JPH0235454A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH0235454A JPH0235454A JP18648388A JP18648388A JPH0235454A JP H0235454 A JPH0235454 A JP H0235454A JP 18648388 A JP18648388 A JP 18648388A JP 18648388 A JP18648388 A JP 18648388A JP H0235454 A JPH0235454 A JP H0235454A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- weight
- resin composition
- plating
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title description 27
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 34
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- -1 ethylene, propylene, butylene Chemical group 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 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
- 239000012965 benzophenone Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 2
- 229940107698 malachite green Drugs 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- INUMMPHTUPBOEU-UHFFFAOYSA-N 1-phenylacridine Chemical compound C1=CC=CC=C1C1=CC=CC2=NC3=CC=CC=C3C=C12 INUMMPHTUPBOEU-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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 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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- XFOHWECQTFIEIX-UHFFFAOYSA-N 2-nitrofluorene Chemical compound C1=CC=C2C3=CC=C([N+](=O)[O-])C=C3CC2=C1 XFOHWECQTFIEIX-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- ZXABMDQSAABDMG-UHFFFAOYSA-N 3-ethenoxyprop-1-ene Chemical class C=CCOC=C ZXABMDQSAABDMG-UHFFFAOYSA-N 0.000 description 1
- MQMCZRZPDPSXTD-UHFFFAOYSA-N 9-(4-methoxyphenyl)acridine Chemical compound C1=CC(OC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MQMCZRZPDPSXTD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 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
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- XPKFLEVLLPKCIW-UHFFFAOYSA-N ethyl 4-(diethylamino)benzoate Chemical compound CCOC(=O)C1=CC=C(N(CC)CC)C=C1 XPKFLEVLLPKCIW-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、感光性樹脂組成物に関し、さらに詳しくは、
例えば配線板の製造等に用いられる感光性樹脂組成物に
関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition, and more specifically,
For example, it relates to a photosensitive resin composition used for manufacturing wiring boards, etc.
（従来の技術）
配線板を製造するにあたって、支持フィルム層と感光層
と保護フィルム層とからなる３層構造のフィルム状フォ
トレジストを用いた技術が従来がら提案されている（例
えば、特開昭５８−１１４２号公報参照）。このフィル
ム状フォトレジストは、感光性樹脂組成物が溶解された
感光液を支持フィルム層に塗布乾燥することにより感光
層を形成し、その上に保護フィルム層を形成して作成さ
れるものである。(Prior art) In manufacturing wiring boards, a technology using a film-like photoresist with a three-layer structure consisting of a support film layer, a photosensitive layer, and a protective film layer has been proposed (for example, 58-1142). This film-like photoresist is produced by coating a supporting film layer with a photosensitive liquid in which a photosensitive resin composition is dissolved and drying it to form a photosensitive layer, and then forming a protective film layer thereon. .
ところで、最近では上記フィルム状フォトレジストを用
いて、新たな配線板の製造方法もしくは細線パターンを
絶縁板上に形成する方法が考えられている。この技術を
説明すると、まずフィルム状フォトレジストの保護フィ
ルムを取り除いて、感光層と支持フィルム層の２層から
なる積層フィルムとした後、その感光層がステンレス又
はアルミ等の金属板に接するように、積層フィルムを金
属板表面に加熱加圧ラミネートする。次いで、ネガフィ
ルムを用いて感光層に配線パターンを露光した後、支持
フィルムを露光された感光層表面から剥離し、次いで炭
酸ナトリウム水溶液を用いて感光層の未露光部を除去（
現像）することにより、レジスト像を形成する。そして
、このレジスト像が形成された金属板を無電解又は電解
メツキ処理することにより、レジスト像の除去された溝
部分にニッケル、銅、銀等の導電性材料を付着させる。By the way, recently, a new method of manufacturing a wiring board or a method of forming a thin line pattern on an insulating board using the above-mentioned film-like photoresist has been considered. To explain this technology, first, the protective film of the photoresist film is removed to create a laminated film consisting of two layers, a photosensitive layer and a supporting film layer, and then the photosensitive layer is placed in contact with a metal plate such as stainless steel or aluminum. , heat and pressure laminate the laminated film onto the surface of the metal plate. Next, after exposing the wiring pattern on the photosensitive layer using a negative film, the support film is peeled off from the exposed surface of the photosensitive layer, and then the unexposed areas of the photosensitive layer are removed using an aqueous sodium carbonate solution (
(Development) to form a resist image. Then, by subjecting the metal plate on which this resist image has been formed to an electroless or electrolytic plating process, a conductive material such as nickel, copper, silver, etc. is adhered to the groove portion where the resist image has been removed.
その後、このものをベークライト、ガラスエポキシ、セ
ラミック等の絶縁基板に加圧することにより、上記メツ
キ部のみを絶縁基板表面に転写して絶縁基板表面に配線
パターンを形成するのである。Thereafter, this material is pressed against an insulating substrate made of Bakelite, glass epoxy, ceramic, etc., thereby transferring only the plating portion onto the surface of the insulating substrate, thereby forming a wiring pattern on the surface of the insulating substrate.
