CA2072702A1 - Aqueous photosensitive resin composition and print obtained by using the same - Google Patents
Aqueous photosensitive resin composition and print obtained by using the sameInfo
- Publication number
- CA2072702A1 CA2072702A1 CA002072702A CA2072702A CA2072702A1 CA 2072702 A1 CA2072702 A1 CA 2072702A1 CA 002072702 A CA002072702 A CA 002072702A CA 2072702 A CA2072702 A CA 2072702A CA 2072702 A1 CA2072702 A1 CA 2072702A1
- Authority
- CA
- Canada
- Prior art keywords
- resin composition
- photosensitive resin
- aqueous
- carboxyl group
- water
- 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.)
- Abandoned
Links
- 239000011342 resin composition Substances 0.000 title claims description 44
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- -1 amine compound Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000004018 acid anhydride group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- FDUFQLNPPGRIKX-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CC(C)(CO)CO FDUFQLNPPGRIKX-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-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
- KOTFYSVFYYKCRA-UHFFFAOYSA-N 2-(diethylamino)-1-phenylethanone Chemical compound CCN(CC)CC(=O)C1=CC=CC=C1 KOTFYSVFYYKCRA-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-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
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- WWMQIJFJSHVMDM-UHFFFAOYSA-N 2-ethenoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC=C WWMQIJFJSHVMDM-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- CKKQLOUBFINSIB-UHFFFAOYSA-N 2-hydroxy-1,2,2-triphenylethanone Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C(=O)C1=CC=CC=C1 CKKQLOUBFINSIB-UHFFFAOYSA-N 0.000 description 1
- RZCDMINQJLGWEP-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpent-4-en-1-one Chemical compound C=1C=CC=CC=1C(CC=C)(O)C(=O)C1=CC=CC=C1 RZCDMINQJLGWEP-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 241000272470 Circus Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- AJCHRUXIDGEWDK-UHFFFAOYSA-N bis(ethenyl) butanedioate Chemical compound C=COC(=O)CCC(=O)OC=C AJCHRUXIDGEWDK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
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
- G03F7/027—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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An aqueous-based photosensitive resin for the production of printed circuit boards is disclosed.
An aqueous-based photosensitive resin for the production of printed circuit boards is disclosed.
Description
- 2 - 20727~2 Field of the IRve~ltiol~
This invention relates to a method of preparing a printed circuit board by using an aqueous photosensitive resin composition and a method of preparing the aqueous photosensitive resin composition.
Ba~Xaround of the In~ention Heretofore, in the preparation of a printed circuit board, generally a photosensitive film is coated on a laminated board which has been lined with an electrically conductive metal foil such as a copper foil. The coated board is then irradiated with actinic light through a negative and developed. Then, unnecessary portions of the metal foil, i.e., those not forming part of the circu~t pattern, are etched and the photosensitive ilm is stripped. The result is a printed circuit on the laminated board. The board itself acts as an insulat~r. The photosensitive film used in such a method is fairly thick, and accordingly, causes problems such as decreased sharpness of the circuit pattern formed after the irradiation and development, difficulty of uniformly coating the photosensitive film on the metal foil and high cost of the photosensitive film. Another method of preparing a printed circuit board is to coat a liquid photosensitive resin composition directly on a substrate and dry it to form a photo-curable coating.
Since the photosensitive resin composition used for this purpose is dissolved or dispersed in an organic solvent, the organic solvent will create a problem in the working environment and accordingly, this method is hardly acceptable~
This invention relates to a method of preparing a printed circuit board by using an aqueous photosensitive resin composition and a method of preparing the aqueous photosensitive resin composition.
Ba~Xaround of the In~ention Heretofore, in the preparation of a printed circuit board, generally a photosensitive film is coated on a laminated board which has been lined with an electrically conductive metal foil such as a copper foil. The coated board is then irradiated with actinic light through a negative and developed. Then, unnecessary portions of the metal foil, i.e., those not forming part of the circu~t pattern, are etched and the photosensitive ilm is stripped. The result is a printed circuit on the laminated board. The board itself acts as an insulat~r. The photosensitive film used in such a method is fairly thick, and accordingly, causes problems such as decreased sharpness of the circuit pattern formed after the irradiation and development, difficulty of uniformly coating the photosensitive film on the metal foil and high cost of the photosensitive film. Another method of preparing a printed circuit board is to coat a liquid photosensitive resin composition directly on a substrate and dry it to form a photo-curable coating.
Since the photosensitive resin composition used for this purpose is dissolved or dispersed in an organic solvent, the organic solvent will create a problem in the working environment and accordingly, this method is hardly acceptable~
3 20727~2 The preparation of a printed circuit board by the electrodeposition technique has attracted a tremendous attention in recent years. Such a method not only requires expensive facilities, but also has a problem that maintenance of the electrodeposition fluid is difficult.
Bu~ary of the Invention It is an object of the present invention to provide a method of preparing a printed circuit board by using an aqueous photosensitive resin composition.
The resin image is sharp and has good resistance to an acidic etching solution after it has been irradiated with actinic light and developed with water or an aqueous alkaline solution. Furthermore, significant cost savings can be had over the electrodeposition technique, and organic solvents are not required.
Another aspect of the present invention is that this method of preparing a photosensitive resin has no adverse effect on the working environment or natural environment, does not require sa~ety precautions ayainst fire during the c~ating and drying steps, and does not require any solvent recovery system.
A method of preparing a printed circuit board in accordance with the invention comprises the steps of:
(1) coating an aqueous photosensitive resin composition on an insulating substrate having an electrically conductive metal layer thereon to form a photo-curable coating. The aqueous photosensitive resin composition is made of (a) a carboxyl group-containing resin having an acid value of 20 to 500, a number average molecular weight o~ l,000 at lO0,000 and a - 4 - ~ ~727 glass transition temperature, ("Tg") of at least 0C, (b) an amine compound, (c) a photo-curable unsaturated compound having at least two ethylenically unsaturated bonds, (d) a photopolymerization initiator and (e) water as the solvent or the dispersing medium;
(2) drying the coating;
(3) imagewise irradiating the coating with actinic light;
(4) developing the irradiated coating with water or an aqueous alkaline solution; and (5) etching the portions of the electrically conductive metal layer other than image portions with an acidic etching solution.
