of the component (A) includes methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2- Ethylhexyl methacrylate, normal lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate Copolymers having an alicyclic hydrocarbon group in the side chain, such as a similar copolymerizable vinyl ester having an alkyl group of up to about 20 carbon atoms such as cyclohexyl, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate. Polymerizable vinyl ester monomer, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate , 4-hydroxybutyl methacrylate, hydroxyl group-containing monomers such as diethylene glycol monoacrylate, cyclohexane dimethanol monoacrylate, and styrene, α-methyl Vinyl monomers having an aromatic group such as styrene, α-chlorostyrene and vinyl toluene can be used. Further, acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-butoxymethyl acrylamide, methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N (Meth) acrylamides such as ethoxymethyl methacrylamide, N-isobutoxymethyl methacrylamide, N-butoxymethyl methacrylamide, acrylonitrile, vinyl acetate and the like can also be used.
（Ａ）成分の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体を構成するカルボキシル基を有する連鎖移動剤（ｃ）は、ビニル重合の際に開始ラジカル、または、成長ラジカルが連鎖移動することで重合を開始することができるもので、それにより水溶性、または、水分散性ビニル系共重合体の主鎖末端にカルボキシル基を導入できる。
そのため、（Ｂ）成分の１分子につき、平均１から２個の感光性基を有する低分子感光剤との相溶性がきわめて優れ、該感光剤の分散安定性が良好となる。
そして、１分子につき、平均１から２個の感光性基を有する低分子感光剤をコアとしたコアシェル型エマルジョンが形成されるので、１分子につき、平均１から２個の感光性基を有する低分子感光剤の加水分解が抑制され、液の安定性が良好となる。
カルボキシル基を有する連鎖移動剤としては、チオカルボン酸類が好ましく、具体的には、チオグリコール酸、２−チオプロピオン酸、３−チオプロピオン酸、チオ乳酸、メルカプトコハク酸、チオリンゴ酸、Ｎ−（２−メルカプトプロピオニル）グリシン、２−メルカプト安息香酸、２−メルカプトニコチン酸、チオリンゴ酸、チオサリチル酸、３，３−ジチオジプロピオン酸、３，３−ジチオイソ酪酸等があげられるが、なかでも３−チオプロピオン酸が好ましい。
The chain transfer agent (c) having a carboxyl group constituting a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the main chain terminal of the component (A) is an initiation radical or a growth during the vinyl polymerization. Polymerization can be initiated by the chain transfer of radicals, whereby a carboxyl group can be introduced at the end of the main chain of a water-soluble or water-dispersible vinyl copolymer.
Therefore, the compatibility with the low molecular weight photosensitizer having 1 to 2 photosensitive groups on average per molecule of the component (B) is extremely excellent, and the dispersion stability of the photosensitizer is good.
Then, since a core-shell type emulsion having a low molecular weight photosensitizer having an average of 1 to 2 photosensitive groups per molecule as a core is formed, a low average having 1 to 2 photosensitive groups per molecule is formed. Hydrolysis of the molecular photosensitizer is suppressed, and the liquid stability is improved.
As the chain transfer agent having a carboxyl group, thiocarboxylic acids are preferable. Specifically, thioglycolic acid, 2-thiopropionic acid, 3-thiopropionic acid, thiolactic acid, mercaptosuccinic acid, thiomalic acid, N- (2 -Mercaptopropionyl) glycine, 2-mercaptobenzoic acid, 2-mercaptonicotinic acid, thiomalic acid, thiosalicylic acid, 3,3-dithiodipropionic acid, 3,3-dithioisobutyric acid, etc., among which 3-thio Propionic acid is preferred.
（Ａ）成分の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体を重合する際に使用される溶剤は、一般的なものが使用できるが、水溶性又は水分散性という点からイソプロピルアルコール、ノルマルブタノール、イソブタノール等のアルコール類、エチレングリコールモノブチルエーテル、エチレングリコールモノターシャリーブチルエーテル等のセロソルブ類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールエーテル類が望ましい。
（Ａ）成分の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体を重合する際に使用される重合開始剤は、アゾビスイソブチロニトリル、２，２‘−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系開始剤、過酸化ベンゾイル、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン等の過酸化物等が使用できる。
(A) Although the solvent used when superposing | polymerizing the water-soluble or water-dispersible vinyl copolymer which has a carboxyl group in the principal chain terminal of a component can use a general thing, it is water-soluble or water-dispersible. Therefore, alcohols such as isopropyl alcohol, normal butanol and isobutanol, cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monotertiary butyl ether, propylene such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether Glycol ethers are desirable.
The polymerization initiator used when polymerizing a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the main chain terminal of the component (A) is azobisisobutyronitrile, 2,2′-azobis. Azo initiators such as (2,4-dimethylvaleronitrile), peroxides such as benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like can be used.