上記方法によれば、レジスト像が形成された金属板から
、パターンが形成されたメツキ部だけを絶縁板に転写す
ることができるので、金属板表面に一度しシスト像を形
成しておくだけで、繰り返しメツキ転写が可能となり、
従って、配線板を低コストで生産することができる利点
がある。According to the above method, it is possible to transfer only the plating area on which the pattern is formed from the metal plate on which the resist image is formed to the insulating plate, so it is only necessary to form the cyst image once on the surface of the metal plate. , repeat plating transfer is possible,
Therefore, there is an advantage that wiring boards can be produced at low cost.
（発明が解決しようとする課題）
しかしながら、従来の感光性樹脂組成物を上記のような
配線板製造時の感光層として用いる場合、特に以下の２
点が問題となっている。(Problems to be Solved by the Invention) However, when using a conventional photosensitive resin composition as a photosensitive layer during the production of a wiring board as described above, especially the following two
point is the problem.
■金属板と感光層との密着力が低いために、上記のよう
にレジスト像が形成された金属板をメツキ処理する際に
、メツキが感光層と金属板表面との間にもぐり込んでメ
ツキが金属板表面に析出する。また、メツキ部を絶縁板
に転写する際に、レジスト像も絶縁板に転写されること
がある。■Due to the low adhesion between the metal plate and the photosensitive layer, when plating the metal plate on which the resist image has been formed as described above, the plating gets stuck between the photosensitive layer and the surface of the metal plate, causing the plating to deteriorate. Precipitates on the metal plate surface. Further, when transferring the plating portion to the insulating plate, the resist image may also be transferred to the insulating plate.
■金属板とメツキ部間の密着力が強いために、メツキ部
分を絶縁板表面へ転写させる際に、メツキ部分が金属板
に付着した状態となり、転写が十分に行われない。■Because the adhesion between the metal plate and the plated portion is strong, when the plated portion is transferred to the surface of the insulating plate, the plated portion adheres to the metal plate, and the transfer is not performed sufficiently.
以上の■及び■の理由から、絶縁板への十分なメツキ部
の転写が行われず、しかもレジスト像が形成された金属
板を繰り返し使用することができないものであった。For reasons of (1) and (2) above, the plating portion was not sufficiently transferred to the insulating plate, and furthermore, the metal plate on which the resist image was formed could not be used repeatedly.
本発明は上記欠点を解決するものであり、その目的は、
感光層と金属板との密着性が良好で、かつメツキ部と金
属板との密着力が従来に比べて弱く、従って転写特性が
良好であって、繰り返し転写に耐えうるレジスト像が形
成された金属板を得ることができる感光性樹脂組成物を
提供することにある。The present invention solves the above-mentioned drawbacks, and its purpose is to:
The adhesion between the photosensitive layer and the metal plate is good, and the adhesion between the plated part and the metal plate is weaker than before, so the transfer characteristics are good, and a resist image that can withstand repeated transfers is formed. An object of the present invention is to provide a photosensitive resin composition from which a metal plate can be obtained.
（課題を解決するための手段）
本発明の感光性樹脂組成物は、（ａ）α、β−不飽和エ
チレン系単量体を構成単位とし、そのうちカルボン酸を
有する単量体を１０〜４０重量％含存するアルカリ水溶
液に可溶な樹脂と、
（ｂ）下記式〔Ｉ〕で示される付加重合性物質と、（式
中、Ｒ３、Ｒ２、Ｒ１、Ｒ４は１１又はＣ１（、であり
、これらは同一であっても相異してもよく、ｎ及びｍは
ｎ＋ｍ＝ ２〜４となる正の整数である）（Ｃ）活性光
線に増感する光重合開始剤と、（ｄ）下記式（ＩＩ）で
示される化合物と、（式中、Ｒ２はオルト芳香族炭化水
素、ＺはＮｉｌ、０又はＳである）を含有し、樹脂（ａ
） １００重量部に対して、付加重合性物質（ｂ）が５
〜１５０重量部配合され、光重合開始剤（Ｃ）が０．０
１〜１０重量部配合され、式（ＩＩ）で示される化合物
（ｄ）が０．０１〜１重量部配合されており、そのこと
により上記目的が達成される。(Means for Solving the Problems) The photosensitive resin composition of the present invention has (a) an α,β-unsaturated ethylenic monomer as a constituent unit, of which 10 to 40 monomers having a carboxylic acid are included. (b) an addition polymerizable substance represented by the following formula [I], (wherein R3, R2, R1, R4 are 11 or C1 (, These may be the same or different, and n and m are positive integers such that n + m = 2 to 4) (C) a photopolymerization initiator that sensitizes to actinic rays, and (d) the following a compound represented by formula (II), (wherein R2 is an orthoaromatic hydrocarbon, Z is Nil, 0 or S), and a resin (a
) 5 parts of addition polymerizable substance (b) per 100 parts by weight
~150 parts by weight is blended, and the photopolymerization initiator (C) is 0.0
1 to 10 parts by weight are blended, and 0.01 to 1 part by weight of the compound (d) represented by formula (II) is blended, thereby achieving the above object.