In another aspect of the invention a method of preparing an aqueous photosensitive resin composition is mixing or dispersing ~a) a carboxyl group-containing re~in, (b) an amine compound, (c) a photo-curable unsaturated compound and (d) a photopolymerization initiator in water.
et~ile~ Desari~ion o~ ~he Invent~on The carboxyl group-containing resin used in the present invention is any conventional resin having an acid value of 20 to 500, a number average molecular weight of 1,000 to 100,000, and a Tg of not less than 0C. When the acid value is lower than 20, its a~finity to water will be decreased even in the presence o~ an amine compound, and thus, it is _ 5 - 2~727~2 difficult to obtain the aqueous photosensitive resin composition of the present invention. On the other hand, when the acid value exceeds 500, it will be difficult to obtain a clear image by development with water or an aqueous alkaline solution because i~s affinity to water is too high. When the number average molecular weight is less than 1,000, the mechanical strength of the unexposed photosensitive resin coating will be decreased, and the coating may be easily damaged in the irradiation step. On the other hand, when the number average molecular weight exceeds 100,000, the viscosity of thP photosensitive resin composition will be remarkably increa~ed. As a result, the dissolving or mixing step is more difficult, and also the developing time will be increased. The Tg of the carboxyl group-containing resin of lower than 0C tends to increase the stickiness of the photosensitive resin composition and causes a problem in the irradiation step.
Resins obtained by copolymerizing acrylic acid or methacrylic acid with an unsaturated monomer such as a ~meth)acrylic acid ester, styrene, (meth)acrylonitrile or asrylamide and acid anhydride group-containing resins such as a styrene-maleic anhydride polymer whose acid anhydride groups have been ring-opened with water, an alcohol or an amine can be included in preferred examples of the carboxyl group-containing resin of the present invention.
Although any conventional alcohols can be used to ring-open the acid anhydride groups of the resin, it is preerred to use a primary or secondary alcohol due to their reactivity. For example, methyl alcohol, ethyl alcohol, butyl alcohol, butoxy ethanol and ethyleneglycol monomethyl ether can be used. Also, 20727~2 primary amines and secondary amines can be used for this purpose. Examples of such amines include ammonia; alkylamines such as diethylamine, monoethylamine, diisopropylemine and diisobutylamine;
alkanolamines such as monoethanolamine and diethanolamine; alkylalkanol amines such as dimethylamino ethanol; and alicycilc amines such as cyclohexylamine.
Preferred ~arboxyl group-containing resins which can be used in the photosensitive composition of the present invention have a polymerizable unsaturated bond in the molecule. Such resins can be synthesized by any known method, for example, by esterifying part of the carboxyl groups of the carboxyl group containing resin with glycidyl acrylate in the presence of a catalyst. Or, alcohols or amines having a polymerizable unsaturated bond can be used as the alcohol or the amine to ring-open the acid anhydride groups of the above described styrene- maleic anhydride polymer. Examples of ~3uch alcohols and amines suitable for such a purpo~;e are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol and allylamine.
The photosensitive resin composition of the present invention also includes an amine compound for the purpose of dissolving or dispersing the carboxyl group-containing resin in water. Any conventional amine compounds can be used for this purpose.
Examples of such amine compounds include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine and diisobutylamine; alkylalkanolamines such as dimethylaminoethanol; alicyclic amines such as 2~727~2 cyclohexylamine; and ammonia. ~mine compounds having a polymerizable unsaturated ~ond in the molecule are particularly preferred for such a purpose and examples of such amine compounds include dimethylaminopropyl acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and allylamine. To reduce generation of amine odor in the coating and drying steps, amine compounds having a boiling point of at least 100C are preferred. The amount of the amine compound which can be employed in the present invention is typically 0.2 to 2 mols per mol of the free carboxyl group of the carboxyl group-containing resin. The type photocurable unsaturated compound which can be incorporated in the photosensitive composition of the present invention i~ one having at least two ethylenically unsaturated bonds in the molecule. Examples of such ethylenically unsaturated compounds include (meth)acrylic acid esters, allyl compounds, vinyl ethers, vinyl esters and cinnamic acid esters. Examples o~ the (meth)acrylic acid esters include epoxy (meth)acrylates obtained by the reaction of an epoxy resin having two or more functional groups and a carboxylic acid having an ethylenically unsaturated bond; urethane (meth)acrylates obtained by the reaction of a polyvalent aliphatic isocyanate or a polyvalent aromatic isocyanate and a monoester of (meth)acrylic acid with a divalent alcohol; and (meth)acrylates of a polyvalent alcohol. Examples of tha allyl compound include diallyl esters of phthalic acid, adipic acid and malonic acid. Examples of the vinyl ethers include vinyl ethers of a polyvalent alcohol.
Examples of the vinyl esters include divinyl succinate and vinyl phthalate. In addition, the so-called - 8 - 2 ~ 72 7 ~ 2 mono-functional monomers having one ethylenically unsaturated bond can be used together with the above described photo-curable unsaturated compound. The amount of the photo-curable unsaturated compound which can be used in the present invention is typically 0.2 to 3 times the total weight of the carboxyl group-containing resin.
According to another embodiment of the present invention, an aqueous photosensitive resin composition can be obtained by using a carboxyl group-containing resin and/or an amine compound which has a photopolymerizable unsaturated bond instead of or together with the above described photo-curable unsaturated compound. Such an aqueous photosensitive resin composition can form an image when coated, dried on a substrate and then developed with water or an aqueous alkaline solution after irradiation with actinic light, and can form a photo-curable coating having good resistance to an acidic etching solution.
Any conventional photopolymerization initiators can be used as the photopolymerization initiator in the photosensitive composition o~ the present invention.
For example, benzophenones such as benzophenone, benzophenone methyl ether and Michler's ketone;
~5 benzoins such as benzoin, alpha-methylbenzoin, alpha-phenylbenzoin, alpha-allylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin isobutyl ether;
acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-p~enylacetophenone and N,N-diethylaminoacetophenone; benzil; k~tals such as benzyl dimethyl ketal; anthraquinones such as 2-- 9 - 2~727~2 methylanthraquinone, 2-ethylanthraquinone, 2-amylan-thraquinone and 2-aminoanthraquinone; and thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone can be preferably used~ The amount of this photopolymerization initiator to be added in the photosensitive resin composition is typically 0.10 to lO~ by weight based on the total weight of the photosensitive composition.
It is preferred to employ an appropriate polymerization inhibitor in the photosensitive resin composition of the present invention. Any conventional inhibitors can be used as such a polymerization inhibitor. Preferred examples of polymerization inhlbitors are phenols such as 2,4-dimethyl-6-tert-butylphenol and 2,6-di-tert-butyl-p-cresol; hydroguinones such as hydroquinone, methylhydroquinone, 1,4-benzo~uinone and hydroquinone monomethyl ether; and catechols such as tert-butylcatechol and pyrogallol. The amount of the polymerization inhibitors which can be used is typically 0.001 to 5% by weight based on the total weight o~ the photosensitive resin composition.
Any conventional appropriate surfactants may be added to improve the dispersibility resins in water.