（Ｂ）成分の１分子につき、平均１から２個の感光性基を有する低分子感光剤としては、通常のポジ型液状レジストと異なり制限があり、非ベンゾフェノン系の分子量１０００未満の低分子ポリフェノール化合物とナフトキノンジアジドスルホン酸（６−ジアゾ−５，６−ジヒドロ−５−オキソ−ナフタレン−１−スルホン酸）のエステル化物を用いることが好ましい。
すなわち一般にポジ型液状レジストに用いられる感光剤であるノボラック樹脂のナフトキノンジアジドスルホン酸のエステル化物やフェノール性水酸基を複数個有するベンゾフェノン誘導体のナフトキノンジアジドスルホン酸のエステル化物、及び、分子量１０００
以上のポリフェノール化合物とナフトキノンジアジドスルホン酸とナフトキノンジアジドスルホン酸のエステル化物は本発明の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）を用いても分散安定性が悪く、電着特性や経時安定性に悪影響を与えるために使用することはできない。
The low molecular weight photosensitizer having an average of 1 to 2 photosensitive groups per molecule of the component (B) is limited unlike a normal positive liquid resist, and is a non-benzophenone low molecular weight polyphenol having a molecular weight of less than 1000. It is preferable to use an esterified product of the compound and naphthoquinonediazidesulfonic acid (6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid).
That is, an esterified product of naphthoquinone diazide sulfonic acid of a novolak resin which is a photosensitive agent generally used for a positive type liquid resist, an esterified product of naphthoquinone diazide sulfonic acid of a benzophenone derivative having a plurality of phenolic hydroxyl groups, and a molecular weight of 1000
The above esterified product of polyphenol compound, naphthoquinone diazide sulfonic acid and naphthoquinone diazide sulfonic acid is stable even when the water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the main chain terminal of the present invention is used. However, it cannot be used to adversely affect electrodeposition characteristics and stability over time.
本願の１分子につき、平均１から２個の感光性基を有する低分子感光剤である非ベンゾフェノン系の分子量１０００以下の低分子ポリフェノール化合物とナフトキノンジアジドスルホン酸のエステル化物の合成に使用できる特定の低分子ポリフェノール化合物としては、４，４’−（３，３，５−トリメチルシクロヘキシリデン）ビスフェノール，４，４‘−（１−メチルエチリデン）ビス（２−メチルフェノール），４，４’−シクロヘキシリデンビスフェノール，４，４‘−（１−α−メチル−ベンジリデン）ビスフェノール，４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノール、ビス（４−ヒドロキシフェニル）フェニルメタン、トリス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシ−３−メチルフェニル）−４−ヒドロキシ−３−メトキシフェニルメタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（４−ヒドロキシ−３−メチルフェニル）エタン等があげられるが、これらに限定されない。 Specific molecules that can be used for the synthesis of a non-benzophenone low molecular weight polyphenol compound having a molecular weight of 1000 or less and an esterified product of naphthoquinonediazide sulfonic acid, which is a low molecular weight photosensitizer having an average of 1 to 2 photosensitive groups per molecule of the present application Examples of the low molecular weight polyphenol compound include 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol, 4,4 ′-(1-methylethylidene) bis (2-methylphenol), 4,4′-. Cyclohexylidene bisphenol, 4,4 ′-(1-α-methyl-benzylidene) bisphenol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene ] Bisphenol, bis (4-hydroxyphenyl) phenylmethane, tris (4-hydroxyphenyl) Methane, bis (4-hydroxy-3-methylphenyl) -4-hydroxy-3-methoxyphenylmethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis Examples include (4-hydroxy-3-methylphenyl) ethane, but are not limited thereto.
本発明における主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）のカルボキシル基の中和には、３級アミンを用いることが好ましい。
一般的なアニオン電着の中和剤として用いられる水酸化ナトリウム等無機アルカリやアンモニア、ジプロピルアミン等の１級、２級アミン類は強塩基性であるので、主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）を中和した後に、１分子につき、平均１から２個の感光性基を有する低分子感光剤を加えた際に感光剤の劣化を引き起こし、本願発明で使用する中和剤としては好ましくない。
In the present invention, a tertiary amine is preferably used for neutralizing the carboxyl group of the water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the end of the main chain.
Inorganic alkali such as sodium hydroxide used as a neutralizing agent for general anion electrodeposition, and primary and secondary amines such as ammonia and dipropylamine are strongly basic, and thus have a carboxyl group at the end of the main chain. After neutralizing the water-soluble or water-dispersible vinyl copolymer (A), when a low molecular weight photosensitive agent having an average of 1 to 2 photosensitive groups per molecule is added, the photosensitive agent is deteriorated. The neutralizing agent used in the present invention is not preferable.