上記樹脂の構成単位であるα、β−不飽和エチレン系単
量体としては、エチレン、プロピレン、ブチレン、Ｃ７
〜Ｃ３゜及びそれ以上のα−オレフィン類；塩化ビニル
、臭素ビニル、フッ化ビニル等のハロゲン化ビニル類；
酢酸ビニル、プロピオン酸ビニル、酪酸ビニル等のビニ
ルエステル類；アクリル酸メチル、アクリル酸エチル、
アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル
酸イソブチル、アクリル酸ｎ−オクチル、アクリル酸ラ
ウリル、アクリル酸２−エチルヘキシル、アクリル酸２
−クロロエチル、アクリル酸フェニル、α−クロロアク
リル酸メチル、メタクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、
メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、
メタクリル酸ラウリル、メタクリル酸２−エチルヘキシ
ル、メタクリル酸フェニル、メタクリル酸ジメチルアミ
ノエチル等のα−メチレン脂肪族モノカルボン酸エステ
ル類や；アクリロニトリル、メタクリロニトリル、アク
リルアミド等のアクリル及びメタアクリル誘導体；ビニ
ルメチルエーテル、ビニルエチルエーテル等のビニルエ
ーテル類；ビニルメチルケトン、ビニルエチルケトン等
のビニルケトン類；Ｎ−ビニルビロール、Ｎ−ビニルカ
ルバゾール、Ｎ−ビニルインドール等のＮ−ビニル化合
物、アクリル酸、メタクリル酸、マレイン酸等のカルボ
ン酸を有する単量体等が挙げられる。The α,β-unsaturated ethylenic monomers that are the constituent units of the resin include ethylene, propylene, butylene, C7
α-olefins of ~C3° and higher; vinyl halides such as vinyl chloride, vinyl bromine, and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; methyl acrylate, ethyl acrylate,
Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-acrylate
-chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as lauryl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, and dimethylaminoethyl methacrylate; acrylic and methacrylic derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; vinylmethyl Vinyl ethers such as ether and vinyl ethyl ether; Vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N-vinyl compounds such as N-vinylvirol, N-vinyl carbazole, and N-vinylindole; acrylic acid, methacrylic acid, and maleic acid. Examples include monomers having carboxylic acids such as.
カルボン酸を有する単量体は樹脂（ａ）中に１０〜４０
重量％含有される。カルボン酸を有する単量体の含有量
が１０重量％より少ないと、樹脂（ａ）がアルカリ水溶
液に対して不溶となる。また、カルボン酸を有する単量
体の含有量が、４０重量％より多いと、解像性が著しく
低下する。The monomer having carboxylic acid is present in the resin (a) in an amount of 10 to 40
Contains % by weight. When the content of the monomer having carboxylic acid is less than 10% by weight, the resin (a) becomes insoluble in the alkaline aqueous solution. Moreover, if the content of the monomer having carboxylic acid is more than 40% by weight, the resolution will be significantly reduced.
本発明に用いられる式〔Ｉ〕で示される付加重合性物質
う）としては、２．２゛−ビス（４−メタクリロキシジ
ェトキシフェニル）プロパン、２．２′−ビス（４−ア
クリロキシジェトキシフェニル）プロパン等があり、市
販品としては、例えば、Ａ−ＢＰＥ４ 、［１ＰＥ−２
００（共に新中村化学工業■製）がある。The addition polymerizable substances represented by formula [I] used in the present invention include 2.2'-bis(4-methacryloxyjethoxyphenyl)propane, 2.2'-bis(4-acryloxyjethoxyphenyl), commercially available products include A-BPE4, [1PE-2
00 (both manufactured by Shin-Nakamura Chemical Industry ■).
式（ｒ）で示される付加重合性物質は、上記した化合物
の一種だけを用いても良いが、２種以上の化合物の混合
物として用いても良い。この付加重合性物質は感光性樹
脂組成物を繰り返し転写する場合の、耐久性を付与する
ものである。上記で示したＣＩ）で示される式中、ｎ＋
ｍが５以上の場合には、解像力が低下する。As the addition polymerizable substance represented by formula (r), only one type of the above-mentioned compounds may be used, or a mixture of two or more types of compounds may be used. This addition polymerizable substance provides durability when the photosensitive resin composition is repeatedly transferred. In the formula represented by CI) shown above, n+
When m is 5 or more, the resolution decreases.