For this purpose, anionic, cationic or nonionic surfactants can be used. If desired or necessary, the resin may be mixed with a known filler such as barium sulfate, silicon oxide, talc, clay and barium carbonate; a known coloring agent such as phthalocyanin green and titanium oxide; a dye; a leveling agent; an adhesion promotor; thixotropic agent; and a plasticizer.
The amount of water which can be employed in the lo- 2~7~7~
photosensitive resin composition is 30 to 90% by weight based on the total weight of the photosensitive resin composition, and the total amount of the carboxyl group-containing resin, the amine compound, the photo-curable unsaturated compound, the photopolymerization initiator and, if desired, other additives which can be employed in the photosensitive resin composition is 10 to 70% by weight based on the total weight of the photosensitive resin composition.
The aqueous photosensitive resin composition of the present invention can easily be prepared by the following methods which are given for illustrative purposes and are not meant to limit the invention.
(1) A carboxyl group-containing resin or an acid anhydride group-containing resin is mixed with water containing an amine compound and heated to dissolve or disperse the resin in water. Then a photo-curable unsaturated compound and a photopolymerization initiator are added to the resulting solution or dispersion, and the solution or dispersion is mixed and dispersed.
(2) After a carboxyl group-containing resin or an acid anhydride group-containing resin is dissolved in a photo-curable unsaturated compound under heating, a photopolymer-zation initiator is added to the resulting solution and then the water containing an amine compound is blended in.
(3) An acid anhydride group-containing resin and an alcohol or an amine compound are reacted with a photocurable unsaturated compound to ring-open the acid anhydride groups. Then, a photopolymerization initiator and 20727~2 subsequently, water containing an amine compound are mixed into the reaction solution and the solution.
(4) An acid anhydride group-containing resin and an alcohol or an amine compound having a polymerizable unsaturated bond are reacted, if desired, in a photo-curable unsaturated compound to ring-open the acid anhydride groups to introduce an unsaturated group in the resin~ Then, a photopolymerization initiator and subsequently, water containing an amine compound are blended into the reaction solution~
(5) An acid anhydride group-containing resin and a primary or a secondary amine are reacted in water to rin~-open the acid anhydride groups, and then an amine compound to render the resin easily dissolved or dispersed in wat~r, a photo-curable unsaturated compound and a photopolymerization initiator are added to the reaction solution, and the solution or dispersion is mixed. These components which are to be added later may be previously added in the reaction system and the ring-opening reaction may be carried out in the presence o~ these components.
or, an amine compound having a polymerizable unsaturated bond may be used as the amine compound to ring-open the acid anhydride groups and/or as the amine compound to render the resin easily dissolved or dispersed in water.
The aqueous photosensitive resin composition o~
the present inventic3n can ba prepared by the methods - 12 - 20 72 7~2 as described above without using any volatile organic solvent. However, a small amount, at most 20~ by weight, based on the total weight of the water, o~ a volatile organic solvent such as ethanol may be used to lower the viscosity of the photosensitive resin composition.
The preparation of a printed circuit board by using the aqueous photosensitive resin composition of the present invention can be typically carried out in the following manner.
The aqueous photosensitive resin composition of the present invention is coated on a substrate having an electrically conductive metal layer such as a copper foil. Coating can be done by any conventional device such as an ordinary curtain coater, roll coater, screen coater or electrostatic coater. Any conventional dryer may be used, if needed. In this case, since the aqueous photosensitive resin composition of the present invention contains no volatile organic solvent or contains a very amall amount of such an organic solvent, no special measures for protecting the working environment from fire or explosion are required, and neither is a solv~-nt recovery system.
As with any other conventional photosensitive resist materials, the resist image-forming step is carried out by the irradiativn of the coating with actinic light having a wavelength of 200 to 600 nm.
Preferred light sources include a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a car~on arc lamp and a chemical lamp. The developing step after the irradiation can easily be carried out by an ordinary procedure using water or a dilute aqueous alkaline solution, for example, a 1~ by - 13 - 2~727~2 weight sodium hydroxide solution.
The etching step for forming a circuit can be carried out with an ordinary acidic etching solution such as an aqueous hydrochloric acid solution of cupric chloride. A dilute aqueous alkaline solution such as a 3% by weight sodium hydroxide solution can be used to strip the resist coating after the etching.
Surprisingly, the aqueous photosensitive resin composition of the present invention can form an image when coated and dried on a substrate, irradiated with actinic light and developed with water or an aqueous alkaline water resin despite its ability to dissolve or disperse in water and the presence of an amine compound. In addition, the irradiated coating has a good resistance to an acidic etching solution. Since it does not contain any organic solvent at all or contains only a very small amount of an organic solvent, there is no need to provide safety precautions against fire in the coating and drying steps. Furthermore, it has no adverse effect on the working environment or natural environment which might be caused by organic solvents.
The examples which follow are given for illustrative purposes and are not meant to limit the invention described herein. "Part" means "part by weight" unless otherwise expressly stated.
Ex~pls 1 One hundred parts of an aqueous acrylic resin (I'CARBOSET XL-27", a product of B.F. Goodrich Co., U.S.A., acid value = 80, molecular weight = 40,000) as the carboxyl gxoup-containing resin, 14.4 parts of triethylamine as the amine compound and 330 parts of - 14 - 20727~2 water were mixed and heated at 70C to obtain a homogeneous and clear solution. Thirty three parts of trimethylolpropane triacrylate as the photopolymerizable unsaturated compound, 15 parts of 2,2-dimethoxy-2-phenylacetophenone as the polymerization initiator and 0.5 part of hydroquinone monomethyl ether as the polymerization inhibitor were added to the solution, and then the mixture was cooled to room temperature with agitation to ~orm an opaque, creamy aqueous photosensitive resin.
The resin was coated on a laminated board having an 18 micron copper foil layer using a doctor blade, and dried at 100C for 5 minutes to give a dri~d film having a thickness of about 20 microns.
A negative film was tightly contacted with the dried film with rays from a high pressure mercury lamp at an exposure energy of 400 mJfcm2, and then, developed b~ spraying with a 1% by weight aqueous sodium carbonate solution at 25C to give a resist film with a clear image showiny a line width as small as 50 microns.
The copper-lined laminated board having the resist film was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature for 20 minutes. With the exclusion of the area of the resist film, the copper foil was etched and removed. There was no damage to the resist ~ilm. Furthermore, the laminated board obtained after the etching was soaked in a 3~ by weight aqueous sodium hydroxide solution at room temperature for one minute. As a result, the resist ~ilm could bP easily stripped to give a circuit board.