しかしながら、本願発明で使用する３級アミンは、そのような劣化反応が抑制され好ましく使用される。本発明に使用できる３級アミンとしては、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、トリヘキシルアミン等のアルキルアミンやメチルジエタノールアミン、ジメチルエタノールアミン、トリエタノールアミン、２−（Ｎ，Ｎ−ジメチルアミノ）−２−メチル−１−プロパノール等のアルカノールアミンなどが挙げられる。特に望ましいものは、アルカノールアミン類である。本発明に使用する３級アミンは、（Ａ）成分中のカルボキシル基に対して、モル比が０．２〜０．９となるように添加すればよい。 However, the tertiary amine used in the present invention is preferably used since such deterioration reaction is suppressed. Examples of the tertiary amine that can be used in the present invention include alkylamines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, trihexylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, 2- (N, N- And alkanolamines such as dimethylamino) -2-methyl-1-propanol. Particularly desirable are alkanolamines. What is necessary is just to add the tertiary amine used for this invention so that molar ratio may be 0.2-0.9 with respect to the carboxyl group in (A) component.
主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）により得られた電着塗膜は、優れた液安定性を有し、置換基としてカルボキシル基を有する共重合性ビニル系単量体（ａ）２〜１５重量部、好ましくは４〜１０重量部、（ａ）以外の共重合性ビニル系単量体（ｂ）が８５〜９８重量部、好ましくは９０〜９６重量部、共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、カルボキシル基を有する連鎖移動剤（ｃ）０．０５〜１０重量部、好ましくは０．５重量部〜５重量部を重合し作製した主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体により得られた電着塗料用組成物は、水分散性が特に良好であり、それにより得られた電着塗膜は、現像性、耐エッチング性等の回路形成特性に優れている。 The electrodeposition coating film obtained from the water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the main chain terminal has excellent liquid stability and has a carboxyl group as a substituent. 2-15 parts by weight of the polymerizable vinyl monomer (a), preferably 4-10 parts by weight, 85-98 parts by weight of the copolymerizable vinyl monomer (b) other than (a), preferably 90-90 parts by weight. The chain transfer agent (c) having a carboxyl group is 0.05 to 10 parts by weight, preferably 0.5 parts, based on 96 parts by weight and a total of 100 parts by weight of the copolymerizable vinyl monomers (a) and (b). The electrodeposition coating composition obtained from a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the end of the main chain produced by polymerizing parts by weight to 5 parts by weight has particularly good water dispersibility. The electrodeposition coating film thus obtained has a developing property, etching resistance, etc. It has excellent forming properties.
主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）の構成である置換基としてカルボキシル基を有する共重合性ビニル系単量体（ａ）が２重量部未満である電着塗料用組成物は液安定性が悪く、現像液への溶解性が低いために現像性が悪い。
また、１５重量部を超えると得られた塗膜の耐薬品性が悪く、現像液に溶けすぎてパタ
ーン形成ができない。
共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、メルカプトカルボン酸（ｃ）が０．０５重量部未満であると現像性が低下し、１０重量部を超えると現像液に溶けすぎてパターン形成ができない。
The copolymerizable vinyl monomer (a) having a carboxyl group as a substituent which is the constitution of the water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the main chain terminal is less than 2 parts by weight. Certain electrodeposition coating compositions have poor liquid stability and poor developability due to low solubility in the developer.
Moreover, when it exceeds 15 weight part, the chemical resistance of the obtained coating film is bad, and it cannot melt | dissolve in a developing solution and pattern formation cannot be performed.
If the amount of mercaptocarboxylic acid (c) is less than 0.05 parts by weight relative to 100 parts by weight of the total copolymerizable vinyl monomers (a) and (b), the developability is reduced and the amount exceeds 10 parts by weight. It is too soluble in the developer to form a pattern.
本発明の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）６０〜９５重量部、好ましくは、８０〜９３重量部、１分子につき、平均１から２個の感光性基を有する低分子感光剤（Ｂ）５〜４０重量部、好ましくは、１０〜２０重量部で用いる。水溶性又は水分散性ビニル系共重合体（Ａ）の割合が６０重量部未満では、十分な水分散性が得られず液安定性が悪く沈降を生じやすく、９５重量部を超えると十分な回路形成性能が得られない。
１分子につき、平均１から２個の感光性基を有する低分子感光剤（Ｂ）の割合が５重量部未満では、十分な回路形成性能が得られず、４０重量部を超えると、十分な水分散性が得られず、電着塗布しても平滑な塗膜が得られないため充分な解像度が得られず耐エッチング性が劣る。また、製造コストも上昇する。
The water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the end of the main chain of the present invention is preferably 60 to 95 parts by weight, preferably 80 to 93 parts by weight, and an average of 1 to 2 per molecule. The low molecular weight photosensitizer (B) having a photosensitive group is used in an amount of 5 to 40 parts by weight, preferably 10 to 20 parts by weight. If the proportion of the water-soluble or water-dispersible vinyl copolymer (A) is less than 60 parts by weight, sufficient water dispersibility cannot be obtained, the liquid stability is poor, and precipitation tends to occur. Circuit formation performance cannot be obtained.