また、式（１）以外の付加重合性物質を加えても良く、
この付加重合性物質は通常常温で液状の単量体であれば
良い。これらには、例えばトリエチレングリコールジ（
メタ）アクリレート、テトラエチレングリコールジ（メ
タ）アクリレート、ノナエチレングリコールジ（メタ）
アクリレート、ポリエチレングリコールジ（メタ）アク
リレート、トリプロピレン、グリコールジ（メタ）アク
リレート、ペンタエリスリトールトリ （メタ）アクリ
レート、ジペンタエリスリトールペンタ （メタ）アク
リレート、ジペンタエリスリトールヘキサ（メタ）アク
リレート、トリメチロールプロパントリ （メタ）アク
リレート、３−フェノキシ−２プロパノイルアクリレー
ト、ポリメチレンジ（メタ）アクリレート等のポリ （
メタ）アクリレート系単量体が挙げられる。Furthermore, an addition polymerizable substance other than formula (1) may be added,
This addition polymerizable substance may be a monomer that is normally liquid at room temperature. These include, for example, triethylene glycol di(
meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate
Acrylate, polyethylene glycol di(meth)acrylate, tripropylene, glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate (meth)acrylate, 3-phenoxy-2propanoyl acrylate, polymethylene di(meth)acrylate, etc.
Examples include meth)acrylate monomers.
本発明に用いられる活性光線に増感する光重合開始剤（
Ｃ）としては、ベンゾフェノン、ミヒラーズケトン、Ｎ
、Ｎ、Ｎ”、Ｎ′−ビス（ジエチルアミノ）ベンゾフェ
ノン、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジエチ
ルアミノ安息香酸エチル等のケトン類；チオキサントン
、２−エチルチオキサントン、２，４−ジエチルチオキ
サントン、２−クロルチオキサントン等のチオキサント
ン類；ベンゾイン、ベンゾインエーテル等のベンゾイン
誘導体、２−エチルアントラキノン等の多核キノン；９
−フェニル−アクリジン、９−ｐ−メトキシフェニルア
クリジン等のアクリシン誘導体；９．１０−ジメチルベ
ンズフェナジン等のフェナジン誘導体；６．４’、４”
−１−ジメトキシ−２，３−ジフエニルーキノキサリン
等のキノキサリン誘導体；ベンゾイルバーキシド、ジ−
ｔ−ブチルパーオキシド、ジクミルパーオキシド、キュ
メンハイドロパーオキシド等の過酸化物等があげられる
。また、可視光に増感する開始剤も使用でき、これには
２−ニトロフルオレン、２，４．６−トリフ、エニルピ
リリウム四フッ化ホウ素塩、２，４．６− ）リス（ト
リクロロメチル） −１，３，５−１−リアジン、３，
３°−カルボニルビス （クマリン）、チオミヒラーケ
トン等が挙げられる。The photopolymerization initiator used in the present invention (
C) includes benzophenone, Michler's ketone, N
, N, N'', N'-bis(diethylamino)benzophenone, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and other ketones; thioxanthone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthone such as chlorothioxanthone; benzoin, benzoin derivatives such as benzoin ether, polynuclear quinone such as 2-ethylanthraquinone; 9
-Acrisin derivatives such as phenyl-acridine and 9-p-methoxyphenylacridine; phenazine derivatives such as 9.10-dimethylbenzphenazine; 6.4', 4"
-quinoxaline derivatives such as -1-dimethoxy-2,3-diphenyl-quinoxaline; benzoyl biroxide, di-
Examples include peroxides such as t-butyl peroxide, dicumyl peroxide, and cumene hydroperoxide. Initiators that are sensitized to visible light can also be used, including 2-nitrofluorene, 2,4,6-trif, enylpyrylium tetrafluoroborate salt, 2,4,6-)lis(trichloromethyl ) -1,3,5-1-riazine, 3,
Examples include 3°-carbonylbis (coumarin) and thiomichler ketone.
この光重合開始剤は、１０〜５０％の光が感光性樹脂組
成物を透過するようにその添加量を調整するのが好まし
い。The amount of the photopolymerization initiator added is preferably adjusted so that 10 to 50% of light passes through the photosensitive resin composition.
すなわち、光重合開始剤の添加部数は、次のようにして
決定することができる。That is, the number of parts of the photopolymerization initiator to be added can be determined as follows.
例えば、感光性樹脂組成物中の光重合開始剤の濃度をＣ
ｍｏｌ ／ １とし、露光ＩＩ。に対し、厚みＸｃｍの
感光性樹脂組成物を透過した後の光の強度を１とすると
、
１ｏｇｒｏ／Ｉ＝εＣＸ・（ＩＩＩ）
ランバート・ビアー則が成立する。For example, the concentration of the photopolymerization initiator in the photosensitive resin composition is C
mol/1 and exposure II. On the other hand, if the intensity of light after passing through a photosensitive resin composition having a thickness of X cm is set to 1, then the Lambert-Beer law holds: 1 ogro/I=εCX·(III).
ここで、εは光重合開始剤の分子吸光係数（２／ｍｏｌ
−ｃｍ）である。Here, ε is the molecular extinction coefficient of the photopolymerization initiator (2/mol
-cm).