- 15 - 2~727~2 ~x~mpl~ 2 The procedure of Example 1 was repeated except that 22.3 parts of dimethylaminopropyl acrylamide were employed instead of the triethylamine to obtain an opaque, creamy, aqueous photosensitive resin composition.
When the subsequent coating, drying, irradiation with light and development were carried out under the same conditions as in Example 1, a resist image which had reproduced clearly to a line width of 30 microns was obtained. In the same manner as in Example 1, etching and stripping of the resist film after the etching could be carried out without any problem.
~x .am~
A mixture containing 150 pa:rts of a styrene-maleic anhydride copolymlsr ('ISMA--lOOo", styrene/maleic anhydride = 1/1, a product o~ Sartomer CO. I U~ SoA~ ) ~ 150 parts o~ trimethylolpropane triacrylate, 54 parts of butyl alcohol, 8 parts of dimethylolpropane triacrylate, 47 parts of N-butylbenzene sulfonamide as the plasticizer and 0.5 part of hydroquinone monomethyl ether was heated and agitated at 80C for 2 hours to obtain a viscous substance. Four parts of a surfactant ("EMULGEN 903", a product of Kao K.K., Japan), 20 parts of 2,~.-dimethoxy-2-phenylacetophenone and 35 parts of ethyl alcohol as the solvent were added to the viscous substance, and then th~ mixture was cooled to room temperature. Furthermore, 55 parts of dimethylamino~
propyl acrylamide were added in 300 parts of watex to prepare a solution. This solution was added to the - 16 - 2~72~2 above obtained mixture with constant and vigorous agitation to yield an aqueous photosensitive resin.
The resin was coated on a laminated board having a 18 micron thick copper foil layer using a doctor blade, and then dried at 100C for 5 minutes to give a dried film having a thickness of about 20 microns.
A negative film was contacted with the dried film, irradiated with rays from a high pressure mercury lamp at an exposure energy of 400 mJ/cm2, and then developed with tap water at 25C to give a resist film having a clear image which showed a line width of 50 microns.
When the copper-lined laminated board having the resist ~ilm was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature f or 20 minutes, the copper foil was etched and removed except the area of the resist film, and there was no damage in the resist film. Furthermore, when the laminated, etched board was subsequently soaked in a 3% by weight aqueous sodium hydroxide solution at room temperature for one minute, the resist film could be easily striped to give a circuit board.
~xAmpla 4 The procedure of Example 3 was repeated except that 85 parts of hydroxyethyl acrylate to ring-open the acid anhydride groups to introduce a double bond in the resin were employed instead of the butyl alcohol to prepare an aqueous photosensitive resin composition~ When the subsequent coating, drying, irradiation with actinic light and development with - 17 - 2~727~2 tap water were carried out under the same conditions as in Example 3, a resist image which had repro~uced an image clearly to a line width of 30 microns was obtained. In the same manner as in Example 3, the resist film could be etched and stripped without any problem.
E~nmple 5 A mixture containing 150 parts of a styrene-maleic anhydride copolymer ("SMA-20001', styrene/maleic anhydride = 2/1, a product of Sartomer Co., ~.S.A.), 150 parts of trimethylolpropane triacrylata, 28 parts of allylamine ~or ring-opening of the acid anhydride groups in the above described copolymer to introduce a photopolymerizable unsaturated bond in the resin, 77 parts of dimethylaminoethyl methacrylate, 47 parts of N-butylbenzene sulfonamide as the plasticizer, 0.5 part of hydroquinone monomethyl ether as the polymerization inhibitor, ~0 parts of 2,2-dimethoxy-~-phenylacetophenone and 300 parts of water was agitat2d at room temperature for 3 hours, and then the mixture was heated and agitated at 80C for one hour to obtain an aqueous photosensitive resin composition.
The composition was coated on a laminated board having a 18 micron thick coppar foil layer using a doctor blade, and then drisd at 100C for 5 minutes to give a dried ~ilm having a ~hickness of about 20 microns.
A negative film was tightly contacted with the dried film, and irradiated with rays from a high pressure mercury lamp at an exposure enargy of 200 - 18 - 2~727~2 mJ/cm2, and then developed by spraying with a 1% by weight aqueous sodium carbonate solution at 25C to give a resist film having a clear image with a line width of 30 microns.
When the copper-lined laminated board formed with a resist film was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature for 20 minutes, the copper foil was etched and remo~ed except the area of the resist film which did not show any damage.
Furthermore, when the laminated, etched board was soaked in a 3~ by weight aqueous sodium hydroxide solution at room temperature for one minute, the ~esist film could be easily stripped to give a circuit board.
Bu~ary of the Invention It is an object of the present invention to provide a method of preparing a printed circuit board by using an aqueous photosensitive resin composition.
The resin image is sharp and has good resistance to an acidic etching solution after it has been irradiated with actinic light and developed with water or an aqueous alkaline solution. Furthermore, significant cost savings can be had over the electrodeposition technique, and organic solvents are not required.
Another aspect of the present invention is that this method of preparing a photosensitive resin has no adverse effect on the working environment or natural environment, does not require sa~ety precautions ayainst fire during the c~ating and drying steps, and does not require any solvent recovery system.
A method of preparing a printed circuit board in accordance with the invention comprises the steps of:
(1) coating an aqueous photosensitive resin composition on an insulating substrate having an electrically conductive metal layer thereon to form a photo-curable coating. The aqueous photosensitive resin composition is made of (a) a carboxyl group-containing resin having an acid value of 20 to 500, a number average molecular weight o~ l,000 at lO0,000 and a - 4 - ~ ~727 glass transition temperature, ("Tg") of at least 0C, (b) an amine compound, (c) a photo-curable unsaturated compound having at least two ethylenically unsaturated bonds, (d) a photopolymerization initiator and (e) water as the solvent or the dispersing medium;
(2) drying the coating;
(3) imagewise irradiating the coating with actinic light;
(4) developing the irradiated coating with water or an aqueous alkaline solution; and (5) etching the portions of the electrically conductive metal layer other than image portions with an acidic etching solution.
In another aspect of the invention a method of preparing an aqueous photosensitive resin composition is mixing or dispersing ~a) a carboxyl group-containing re~in, (b) an amine compound, (c) a photo-curable unsaturated compound and (d) a photopolymerization initiator in water.
et~ile~ Desari~ion o~ ~he Invent~on The carboxyl group-containing resin used in the present invention is any conventional resin having an acid value of 20 to 500, a number average molecular weight of 1,000 to 100,000, and a Tg of not less than 0C. When the acid value is lower than 20, its a~finity to water will be decreased even in the presence o~ an amine compound, and thus, it is _ 5 - 2~727~2 difficult to obtain the aqueous photosensitive resin composition of the present invention. On the other hand, when the acid value exceeds 500, it will be difficult to obtain a clear image by development with water or an aqueous alkaline solution because i~s affinity to water is too high. When the number average molecular weight is less than 1,000, the mechanical strength of the unexposed photosensitive resin coating will be decreased, and the coating may be easily damaged in the irradiation step. On the other hand, when the number average molecular weight exceeds 100,000, the viscosity of thP photosensitive resin composition will be remarkably increa~ed. As a result, the dissolving or mixing step is more difficult, and also the developing time will be increased. The Tg of the carboxyl group-containing resin of lower than 0C tends to increase the stickiness of the photosensitive resin composition and causes a problem in the irradiation step.