If the ratio of the low molecular weight photosensitizer (B) having an average of 1 to 2 photosensitive groups per molecule is less than 5 parts by weight, sufficient circuit forming performance cannot be obtained, and if it exceeds 40 parts by weight, sufficient Since water dispersibility cannot be obtained and a smooth coating film cannot be obtained even by electrodeposition coating, sufficient resolution cannot be obtained and etching resistance is poor. In addition, the manufacturing cost increases.
本発明の主鎖末端にカルボキシル基を有する水溶性又は水分散性ビニル系共重合体（Ａ）のカルボキシル基１モルに対し、中和剤としての３級アミン（Ｃ）は、０．２〜０．９モル、好ましくは、０．３〜０．５モルで用いる。３級アミン（Ｃ）が、０．２モル未満では、十分な水分散性が得られず液安定性が悪く沈降を生じやすく、０．９モルを超えると、塩基性が増加するため感光剤の劣化が起こり、液安定性が悪くなる。 The tertiary amine (C) as a neutralizing agent is 0.2 to 1 mol of the carboxyl group of the water-soluble or water-dispersible vinyl copolymer (A) having a carboxyl group at the end of the main chain of the present invention. 0.9 mol, preferably 0.3 to 0.5 mol is used. If the tertiary amine (C) is less than 0.2 mol, sufficient water dispersibility cannot be obtained, resulting in poor liquid stability and easy precipitation, and if it exceeds 0.9 mol, the basicity increases, so the photosensitizer. Deterioration of the liquid occurs, resulting in poor liquid stability.
本発明により構成されるポジ型感光性アニオン電着塗料用組成物は基板上に電着塗装されるが、基板としては銅箔などの導電性の被膜層を有するリジット及びフレキシブルプリント基板、銅、ステンレス、ニッケル、アルミニウムなどの金属板及びニッケルめっき、スズめっき、クロムめっきなどのめっき処理したものが使用できる。
電着前処理として各基材に適した脱脂やエッチング処理を行うことができ、電着前に充分脱イオン水で水洗する。電着前なじみとして、被塗物を電着槽に入槽する。通常バッチ処理で行われるリジッドプリント基板にはスルーホールがある。その微細孔に塗膜を析出させるため電着槽にプリント基板を入槽する時、電着塗料液を循環させてスルーホール内に電着塗料液を入れる。必要があればその吹き出し口をプリント基板に当てエアーポケットが発生しないようにする。プリント基板に振動を加えエアーを抜く方法もある。リールトゥリールなどの連続式処理方法で行われるフレキシブルプリント基板は、前なじみ槽を設置することが望ましい。電着条件としては、通電工程において印加される電圧は１０〜４００Ｖ、好ましくは１００〜２５０Ｖであり、通電時間は０．１分〜５分、好ましくは０．５〜４分である。電圧が高いほど通電時間は短く、電圧が低ければ通電時間を長くする。印加電圧は通電と同時に設定電圧をかけるハードスタート、あるいは徐々に設定電圧まで電圧を上げていくソフトスタートのいずれでもかまわない。また、スルーホール内に充分な塗膜厚になるように、通電時間は２〜４分が望ましい。フレキシブルプリント基板で採用されるリールトゥリールなどの連続式処理方法では、電着槽スペースの制約上から通電時間は０．１分〜０．５分で行われる。本組成物を用いれば通電時間０．１分からの電着処理が可能であり、処理速度が上がり生産性の向上が図れる。
The composition for positive photosensitive anionic electrodeposition coating composition constituted according to the present invention is electrodeposited on a substrate, and the substrate has a rigid and flexible printed circuit board having a conductive coating layer such as copper foil, copper, Metal plates such as stainless steel, nickel, and aluminum and those plated with nickel, tin, or chromium can be used.
Degreasing and etching processes suitable for each substrate can be performed as a pretreatment for electrodeposition, and it is sufficiently washed with deionized water before electrodeposition. As familiarity before electrodeposition, the object to be coated is placed in the electrodeposition tank. There is a through hole in a rigid printed circuit board usually performed in batch processing. When the printed circuit board is placed in the electrodeposition tank in order to deposit the coating film in the fine holes, the electrodeposition paint liquid is circulated to put the electrodeposition paint liquid in the through hole. If necessary, the air outlet is applied to the printed circuit board to prevent air pockets from being generated. There is also a method of drawing air by applying vibration to the printed circuit board. It is desirable to install a pre-familiarizing tank for a flexible printed circuit board that is performed by a continuous processing method such as reel-to-reel. As electrodeposition conditions, the voltage applied in the energization step is 10 to 400 V, preferably 100 to 250 V, and the energization time is 0.1 minutes to 5 minutes, preferably 0.5 to 4 minutes. The higher the voltage, the shorter the energization time, and the lower the voltage, the longer the energization time. The applied voltage may be either a hard start in which a set voltage is applied simultaneously with energization, or a soft start in which the voltage is gradually raised to the set voltage. The energization time is preferably 2 to 4 minutes so that a sufficient coating thickness is obtained in the through hole. In a continuous processing method such as a reel-to-reel employed in a flexible printed circuit board, the energization time is 0.1 minutes to 0.5 minutes due to restrictions on the electrodeposition tank space. If this composition is used, the electrodeposition process can be performed from an energization time of 0.1 minutes, and the processing speed can be increased to improve the productivity.