上記（ＩＩＩ３式において、ｉｏ／Ｉの値は、金属の表
面に形成されるレジスト像の断面形状に大きな影響を与
える。In the above formula (III3), the value of io/I has a large effect on the cross-sectional shape of the resist image formed on the metal surface.
（１）１．／Ｉの値がＯ〜０．１の場合では、レジスト
像１の断面形状は第１図（ａ）に示すように逆台形とな
り、従って、メツキ部２を絶縁板へ転写する際に、レジ
スト像ｌが金属板３表面から剥がれる可能性が高い。(1)1. When the value of /I is O to 0.1, the cross-sectional shape of the resist image 1 becomes an inverted trapezoid as shown in FIG. There is a high possibility that the image l will be peeled off from the surface of the metal plate 3.
（２）１．／Ｉの値が０．１〜０．５の場合では、レジ
スト像１の断面形状は第１図（ｂ）に示すように、台形
となり、メツキは良好に転写される。(2)1. When the value of /I is 0.1 to 0.5, the cross-sectional shape of the resist image 1 becomes a trapezoid as shown in FIG. 1(b), and the plating is transferred well.
（３）１０／Ｉの値が０．５を超える場合では、第１図
（Ｃ）に示すように、金属板３の表面が露出しない場合
を生じ、レジスト像１の解像性は著しく低下する。(3) When the value of 10/I exceeds 0.5, the surface of the metal plate 3 may not be exposed as shown in FIG. 1(C), and the resolution of the resist image 1 is significantly reduced. do.
今、この種の光重合開始剤について、その添加量を最適
化する感光層の厚みを２５μｍとすると、２．４−ジエ
チルチオキサントンを用いる場合と、Ｎ、Ｎ、Ｎ’、Ｎ
’ −ビス （ジエチルアミノ）ベンゾフェノンを用
いる場合の添加量は次のようになる。Now, for this type of photopolymerization initiator, assuming that the thickness of the photosensitive layer for which the amount of addition is optimized is 25 μm, there is a case where 2,4-diethylthioxanthone is used, a case where N, N, N', N
When using '-bis(diethylamino)benzophenone, the amount to be added is as follows.
（１） ２．４−ジエチルチオキサントンを用いる場合
■Ｉｏ／ Ｉの値を０．１ とすると、上記（ＴＩ［）
式％式％
またこのものの分子量は２６８であるから、ｌｏｇ １
０／ １ ＝ｓｏｏｏｘｃ Ｘｏ、００２５Ｃ＝０．０
６６７ｍｏｌ／ｊ！ ＝１．７８ｇ／ｄｉとなり、２，
４−ジエチルチオキサントンの添加部数は１．７８重量
％となる。(1) When using 2.4-diethylthioxanthone■If the value of Io/I is 0.1, the above (TI[)
Formula % Formula % Also, since the molecular weight of this substance is 268, log 1
0/ 1 = soooxc Xo, 0025C = 0.0
667mol/j! =1.78g/di, 2,
The number of parts of 4-diethylthioxanthone added is 1.78% by weight.
■Ｉ０／ ■の値を０．５ とすると、式〔■〕よりｌ
ｏｇ ２／ １ ＝６０００ＸＣｘｏ、００２５Ｃ＝
０．０２０１ｍｏｌ／ ｊ２ ＝０．５４８／ｄｌとな
り、２．４−ジエチルチオキサントンの添加部数は０．
５４重量％となる。■If the value of I0/■ is 0.5, then l
og 2/ 1 =6000XCxo,0025C=
0.0201 mol/j2 = 0.548/dl, and the number of parts of 2.4-diethylthioxanthone added was 0.0201 mol/j2 = 0.548/dl.
It becomes 54% by weight.
従って、転写用に最適な２，４−ジエチルチオキサント
ンの添加量は０．５４〜１．８重量％となる。Therefore, the optimum amount of 2,4-diethylthioxanthone added for transfer is 0.54 to 1.8% by weight.
（２） Ｎ、Ｎ、Ｎ’、Ｎ” −ビス （ジエチルアミ
ノ）ベンズフェノンを用いる場合
■１．／Ｉの値を０．１ とすると、上記ＣＩ［［］式
％式％
またこのものの分子量は２９６であるから、ｌｏｇ
１０／ １ ＝３３０００ ＸＣＸｏ、００２５Ｃ
＝０．３６ｇ／ ｄｊ２となり、Ｎ、Ｎ、Ｎ’ 、Ｎ’
−ビス （ジエチルアミノ）ベンズフェノンの添加
部数は０．３６重量％となる。(2) When using N,N,N',N"-bis(diethylamino)benzphenone■1.If the value of /I is 0.1, the above CI[[]formula%formula%Also, the molecular weight of this substance is Since it is 296, log
10/1 = 33000 XCXo, 0025C
=0.36g/dj2, N, N, N', N'
The amount of -bis(diethylamino)benzphenone added is 0.36% by weight.