Resins obtained by copolymerizing acrylic acid or methacrylic acid with an unsaturated monomer such as a ~meth)acrylic acid ester, styrene, (meth)acrylonitrile or asrylamide and acid anhydride group-containing resins such as a styrene-maleic anhydride polymer whose acid anhydride groups have been ring-opened with water, an alcohol or an amine can be included in preferred examples of the carboxyl group-containing resin of the present invention.
Although any conventional alcohols can be used to ring-open the acid anhydride groups of the resin, it is preerred to use a primary or secondary alcohol due to their reactivity. For example, methyl alcohol, ethyl alcohol, butyl alcohol, butoxy ethanol and ethyleneglycol monomethyl ether can be used. Also, 20727~2 primary amines and secondary amines can be used for this purpose. Examples of such amines include ammonia; alkylamines such as diethylamine, monoethylamine, diisopropylemine and diisobutylamine;
alkanolamines such as monoethanolamine and diethanolamine; alkylalkanol amines such as dimethylamino ethanol; and alicycilc amines such as cyclohexylamine.
Preferred ~arboxyl group-containing resins which can be used in the photosensitive composition of the present invention have a polymerizable unsaturated bond in the molecule. Such resins can be synthesized by any known method, for example, by esterifying part of the carboxyl groups of the carboxyl group containing resin with glycidyl acrylate in the presence of a catalyst. Or, alcohols or amines having a polymerizable unsaturated bond can be used as the alcohol or the amine to ring-open the acid anhydride groups of the above described styrene- maleic anhydride polymer. Examples of ~3uch alcohols and amines suitable for such a purpo~;e are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol and allylamine.
The photosensitive resin composition of the present invention also includes an amine compound for the purpose of dissolving or dispersing the carboxyl group-containing resin in water. Any conventional amine compounds can be used for this purpose.
Examples of such amine compounds include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine and diisobutylamine; alkylalkanolamines such as dimethylaminoethanol; alicyclic amines such as 2~727~2 cyclohexylamine; and ammonia. ~mine compounds having a polymerizable unsaturated ~ond in the molecule are particularly preferred for such a purpose and examples of such amine compounds include dimethylaminopropyl acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and allylamine. To reduce generation of amine odor in the coating and drying steps, amine compounds having a boiling point of at least 100C are preferred. The amount of the amine compound which can be employed in the present invention is typically 0.2 to 2 mols per mol of the free carboxyl group of the carboxyl group-containing resin. The type photocurable unsaturated compound which can be incorporated in the photosensitive composition of the present invention i~ one having at least two ethylenically unsaturated bonds in the molecule. Examples of such ethylenically unsaturated compounds include (meth)acrylic acid esters, allyl compounds, vinyl ethers, vinyl esters and cinnamic acid esters. Examples o~ the (meth)acrylic acid esters include epoxy (meth)acrylates obtained by the reaction of an epoxy resin having two or more functional groups and a carboxylic acid having an ethylenically unsaturated bond; urethane (meth)acrylates obtained by the reaction of a polyvalent aliphatic isocyanate or a polyvalent aromatic isocyanate and a monoester of (meth)acrylic acid with a divalent alcohol; and (meth)acrylates of a polyvalent alcohol. Examples of tha allyl compound include diallyl esters of phthalic acid, adipic acid and malonic acid. Examples of the vinyl ethers include vinyl ethers of a polyvalent alcohol.
Examples of the vinyl esters include divinyl succinate and vinyl phthalate. In addition, the so-called - 8 - 2 ~ 72 7 ~ 2 mono-functional monomers having one ethylenically unsaturated bond can be used together with the above described photo-curable unsaturated compound. The amount of the photo-curable unsaturated compound which can be used in the present invention is typically 0.2 to 3 times the total weight of the carboxyl group-containing resin.
According to another embodiment of the present invention, an aqueous photosensitive resin composition can be obtained by using a carboxyl group-containing resin and/or an amine compound which has a photopolymerizable unsaturated bond instead of or together with the above described photo-curable unsaturated compound. Such an aqueous photosensitive resin composition can form an image when coated, dried on a substrate and then developed with water or an aqueous alkaline solution after irradiation with actinic light, and can form a photo-curable coating having good resistance to an acidic etching solution.
Any conventional photopolymerization initiators can be used as the photopolymerization initiator in the photosensitive composition o~ the present invention.
For example, benzophenones such as benzophenone, benzophenone methyl ether and Michler's ketone;
~5 benzoins such as benzoin, alpha-methylbenzoin, alpha-phenylbenzoin, alpha-allylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin isobutyl ether;
acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-p~enylacetophenone and N,N-diethylaminoacetophenone; benzil; k~tals such as benzyl dimethyl ketal; anthraquinones such as 2-- 9 - 2~727~2 methylanthraquinone, 2-ethylanthraquinone, 2-amylan-thraquinone and 2-aminoanthraquinone; and thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone can be preferably used~ The amount of this photopolymerization initiator to be added in the photosensitive resin composition is typically 0.10 to lO~ by weight based on the total weight of the photosensitive composition.
It is preferred to employ an appropriate polymerization inhibitor in the photosensitive resin composition of the present invention. Any conventional inhibitors can be used as such a polymerization inhibitor. Preferred examples of polymerization inhlbitors are phenols such as 2,4-dimethyl-6-tert-butylphenol and 2,6-di-tert-butyl-p-cresol; hydroguinones such as hydroquinone, methylhydroquinone, 1,4-benzo~uinone and hydroquinone monomethyl ether; and catechols such as tert-butylcatechol and pyrogallol. The amount of the polymerization inhibitors which can be used is typically 0.001 to 5% by weight based on the total weight o~ the photosensitive resin composition.
Any conventional appropriate surfactants may be added to improve the dispersibility resins in water.
For this purpose, anionic, cationic or nonionic surfactants can be used. If desired or necessary, the resin may be mixed with a known filler such as barium sulfate, silicon oxide, talc, clay and barium carbonate; a known coloring agent such as phthalocyanin green and titanium oxide; a dye; a leveling agent; an adhesion promotor; thixotropic agent; and a plasticizer.