電着塗装された被塗装物は、数秒から数分間の浸漬水洗又はシャワー式水洗を行う。次いで１００℃で１０分間程度加熱して乾燥するが最適加熱条件は、基材が紙フェノール、ガラスエポキシ、セラミック等の材質の種類と厚みにより異なり、８０℃〜１２０℃で数分から２０分程度の範囲で最適条件を確認する必要がある。また、加熱乾燥を２回に分割し、初期乾燥として１００℃３分程度行った後に数時間から数日後に８０℃〜１２０℃１０分程度再乾燥しても構わない。塗装膜中の水分を乾燥した後に配線パターンを描画したフォトマスクを当てメタルハライドランプの紫外線光源を用い、積算光量１００ｍＪ／ｃ
ｍ２〜５００ｍＪ／ｃｍ２を照射する。本組成物の感光性基はi線波長３６５ｎｍに感光するので、この波長の積算光量を確認する。その後、現像液０．５％メタケイ酸ナトリウム水溶液を用いて、３２℃２分間浸漬して現像する。メタケイ酸ナトリウム水溶液は、０．２％〜１．０％濃度で現像可能である。同様に０．２％〜１．０％の炭酸ナトリウム水溶液で現像することも出来るが、現像時間は２倍程度長くかかる。その後塩化第二鉄又は塩化第二銅のエッチング液を用い、銅箔をエッチングして配線パターンを形成する。エッチング条件は、プリント基板の銅箔の厚さにより異なる。通常、銅箔の厚さは８μ〜７０μとその用途により異なりエッチング時間が数分以内に可能となるようスプレー圧力、エッチング液温度が調整される。その後、電着塗膜は、３％水酸化ナトリウム水溶液に５０℃で２分から３分浸漬して剥離し回路パターン形成を行う。
The electrodeposition-coated object is subjected to immersion water washing or shower type water washing for several seconds to several minutes. Next, it is heated at 100 ° C. for about 10 minutes to dry, but the optimum heating condition depends on the type and thickness of the material such as paper phenol, glass epoxy, ceramic, etc., and it is about 80 minutes to 20 minutes at 80 ° C. to 120 ° C. It is necessary to confirm the optimum conditions in the range. Further, the heat drying may be divided into two, and after initial drying at about 100 ° C. for about 3 minutes, after several hours to several days, it may be re-dried at about 80 ° C. to 120 ° C. for about 10 minutes. Applying a photomask on which a wiring pattern has been drawn after drying the moisture in the coating film and using an ultraviolet light source of a metal halide lamp, an integrated light quantity of 100 mJ / c
Irradiation with m 2 to 500 mJ / cm 2 is performed. Since the photosensitive group of the present composition is sensitive to an i-line wavelength of 365 nm, the integrated light quantity at this wavelength is confirmed. Thereafter, development is performed by immersing in a 0.5% aqueous sodium metasilicate solution at 32 ° C. for 2 minutes. A sodium metasilicate aqueous solution can be developed at a concentration of 0.2% to 1.0%. Similarly, development can be performed with a 0.2% to 1.0% aqueous sodium carbonate solution, but the development time is about twice as long. Thereafter, the copper foil is etched using a ferric chloride or cupric chloride etchant to form a wiring pattern. Etching conditions differ depending on the thickness of the copper foil of the printed board. Usually, the thickness of the copper foil varies from 8 μm to 70 μm depending on its application, and the spray pressure and the etchant temperature are adjusted so that the etching time can be within a few minutes. Thereafter, the electrodeposition coating film is immersed in a 3% aqueous sodium hydroxide solution at 50 ° C. for 2 to 3 minutes to separate and form a circuit pattern.
以下に本発明の実施例および比較例を挙げてさらに具体的に説明するが、これによって本発明が限定されるものではない。なお、実施例、比較例中の部は、特に断りのない限り重量部である。
製造例１
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、ブチルセロソルブ１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール１６．０部、アクリル酸６部、２−ヒドロキシエチルアクリレート１部、２−エチルヘキシルアクリレート１４部、エチルアクリレート１０部、ｎ−ブチルアクリレート３４部、メチルメタクリレート３５部、メルカプト酢酸１部、アゾビスイソブチロニトリル２部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにイソプロパノール２部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた後に、冷却し共重合体の温度が５０℃以下でジメチルアミノエタノールを２．３部添加後に攪拌を終了した。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example is a weight part unless there is particular notice.