■１．／Ｉの値を０．５とすると、式（ＩＩＩ）よりｌ
ｏｇ ２／ １ ＝３３０００ ＸＣＸｏ、００２５
Ｃ＝０．１１ｇ／ｄｉとなり、Ｎ、 Ｎ、 Ｎ’ 、
Ｎ’ −ビス（ジエチルアミノ）ベンズフェノンの添
加部数は０．１１重量％となる。■1. If the value of /I is 0.5, then l
og 2/ 1 = 33000 XCXo, 0025
C=0.11g/di, N, N, N',
The amount of N'-bis(diethylamino)benzphenone added is 0.11% by weight.
従って、転写用に最適なＮ、Ｎ、Ｎ’、Ｎ’ −ビス（
ジエチルアミノ）ベンズフェノンの添加量は０．１１〜
０．３６重量％となる。Therefore, N, N, N', N'-bis(
The amount of diethylamino)benzphenone added is 0.11~
The amount is 0.36% by weight.
本発明で用いられる式（ＩＩ）で示される化合物（ｄ）
は密着改良剤であり、例えば、２−メルカプトベンズイ
ミダゾール、２−メルカプトベンズキサゾール、２−メ
ルカプトベンズチアゾール等が挙げられる。Compound (d) represented by formula (II) used in the present invention
is an adhesion improver, and examples thereof include 2-mercaptobenzimidazole, 2-mercaptobenzixazole, 2-mercaptobenzthiazole, and the like.
本発明においては、上記構成よりなるアルカリ水溶液に
対して可溶な樹脂（ａ） １００重量部に対して、式〔
Ｉ〕で示される付加重合性物質（ｂ）が５〜１５０重量
部、好ましくは１０〜１００重量部配合され、光重合開
始剤（Ｃ）は０．１〜１０重量部配合され、さらに上記
式〔■〕で示される化合物（ｄ）が０．０１〜１重量部
配合されて感光性樹脂組成物が作成される。In the present invention, the formula [
5 to 150 parts by weight, preferably 10 to 100 parts by weight, of an addition polymerizable substance (b) represented by I], 0.1 to 10 parts by weight of a photopolymerization initiator (C), and further compounded by the above formula A photosensitive resin composition is prepared by adding 0.01 to 1 part by weight of the compound (d) represented by [■].
樹脂（ａ） １００重量部に対する式〔Ｉ〕で示される
付加重合性物質（ｂ）の配合量が上記範囲を外れる場合
には、感光性樹脂組成物の露光硬化部の繰り返し耐久性
が低下する。樹脂（ａ） １００重量部に対する光重合
開始剤ω）の配合量が０．１重量部未満の場合には感光
性樹脂組成物の感度が低下し、また光重合開始剤の配合
量が１０重量部を超えても添加効果がそれほど向上しな
い。If the amount of addition polymerizable substance (b) represented by formula [I] based on 100 parts by weight of resin (a) is out of the above range, the repeated durability of the exposed and cured portion of the photosensitive resin composition will decrease. . If the amount of photopolymerization initiator ω) is less than 0.1 part by weight with respect to 100 parts by weight of resin (a), the sensitivity of the photosensitive resin composition will decrease, and if the amount of photopolymerization initiator is less than 10 parts by weight. Even if the amount is exceeded, the effect of addition will not improve much.
また、式（ＩＩ）で示される化合物（ｄ）はメルカプト
基を有しているために、このメルカプト基が金属表面と
化学結合することにより、感光性樹脂組成物と金属間の
密着力を著しく向上させることができる。その結果、い
わゆるメツキもぐりがなくなり、表面にレジスト像が形
成された金属板を使用して繰り返し転写を行う場合に、
感光性樹脂組成物にて形成されるレジスト像が金属表面
から剥かれることはないのである。In addition, since the compound (d) represented by formula (II) has a mercapto group, this mercapto group chemically bonds with the metal surface, thereby significantly increasing the adhesion between the photosensitive resin composition and the metal. can be improved. As a result, so-called plating is eliminated, and when performing repeated transfers using a metal plate with a resist image formed on its surface,
The resist image formed with the photosensitive resin composition will not be peeled off from the metal surface.
また、式（ＩＩ）で示される化合物（ｄ）を感光性樹脂
組成物に所定量配合することにより、感光層の未露光部
がアルカリ水溶液により溶解除去された後でも、メツキ
される部分の金属界面には化合物（ｄ）が薄層状態で残
っているために、メツキ部と金属界面との密着力が低下
し、メツキ部が容易に転写されるのである。樹脂に対す
る式（ＩＩ）で示される化合物（ロ）の配合量がｏ、ｏ
ｉ重量部未満では、添加効果が小さく上記効果は小さく
なる。また、樹脂に対する式〔■〕で示される化合物（
ｄ）の配合量が１重量部を超えると、感光層と金属との
界面で化合物（ｄ）が多重の層を形成するために、レジ
スト像と金属との界面密着力は低下する。In addition, by blending a predetermined amount of the compound (d) represented by formula (II) into the photosensitive resin composition, even after the unexposed areas of the photosensitive layer are dissolved and removed by an aqueous alkaline solution, the metal of the plated area can be removed. Since the compound (d) remains in a thin layer at the interface, the adhesion between the plated portion and the metal interface is reduced, and the plated portion is easily transferred. The amount of the compound (b) represented by formula (II) relative to the resin is o, o
If it is less than i parts by weight, the effect of addition is small and the above effects are reduced. In addition, the compound represented by the formula [■] for the resin (
If the amount of d) exceeds 1 part by weight, compound (d) forms multiple layers at the interface between the photosensitive layer and the metal, resulting in a decrease in interfacial adhesion between the resist image and the metal.