The amount of water which can be employed in the lo- 2~7~7~
photosensitive resin composition is 30 to 90% by weight based on the total weight of the photosensitive resin composition, and the total amount of the carboxyl group-containing resin, the amine compound, the photo-curable unsaturated compound, the photopolymerization initiator and, if desired, other additives which can be employed in the photosensitive resin composition is 10 to 70% by weight based on the total weight of the photosensitive resin composition.
The aqueous photosensitive resin composition of the present invention can easily be prepared by the following methods which are given for illustrative purposes and are not meant to limit the invention.
(1) A carboxyl group-containing resin or an acid anhydride group-containing resin is mixed with water containing an amine compound and heated to dissolve or disperse the resin in water. Then a photo-curable unsaturated compound and a photopolymerization initiator are added to the resulting solution or dispersion, and the solution or dispersion is mixed and dispersed.
(2) After a carboxyl group-containing resin or an acid anhydride group-containing resin is dissolved in a photo-curable unsaturated compound under heating, a photopolymer-zation initiator is added to the resulting solution and then the water containing an amine compound is blended in.
(3) An acid anhydride group-containing resin and an alcohol or an amine compound are reacted with a photocurable unsaturated compound to ring-open the acid anhydride groups. Then, a photopolymerization initiator and 20727~2 subsequently, water containing an amine compound are mixed into the reaction solution and the solution.
(4) An acid anhydride group-containing resin and an alcohol or an amine compound having a polymerizable unsaturated bond are reacted, if desired, in a photo-curable unsaturated compound to ring-open the acid anhydride groups to introduce an unsaturated group in the resin~ Then, a photopolymerization initiator and subsequently, water containing an amine compound are blended into the reaction solution~
(5) An acid anhydride group-containing resin and a primary or a secondary amine are reacted in water to rin~-open the acid anhydride groups, and then an amine compound to render the resin easily dissolved or dispersed in wat~r, a photo-curable unsaturated compound and a photopolymerization initiator are added to the reaction solution, and the solution or dispersion is mixed. These components which are to be added later may be previously added in the reaction system and the ring-opening reaction may be carried out in the presence o~ these components.
or, an amine compound having a polymerizable unsaturated bond may be used as the amine compound to ring-open the acid anhydride groups and/or as the amine compound to render the resin easily dissolved or dispersed in water.
The aqueous photosensitive resin composition o~
the present inventic3n can ba prepared by the methods - 12 - 20 72 7~2 as described above without using any volatile organic solvent. However, a small amount, at most 20~ by weight, based on the total weight of the water, o~ a volatile organic solvent such as ethanol may be used to lower the viscosity of the photosensitive resin composition.
The preparation of a printed circuit board by using the aqueous photosensitive resin composition of the present invention can be typically carried out in the following manner.
The aqueous photosensitive resin composition of the present invention is coated on a substrate having an electrically conductive metal layer such as a copper foil. Coating can be done by any conventional device such as an ordinary curtain coater, roll coater, screen coater or electrostatic coater. Any conventional dryer may be used, if needed. In this case, since the aqueous photosensitive resin composition of the present invention contains no volatile organic solvent or contains a very amall amount of such an organic solvent, no special measures for protecting the working environment from fire or explosion are required, and neither is a solv~-nt recovery system.
As with any other conventional photosensitive resist materials, the resist image-forming step is carried out by the irradiativn of the coating with actinic light having a wavelength of 200 to 600 nm.
Preferred light sources include a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a car~on arc lamp and a chemical lamp. The developing step after the irradiation can easily be carried out by an ordinary procedure using water or a dilute aqueous alkaline solution, for example, a 1~ by - 13 - 2~727~2 weight sodium hydroxide solution.
The etching step for forming a circuit can be carried out with an ordinary acidic etching solution such as an aqueous hydrochloric acid solution of cupric chloride. A dilute aqueous alkaline solution such as a 3% by weight sodium hydroxide solution can be used to strip the resist coating after the etching.
Surprisingly, the aqueous photosensitive resin composition of the present invention can form an image when coated and dried on a substrate, irradiated with actinic light and developed with water or an aqueous alkaline water resin despite its ability to dissolve or disperse in water and the presence of an amine compound. In addition, the irradiated coating has a good resistance to an acidic etching solution. Since it does not contain any organic solvent at all or contains only a very small amount of an organic solvent, there is no need to provide safety precautions against fire in the coating and drying steps. Furthermore, it has no adverse effect on the working environment or natural environment which might be caused by organic solvents.
The examples which follow are given for illustrative purposes and are not meant to limit the invention described herein. "Part" means "part by weight" unless otherwise expressly stated.
Ex~pls 1 One hundred parts of an aqueous acrylic resin (I'CARBOSET XL-27", a product of B.F. Goodrich Co., U.S.A., acid value = 80, molecular weight = 40,000) as the carboxyl gxoup-containing resin, 14.4 parts of triethylamine as the amine compound and 330 parts of - 14 - 20727~2 water were mixed and heated at 70C to obtain a homogeneous and clear solution. Thirty three parts of trimethylolpropane triacrylate as the photopolymerizable unsaturated compound, 15 parts of 2,2-dimethoxy-2-phenylacetophenone as the polymerization initiator and 0.5 part of hydroquinone monomethyl ether as the polymerization inhibitor were added to the solution, and then the mixture was cooled to room temperature with agitation to ~orm an opaque, creamy aqueous photosensitive resin.
The resin was coated on a laminated board having an 18 micron copper foil layer using a doctor blade, and dried at 100C for 5 minutes to give a dri~d film having a thickness of about 20 microns.
A negative film was tightly contacted with the dried film with rays from a high pressure mercury lamp at an exposure energy of 400 mJfcm2, and then, developed b~ spraying with a 1% by weight aqueous sodium carbonate solution at 25C to give a resist film with a clear image showiny a line width as small as 50 microns.
The copper-lined laminated board having the resist film was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature for 20 minutes. With the exclusion of the area of the resist film, the copper foil was etched and removed. There was no damage to the resist ~ilm. Furthermore, the laminated board obtained after the etching was soaked in a 3~ by weight aqueous sodium hydroxide solution at room temperature for one minute. As a result, the resist ~ilm could bP easily stripped to give a circuit board.
- 15 - 2~727~2 ~x~mpl~ 2 The procedure of Example 1 was repeated except that 22.3 parts of dimethylaminopropyl acrylamide were employed instead of the triethylamine to obtain an opaque, creamy, aqueous photosensitive resin composition.