Production Example 1
10.0 parts of isopropanol and 10.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 16.0 parts of isopropanol, 6 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate, 14 parts of 2-ethylhexyl acrylate, 10 parts of ethyl acrylate, 34 parts of n-butyl acrylate, 35 parts of methyl methacrylate, 1 part of mercaptoacetic acid, azo A mixed solution of 2 parts of bisisobutyronitrile was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 2 parts of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. Stirring was terminated after 2.3 parts of dimethylaminoethanol was added at a temperature of 50 ° C. or lower.
製造例２
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、ブチルセロソルブ１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール１６．０部、アクリル酸６部、２−ヒドロキシエチルアクリレート１部、２−エチルヘキシルアクリレート１４部、エチルアクリレート１０部、ｎ−ブチルアクリレート３４部、メチルメタクリレート３５部、３−チオプロピオン酸２部、アゾビスイソブチロニトリル２部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにイソプロパノール２部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた後に、冷却し共重合体の温度が５０℃以下でジメチルアミノエタノールを３部添加後に攪拌を終了した。
Production Example 2
10.0 parts of isopropanol and 10.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, isopropanol 16.0 parts, acrylic acid 6 parts, 2-hydroxyethyl acrylate 1 part, 2-ethylhexyl acrylate 14 parts, ethyl acrylate 10 parts, n-butyl acrylate 34 parts, methyl methacrylate 35 parts, 3-thiopropionic acid 2 A mixture of 2 parts of azobisisobutyronitrile was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 2 parts of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. Stirring was terminated after 3 parts of dimethylaminoethanol was added at a temperature of 50 ° C. or lower.
製造例３
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、ブチルセロソルブ１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール１６．０部、アクリル酸６部、２−ヒドロキシエチルアクリレート１部、２−エチルヘキシルアクリレート１４部、エチルアクリレート１０部、ｎ−ブチルアクリレート３４部、メチルメタクリレート３５部、チオグリコール酸１部、アゾビスイソブチロニトリル２部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにイソプロパノール２部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた後に、冷却し共重合体の温度が５０℃以下でジメチルアミノエタノールを２．３部添加後に攪拌を終了した。
Production Example 3
10.0 parts of isopropanol and 10.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 16.0 parts of isopropanol, 6 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate, 14 parts of 2-ethylhexyl acrylate, 10 parts of ethyl acrylate, 34 parts of n-butyl acrylate, 35 parts of methyl methacrylate, 1 part of thioglycolic acid, A mixed solution of 2 parts of azobisisobutyronitrile was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 2 parts of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. Stirring was terminated after 2.3 parts of dimethylaminoethanol was added at a temperature of 50 ° C. or lower.
製造例４
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、ブチルセロソルブ１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール１６．０部、アクリル酸６部、２−ヒドロキシエチルアクリレート１部、２−エチルヘキシルアクリレート１４部、エチルアクリレート１０部、ｎ−ブチルアクリレート３４部、メチルメタクリレート３５部、アゾビスイソブチロニトリル２部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにイソプロパノール２部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた後に、冷却し共重合体の温度が５０℃以下でジメチルアミノエタノールを２．３部添加後に攪拌を終了した。
Production Example 4
10.0 parts of isopropanol and 10.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 16.0 parts of isopropanol, 6 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate, 14 parts of 2-ethylhexyl acrylate, 10 parts of ethyl acrylate, 34 parts of n-butyl acrylate, 35 parts of methyl methacrylate, azobisisobutyronitrile 2 parts of the mixed solution was charged into the dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 2 parts of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. Stirring was terminated after 2.3 parts of dimethylaminoethanol was added at a temperature of 50 ° C. or lower.
製造例５
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、ブチルセロソルブ１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール１６．０部、アクリル酸６部、２−ヒドロキシエチルアクリレート１部、２−エチルヘキシルアクリレート１４部、エチルアクリレート１０部、ｎ−ブチルアクリレート３４部、メチルメタクリレート３５部、メルカプト酢酸１５部、アゾビスイソブチロニトリル２部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにイソプロパノール２部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた後に、冷却し共重合体の温度が５０℃以下でジメチルアミノエタノールを３．８部添加後に攪拌を終了した。
Production Example 5
10.0 parts of isopropanol and 10.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 16.0 parts of isopropanol, 6 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate, 14 parts of 2-ethylhexyl acrylate, 10 parts of ethyl acrylate, 34 parts of n-butyl acrylate, 35 parts of methyl methacrylate, 15 parts of mercaptoacetic acid, azo A mixed solution of 2 parts of bisisobutyronitrile was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 2 parts of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. The stirring was terminated after adding 3.8 parts of dimethylaminoethanol at a temperature of 50 ° C. or lower.