本発明の感光性樹脂組成物には、上記の各種配合成分の
他に、必要に応じて可塑剤、熱重合禁止剤、光発色剤、
着色剤、密着改良剤を含有しても良い。In addition to the above-mentioned various ingredients, the photosensitive resin composition of the present invention may optionally include a plasticizer, a thermal polymerization inhibitor, a photocoloring agent,
It may also contain a colorant and an adhesion improver.
本発明の感光性樹脂組成物は、通常溶剤に溶解された溶
液状態で使用され、この感光液をポリエチレンテレフタ
レート等の支持フィルム上に塗布、乾燥することにより
感光層が形成される。そして、本感光性樹脂組成物は、
例えば、配線板の製造あるいは細線パターン形成のため
に使用され得る。The photosensitive resin composition of the present invention is usually used in the form of a solution dissolved in a solvent, and a photosensitive layer is formed by applying this photosensitive solution onto a support film such as polyethylene terephthalate and drying it. And, this photosensitive resin composition is
For example, it can be used for manufacturing wiring boards or forming fine line patterns.
（実施例） 以下乙こ本発明を実施例に基づいて詳細に説明する。(Example) The present invention will be described in detail below based on examples.
実新Ｉ引１
メタクリル酸メチル／メタクリル酸ｎ−ブチル／メタク
リル酸（５０／２５／２５）共重合体（Ｍｗ） ６０
ｇ２．２−ビス（４−メタクリロキシジェトキシフェニ
ル）プロパン １５’ｇテトラ
エチレングリコールジアクリレート５ｇ
２．４−ジメチルチオキサントン ２．０ｇｐ
−ジメチルアミノ安息香酸エチル ２．０ｇマラカ
イトグリーン ０．０５ ｇパラメ
トキシフェノール ０．１ｇ２−メルカ
プトベンズイミダゾール ０．０４ ｇ上記各成分か
らなる感光性樹脂組成物をメチルエチルケトン２００ｇ
に溶解させて感光液を調製し、この感光液を厚さ２０μ
ｍのポリエチレンテレフタレートフィルム玉に、乾燥後
の膜厚が２５μｍとなるように塗布し、８０°Ｃで１０
分間乾燥することによりフィルム上に感光層を形成した
。次に、この積層フィルムを厚み１ ｍｍのステンレス
板（ＳＵＳ３０４１８−８）にラミネートした。Jitsushin I Reference 1 Methyl methacrylate/n-butyl methacrylate/methacrylic acid (50/25/25) copolymer (Mw) 60
g2.2-bis(4-methacryloxyjethoxyphenyl)propane 15'gtetraethylene glycol diacrylate 5g 2.4-dimethylthioxanthone 2.0gp
- Ethyl dimethylaminobenzoate 2.0 g Malachite green 0.05 g Paramethoxyphenol 0.1 g 2-Mercaptobenzimidazole 0.04 g A photosensitive resin composition consisting of each of the above components was mixed with 200 g of methyl ethyl ketone.
Prepare a photosensitive solution by dissolving it in
It was coated on a polyethylene terephthalate film ball of 100 mL to a film thickness of 25 μm after drying, and heated at 80°C for 10 min.
A photosensitive layer was formed on the film by drying for minutes. Next, this laminated film was laminated onto a stainless steel plate (SUS30418-8) with a thickness of 1 mm.
この状態で、Ｌｉｎｅ／５ｐａｃｅ ＝ ５０ ｐ ｍ
１５０ Ｂ ｍのパターンのネガフィルムを上記積層フ
ィルム上に密着させ、３に一高圧水銀灯から５０ｃｍ離
れた位置で、１００ｍＪ／ｃｉｎ光した。この時６．４
ｍＪ／ｃ４．６．４％の光が組成物を透過した。In this state, Line/5 pace = 50 p m
A negative film with a pattern of 150 Bm was closely adhered to the above laminated film, and at a position 50 cm away from a high-pressure mercury lamp, 100 mJ/cin of light was applied. At this time 6.4
Light of 4.6.4% mJ/c was transmitted through the composition.