When the subsequent coating, drying, irradiation with light and development were carried out under the same conditions as in Example 1, a resist image which had reproduced clearly to a line width of 30 microns was obtained. In the same manner as in Example 1, etching and stripping of the resist film after the etching could be carried out without any problem.
~x .am~
A mixture containing 150 pa:rts of a styrene-maleic anhydride copolymlsr ('ISMA--lOOo", styrene/maleic anhydride = 1/1, a product o~ Sartomer CO. I U~ SoA~ ) ~ 150 parts o~ trimethylolpropane triacrylate, 54 parts of butyl alcohol, 8 parts of dimethylolpropane triacrylate, 47 parts of N-butylbenzene sulfonamide as the plasticizer and 0.5 part of hydroquinone monomethyl ether was heated and agitated at 80C for 2 hours to obtain a viscous substance. Four parts of a surfactant ("EMULGEN 903", a product of Kao K.K., Japan), 20 parts of 2,~.-dimethoxy-2-phenylacetophenone and 35 parts of ethyl alcohol as the solvent were added to the viscous substance, and then th~ mixture was cooled to room temperature. Furthermore, 55 parts of dimethylamino~
propyl acrylamide were added in 300 parts of watex to prepare a solution. This solution was added to the - 16 - 2~72~2 above obtained mixture with constant and vigorous agitation to yield an aqueous photosensitive resin.
The resin was coated on a laminated board having a 18 micron thick copper foil layer using a doctor blade, and then dried at 100C for 5 minutes to give a dried film having a thickness of about 20 microns.
A negative film was contacted with the dried film, irradiated with rays from a high pressure mercury lamp at an exposure energy of 400 mJ/cm2, and then developed with tap water at 25C to give a resist film having a clear image which showed a line width of 50 microns.
When the copper-lined laminated board having the resist ~ilm was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature f or 20 minutes, the copper foil was etched and removed except the area of the resist film, and there was no damage in the resist film. Furthermore, when the laminated, etched board was subsequently soaked in a 3% by weight aqueous sodium hydroxide solution at room temperature for one minute, the resist film could be easily striped to give a circuit board.
~xAmpla 4 The procedure of Example 3 was repeated except that 85 parts of hydroxyethyl acrylate to ring-open the acid anhydride groups to introduce a double bond in the resin were employed instead of the butyl alcohol to prepare an aqueous photosensitive resin composition~ When the subsequent coating, drying, irradiation with actinic light and development with - 17 - 2~727~2 tap water were carried out under the same conditions as in Example 3, a resist image which had repro~uced an image clearly to a line width of 30 microns was obtained. In the same manner as in Example 3, the resist film could be etched and stripped without any problem.
E~nmple 5 A mixture containing 150 parts of a styrene-maleic anhydride copolymer ("SMA-20001', styrene/maleic anhydride = 2/1, a product of Sartomer Co., ~.S.A.), 150 parts of trimethylolpropane triacrylata, 28 parts of allylamine ~or ring-opening of the acid anhydride groups in the above described copolymer to introduce a photopolymerizable unsaturated bond in the resin, 77 parts of dimethylaminoethyl methacrylate, 47 parts of N-butylbenzene sulfonamide as the plasticizer, 0.5 part of hydroquinone monomethyl ether as the polymerization inhibitor, ~0 parts of 2,2-dimethoxy-~-phenylacetophenone and 300 parts of water was agitat2d at room temperature for 3 hours, and then the mixture was heated and agitated at 80C for one hour to obtain an aqueous photosensitive resin composition.
The composition was coated on a laminated board having a 18 micron thick coppar foil layer using a doctor blade, and then drisd at 100C for 5 minutes to give a dried ~ilm having a ~hickness of about 20 microns.
A negative film was tightly contacted with the dried film, and irradiated with rays from a high pressure mercury lamp at an exposure enargy of 200 - 18 - 2~727~2 mJ/cm2, and then developed by spraying with a 1% by weight aqueous sodium carbonate solution at 25C to give a resist film having a clear image with a line width of 30 microns.
When the copper-lined laminated board formed with a resist film was soaked in an etching solution containing 40 parts of anhydrous cupric chloride, 30 parts of concentrated hydrochloric acid and 50 parts of water at room temperature for 20 minutes, the copper foil was etched and remo~ed except the area of the resist film which did not show any damage.
Furthermore, when the laminated, etched board was soaked in a 3~ by weight aqueous sodium hydroxide solution at room temperature for one minute, the ~esist film could be easily stripped to give a circuit board.
Claims (14)
1. A method of preparing a printed circuit board which comprises the steps of:
(1) coating an aqueous photosensitive resin composition on an insulating substrate having an electrically conductive metal layer thereon to form a photo-curable coating, said aqueous photosensitive resin composition comprising (a) a carboxyl group-containing resin having an acid value of 20 to 500, a number average molecular weight of 1,000 at 100,000 and a Tg of not lower than 0°C, (b) an amine compound, (c) photo-curable unsaturated compound having at least two ethylenically unsaturated bonds, (d) a photopolymerization initiator and (e) water as the solvent or the dispersing medium;
(2) drying said coating;
(3) imagewise irradiating said coating with actinic light;
(4) developing said coating thus obtained with water or an aqueous alkaline solution; and (5) etching portions of said electrically conductive metal layer other than image portions with an acidic etching solution.
(1) coating an aqueous photosensitive resin composition on an insulating substrate having an electrically conductive metal layer thereon to form a photo-curable coating, said aqueous photosensitive resin composition comprising (a) a carboxyl group-containing resin having an acid value of 20 to 500, a number average molecular weight of 1,000 at 100,000 and a Tg of not lower than 0°C, (b) an amine compound, (c) photo-curable unsaturated compound having at least two ethylenically unsaturated bonds, (d) a photopolymerization initiator and (e) water as the solvent or the dispersing medium;
(2) drying said coating;
(3) imagewise irradiating said coating with actinic light;
(4) developing said coating thus obtained with water or an aqueous alkaline solution; and (5) etching portions of said electrically conductive metal layer other than image portions with an acidic etching solution.
2. The method of Claim 1, wherein said carboxyl group-containing resin in said aqueous photosensitive resin composition has a photopolymerizable unsaturated bond.
3. The method of Claim 1, wherein said amine compound in said aqueous photosensitive resin composition has a polymerizable unsaturated bond.
4. The method of Claim 1, wherein said carboxyl group-containing resin in said aqueous photosensitive resin composition is a styrene-maleic anhydride copolymer whose acid anhydride groups have been ring-opened with an alcohol, a primary amine or a secondary amine.
5. The method of Claim 4, wherein said alcohol, said primary amine or said secondary amine has a polymerizable unsaturated bond.