実施例１
製造例１で得られたビニル系共重合体１２２部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物１５部を混合し、攪拌を続けながら、脱イオン水を４１８．５部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Example 1
122 parts of the vinyl copolymer obtained in Production Example 1, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazi Mix 15 parts of ester compound with -5,6 dihydro-5-oxonaphthalene-1-sulfonic acid, add 418.5 parts of deionized water while continuing to stir, perform phase inversion emulsification, Obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
実施例２
製造例２で得られたビニル系共重合体１２２．６部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物１５部を混合し、攪拌を続けながら、脱イオン水を４１７．９部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Example 2
122.6 parts of the vinyl copolymer obtained in Production Example 2, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6 -Mixing 15 parts of an ester compound with diazi-5,6dihydro-5-oxonaphthalene-1-sulfonic acid, adding 417.9 parts of deionized water while continuing stirring and performing phase inversion emulsification, electrodeposition A stock solution was obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
実施例３
製造例３で得られたビニル系共重合体１２２部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物１５部を混合し、攪拌を続けながら、脱イオン水を４１８．５部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Example 3
122 parts of the vinyl copolymer obtained in Production Example 3, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diadi Mix 15 parts of ester compound with -5,6 dihydro-5-oxonaphthalene-1-sulfonic acid, add 418.5 parts of deionized water while continuing to stir, perform phase inversion emulsification, Obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
比較例１
製造例４で得られたビニル系共重合体１２２．４部と４、４’−［１−［４−［１−（
４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物１５部を混合し、攪拌を続けながら、脱イオン水を４１８．２部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Comparative Example 1
122.4 parts of the vinyl copolymer obtained in Production Example 4 and 4,4 ′-[1- [4- [1- (
While mixing 15 parts of an ester compound of 4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diadi-5,6 dihydro-5-oxonaphthalene-1-sulfonic acid, while stirring, 418.2 parts of deionized water was added and phase inversion emulsification was performed to obtain a stock solution for electrodeposition. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
比較例２
製造例５で得られたビニル系共重合体１２６．８部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物１３部を混合し、攪拌を続けながら、脱イオン水を４１３．８部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Comparative Example 2
126.8 parts of the vinyl copolymer obtained in Production Example 5, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6 -Mix 13 parts of ester compound with diazi-5,6dihydro-5-oxonaphthalene-1-sulfonic acid, add 413.8 parts of deionized water while continuing stirring, and perform phase inversion emulsification. A stock solution was obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
比較例３
製造例１で得られたビニル系共重合体１３９．２部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物３部を混合し、攪拌を続けながら、脱イオン水を４１３．３部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Comparative Example 3
139.2 parts of the vinyl copolymer obtained in Production Example 1 and 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6 -Mixing 3 parts of ester compound with diazi-5,6dihydro-5-oxonaphthalene-1-sulfonic acid, adding 413.3 parts of deionized water while continuing to stir, and performing phase inversion emulsification, electrodeposition A stock solution was obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
比較例４
製造例１で得られたビニル系共重合体７８．９部と４、４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアジ−５，６ジヒドロ−５−オキソナフタレン−１−スルホン酸とのエステル化合物４５部を混合し、攪拌を続けながら、脱イオン水を４３１．６部加えて転相乳化を行ない、電着用原液を得た。別の容器に脱イオン水を４４４．４部仕込み、攪拌しながら前記電着用原液５５５．５部を投入し電着液を得た。
Comparative Example 4
78.9 parts of the vinyl copolymer obtained in Production Example 1, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6 -Mix 45 parts of ester compound with diazi-5,6dihydro-5-oxonaphthalene-1-sulfonic acid, add 431.6 parts deionized water while continuing stirring, and perform phase inversion emulsification. A stock solution was obtained. In a separate container, 444.4 parts of deionized water was charged, and 555.5 parts of the electrodeposition stock solution was added while stirring to obtain an electrodeposition solution.
電着塗料用組成物の評価
実施例１〜３、比較例１〜４で調整した電着塗料液を使用し、常法に従って陽極に片面に銅箔を貼ってあるサンハヤト（株）プリント基板Ｎｏ．１０番（７．５ｃｍ×１０ｃｍ）を、陰極にＳＵＳ３０４板を用いて、７μｍの塗膜厚が得られる条件で電着塗装を実施した。次いで電着塗装されたプリント基板を取り出して充分に水洗したのち、１００℃の温度で１０分間乾燥して、水分、溶剤分を乾燥し、所定のパターンを描画したフォトマスク越しにメタルハライドランプにて積算光量３００ｍＪ／ｃｍ２を照射して露光した。その後、０．５％メタケイ酸ナトリウム水溶液を用いて、３２℃２分間浸漬して現像した後、充分に水洗した。その後、塩化第二鉄のエッチング液を用い、４０℃で５分エッチング液に浸漬した後に電着塗膜を剥離し、パターン形成を行った。プリント基板上に形成された電着塗膜の特性は表１に示すとおりであった。
Evaluation of the composition for electrodeposition coatings Sanhayato Co., Ltd. printed circuit board No. using the electrodeposition coating liquids prepared in Examples 1 to 3 and Comparative Examples 1 to 4 and having a copper foil on one side of the anode according to a conventional method . No. 10 (7.5 cm × 10 cm) was subjected to electrodeposition coating using a SUS304 plate as a cathode under the condition that a coating thickness of 7 μm was obtained. Next, the electrodeposited printed circuit board is taken out, washed thoroughly with water, dried at a temperature of 100 ° C. for 10 minutes, dried with water and solvent, and passed through a photomask on which a predetermined pattern is drawn with a metal halide lamp. Exposure was performed by irradiating with an integrated light amount of 300 mJ / cm 2 . Thereafter, using a 0.5% aqueous solution of sodium metasilicate, the film was developed by dipping at 32 ° C. for 2 minutes, and then thoroughly washed with water. Thereafter, using an etching solution of ferric chloride, the electrodeposition coating film was peeled off after being immersed in an etching solution at 40 ° C. for 5 minutes to form a pattern. Table 1 shows the properties of the electrodeposition coating film formed on the printed circuit board.
評価方法
（１）液安定性：作製した電着塗料液を２４時間静置して容器底に堆積した沈降物の有無を確認した。
（２）現像性：露光後のプリント基板を０．５％メタケイ酸ナトリウム水溶液に、３２℃で２分間浸漬して現像が可能であるかを確認した。
（３）解像度：ライン／スペースを描画したフォトマスクのテストパターンを使用し何μｍまでの線幅が電着塗膜で形成出来たかを確認した。
（４）耐エッチング液性：現像後のプリント基板を塩化第二鉄のエッチング液４０℃５分
浸漬した後の電着塗膜の割れ、折れの有無を確認した。
Evaluation method (1) Liquid stability: The prepared electrodeposition coating liquid was allowed to stand for 24 hours to confirm the presence or absence of sediment deposited on the bottom of the container.
(2) Developability: It was confirmed whether development was possible by immersing the printed circuit board after exposure in a 0.5% aqueous sodium metasilicate solution at 32 ° C. for 2 minutes.
(3) Resolution: Using a photomask test pattern on which lines / spaces were drawn, it was confirmed how many μm of line width could be formed by the electrodeposition coating film.
(4) Resistance to etching solution: It was confirmed whether or not the electrodeposition coating film was cracked or broken after the developed printed board was immersed in a ferric chloride etching solution at 40 ° C. for 5 minutes.
本発明のポジ型アニオン電着塗料用組成物を使用することで液安定性に優れ、また、当該電着塗料用組成物を用いて形成された電着塗膜は、良好な現像性、解像度、耐エッチング性を有しており、産業上極めて有用である。 By using the positive anion electrodeposition coating composition of the present invention, the liquid stability is excellent, and the electrodeposition coating film formed using the electrodeposition coating composition has good developability and resolution. It has etching resistance and is very useful industrially.
Claims (7)
（ａ）置換基としてカルボキシル基を有する共重合性ビニル系単量体 ２〜１５重量部
（ｂ）（ａ）以外の共重合性ビニル系単量体 ８５〜９８重量部
（ｃ）カルボキシル基を有する連鎖移動剤 共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、０．０５〜１０重量部
（Ｂ） １分子につき、平均１から２個の感光性基を有する低分子感光剤 ５〜４０重量部
（Ｃ） 中和剤としての３級アミン （Ａ）成分のカルボキシル基１モルに対し、０．２〜０．９モルを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用組成物。 (A) 60-95 parts by weight of a water-soluble or water-dispersible vinyl copolymer having a carboxyl group at the end of the main chain, obtained by copolymerization using the following components (a) to (c):
(A) 2-15 parts by weight of a copolymerizable vinyl monomer having a carboxyl group as a substituent (b) 85-98 parts by weight of a copolymerizable vinyl monomer other than (a) (c) a carboxyl group Chain transfer agent having 0.05 to 10 parts by weight (B) of 1 to 2 photosensitive groups per molecule on the basis of a total of 100 parts by weight of the copolymerizable vinyl monomers (a) and (b) 5 to 40 parts by weight of a low molecular weight photosensitizer (C) A tertiary amine as a neutralizing agent (A) 0.2 to 0.9 moles per mole of carboxyl group of component (A) A composition for positive photosensitive anionic electrodeposition coating.
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| KR102360275B1 (en) * | 2019-06-19 | 2022-02-08 | 대한유리공업(주) | Color changeable window structure |
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| JPH03100073A (en) * | 1989-09-14 | 1991-04-25 | Hitachi Chem Co Ltd | Positive photosensitive electrodeposition coating resin composition |
| JP2949391B2 (en) * | 1992-08-04 | 1999-09-13 | 日石三菱株式会社 | Manufacturing method of color filter |
| US5624781A (en) * | 1993-05-28 | 1997-04-29 | Kansai Paint Co., Ltd. | Positive type anionic electrodeposition photo-resist composition and process for pattern formation using said composition |
| JPH07278471A (en) * | 1994-04-15 | 1995-10-24 | Kansai Paint Co Ltd | Positive photosensitive anionic electrodeposition coating composition and pattern formation by using the same |
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