6. The method of Claim 1, wherein said amine compound in said aqueous photosensitive resin composition is used in an amount of 0.2 to 2 mols per mol of the free carboxyl group of said carboxyl group-containing resin.
7. The method of Claim 1, wherein said photo-curable unsaturated compound in said aqueous photosensitive resin composition is used in an amount of 0.2 to 3 times the total weight of the carboxyl group-containing resin.
8. The method of Claim 1, wherein said photopolymerization initiator is used in an amount of 0.01 to 10% by weight of the total weight of the photosensitive resin composition.
9. The method of Claim 1, wherein said water in said aqueous photosensitive composition is used in an amount of 30 to 90% by weight based on the total weight of said aqueous photosensitive resin composition.
10. The method of Claim 1, wherein said aqueous photosensitive resin composition further comprises a polymerization inhibitor in an amount of 0.1 to 10% by weight of the total weight of the photosensitive resin composition.
11. A method of preparing an aqueous photosensitive resin composition comprises mixing or dispersing (a) a carboxyl group-containing resin, (b) an amine compound, (c) a photo-curable unsaturated compound and (d) a photopolymerization initiator in water.
12. The method of Claim 11 which comprises a step of ring-opening the acid anhydride groups of an acid anhydride group-containing resin with an alcohol, a primary amine or a secondary amine to form said carboxyl group-containing resin.
13. The method of Claim 12, wherein said alcohol, said primary amine or said secondary amine has a photopolymerizable unsaturated bond.
14. The method of Claim 11, wherein said water contains a volatile organic solvent in an amount of not greater than 20% by weight based on the weight of said water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3172247A JP3040202B2 (en) | 1991-07-12 | 1991-07-12 | Aqueous photosensitive resin composition and method for producing printed circuit board using the same |
| JP172247/91 | 1991-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2072702A1 true CA2072702A1 (en) | 1993-01-13 |
Family
ID=15938352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002072702A Abandoned CA2072702A1 (en) | 1991-07-12 | 1992-06-29 | Aqueous photosensitive resin composition and print obtained by using the same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3040202B2 (en) |
| CA (1) | CA2072702A1 (en) |
| GB (1) | GB2257711B (en) |
| HK (1) | HK22696A (en) |
| TW (1) | TW236071B (en) |
| ZA (1) | ZA924998B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06258832A (en) * | 1992-11-17 | 1994-09-16 | W R Grace & Co | Photosensitive resin composition |
| US5445919A (en) * | 1993-06-14 | 1995-08-29 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
| AU661438B1 (en) * | 1994-01-25 | 1995-07-20 | Morton International, Inc. | Waterborne photoresists having polysiloxanes |
| US5364737A (en) * | 1994-01-25 | 1994-11-15 | Morton International, Inc. | Waterbone photoresists having associate thickeners |
| AU660881B1 (en) * | 1994-01-25 | 1995-07-06 | Morton International, Inc. | Waterborne photoresists having binders neutralized with amino acrylates |
| AU660882B1 (en) * | 1994-01-25 | 1995-07-06 | Morton International, Inc. | Waterborne photoresists having non-ionic fluorocarbon surfactants |
| JPH08289942A (en) * | 1995-04-25 | 1996-11-05 | Yukio Tsunoda | Golf club |
| US5512607A (en) * | 1995-06-06 | 1996-04-30 | W. R. Grace & Co.-Conn. | Unsaturated epoxy ester with quaternary ammonium and phosphate groups |
| WO1996041240A1 (en) * | 1995-06-07 | 1996-12-19 | W.R. Grace & Co.-Conn. | Water photoresist emulsions and methods of preparation thereof |
| JPH0915857A (en) * | 1995-06-29 | 1997-01-17 | Hitachi Chem Co Ltd | Colored image forming material, photosensitive solution using it, photosensitive element, and manufacture of color filter |
| US20040265730A1 (en) * | 2001-12-03 | 2004-12-30 | Hiroshi Takahashi | Photosensitive composition and production processes for photosensitive film and printed wiring board |
| DE60322278D1 (en) | 2002-05-06 | 2008-08-28 | Sun Chemical Corp | Single-phase energy-curable water-based compositions |
| US7226959B2 (en) | 2003-11-06 | 2007-06-05 | Sun Chemical Corporation | Water soluble energy curable stereo-crosslinkable ionomer compositions |
| JP5624288B2 (en) * | 2009-06-30 | 2014-11-12 | 互応化学工業株式会社 | Manufacturing method of printed wiring board with through hole |
| DE112011101165T5 (en) | 2010-03-29 | 2013-03-28 | Mitsubishi Paper Mills Limited | Photosensitive composition and photosensitive lithographic printing plate material |
| JP7181775B2 (en) * | 2017-12-12 | 2022-12-01 | 三洋化成工業株式会社 | Aqueous (co)polymer composition |
| CN115197381B (en) * | 2022-09-16 | 2022-11-25 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD250593A1 (en) * | 1984-04-03 | 1987-10-14 | Wolfen Filmfab Veb | PHOTOPOLYMERIZABLE MATERIAL |
| PT85756A (en) * | 1986-09-22 | 1988-10-14 | Napp Systems Inc | PROCESS FOR THE PREPARATION OF PHOTOSENSIVE AND REVEALED SHEETS WITH WATER |
| EP0287019A3 (en) * | 1987-04-16 | 1990-07-11 | W.R. Grace & Co.-Conn. | Aqueous developable, radiation curable composition |
| EP0295944A3 (en) * | 1987-06-18 | 1989-09-06 | Napp Systems (Usa) Inc. | Photosensitive resin composition and printing plate prepared therefrom |
| US5403698A (en) * | 1990-10-16 | 1995-04-04 | Hitachi Chemical Company, Ltd. | Negative type photosensitive electrodepositing resin composition |
-
1991
- 1991-07-12 JP JP3172247A patent/JP3040202B2/en not_active Expired - Lifetime
-
1992
- 1992-06-29 CA CA002072702A patent/CA2072702A1/en not_active Abandoned
- 1992-07-06 ZA ZA924998A patent/ZA924998B/en unknown
- 1992-07-13 GB GB9214858A patent/GB2257711B/en not_active Expired - Fee Related
- 1992-07-21 TW TW081105764A patent/TW236071B/zh active
-
1996
- 1996-02-08 HK HK22696A patent/HK22696A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP3040202B2 (en) | 2000-05-15 |
| GB2257711B (en) | 1995-09-20 |
| HK22696A (en) | 1996-02-16 |
| TW236071B (en) | 1994-12-11 |
| GB2257711A (en) | 1993-01-20 |
| GB9214858D0 (en) | 1992-08-26 |
| ZA924998B (en) | 1994-09-26 |
| JPH0527437A (en) | 1993-02-05 |
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