次いで、室温でポリエチレンテレフタレートフィルムを
剥がし、その露光された感光層の表面に１重量％、炭酸
ナトリウム水溶液（３０″Ｃ）を１．０ｋｇ ／ ｃｔ
圧でスプレー現像した。感度をスト−７７２１段ステッ
プタブレットで測定したところ６段であった。Ｌｉｎｅ
／ｓｐａｃｅ＝５０ａｍ１５０ｕｍのパターンは十分解
像されていた。Then, the polyethylene terephthalate film was peeled off at room temperature, and a 1% by weight sodium carbonate aqueous solution (30″C) was added to the surface of the exposed photosensitive layer at 1.0 kg/ct.
Pressure spray developed. The sensitivity was measured using a ST-7721 step tablet and was found to be 6 steps. Line
The pattern with /space=50am150um was sufficiently resolved.
次に、このようにして処理された露光ステンレス板の表
面を以下の■〜■の操作でメツキした。Next, the surface of the exposed stainless steel plate thus treated was plated by the following operations (1) to (4).
■酸性脱脂処理・・・ジブレイ味製シブレイ１０２２の
１０ｗｔ％水溶液を用い、６０°Ｃにて５分間浸漬■ソ
フトエツチング処理・・・過硫酸アンモニウム２５−ｔ
％水溶液を用い、室温にて９０秒間浸漬■酸洗処理・・
・２０ｗ ｔ％硫酸を用い、室温にて６０秒間浸漬
■ニッケルメッキ処理・・・ニッケルーａｔｔ浴を用い
、５０’Ｃ−電流密度３ Ａ／ｄｍ”にて２５分間処理
その結果、ステンレス板の表面には厚さ２５μｍのニッ
ケルメッキが施され、このメツキ部分の表面を顕微鏡で
観察したところ、レジスト像下部へのメツキもぐりは見
られなかった。■Acidic degreasing treatment: Using a 10wt% aqueous solution of Sibley 1022 manufactured by Gibley Aji, immersion at 60°C for 5 minutes ■Soft etching treatment: Ammonium persulfate 25-t
% aqueous solution for 90 seconds at room temperature ■ Pickling treatment...
・Immersed in 20wt% sulfuric acid at room temperature for 60 seconds ■Nickel plating treatment...Using a nickel-ATT bath, treated for 25 minutes at 50'C and current density of 3 A/dm'' As a result, the surface of the stainless steel plate was plated with nickel to a thickness of 25 μm, and when the surface of this plated portion was observed under a microscope, no plating was observed beneath the resist image.
次に、このニッケルメッキによる画線が描かれたステン
レス板をアルミナよりなるセラミックスグリーンシート
に、ニッケルメッキ部がグリーンシート上に接するよう
に圧着し、１０ ｋｇ ／ ｄの圧力で１分間放置した
後、ステンレス板をグリーンシートから剥がしたところ
、グリーンシート上にニッケルメッキ部のみが転写され
た。このグリーンシートを焼結することにより、セラミ
ック回路板が得られた。Next, the stainless steel plate with the nickel-plated lines drawn on it was crimped onto a ceramic green sheet made of alumina so that the nickel-plated part was in contact with the green sheet, and after being left under a pressure of 10 kg/d for 1 minute. When the stainless steel plate was peeled off from the green sheet, only the nickel plated portion was transferred onto the green sheet. A ceramic circuit board was obtained by sintering this green sheet.
このような操作の後、ステンレス板のレジスト像を観察
したところ、全く欠損は見られなかった。After such an operation, when the resist image on the stainless steel plate was observed, no defects were observed.
上記メツキ転写操作を１０回繰り返したところ、レジス
ト像に異常は見られなかった。When the above plating transfer operation was repeated 10 times, no abnormality was observed in the resist image.
止較拠エ
メタクリル酸メチル／メタクリル酸ｎ−ブチル／メタク
リル酸（５０／２５／２５）共重合体（Ｍｗ１５万）６
０ｇトリメチロールプロパントリアクリレート １５ｇ
テトラエチレングリコールジアクリレート１５ｇ２．４
−ジエチルチオキサントン ２．０ｇＰ−ジメ
チルアミノ安息香酸エチル ２．０ｇマラカイトグ
リーン ０．０５ ｇパラメトキシ
フェノール ０．１ｇベンズイミダゾ
ール ０．０４ｇ上記各成分からな
る感光性樹脂組成物を用いて感光液を調製した他は、実
施例１と同様にしてポリエチレンテレフタレートフィル
ム上に感光層ヲ形成した。次に、この感光層を実施例１
と同様にして１００ｍＪ／ｃｎ露光した。この時６．４
ｒ＊Ｊ／ｃｔｌ、６．４％の光が感光層を透過した。感
度をスト−７７２１段ステップタブレットで測定したと
ころ６段であった。Ｌｉｎｅ／ｓｐａｃｅ＝５０ａｍ
１５０１１のパターンは十分に解像していた。Base: Methyl methacrylate/n-butyl methacrylate/methacrylic acid (50/25/25) copolymer (Mw 150,000) 6
0g trimethylolpropane triacrylate 15g
Tetraethylene glycol diacrylate 15g2.4
-Diethylthioxanthone 2.0gP-Ethyl dimethylaminobenzoate 2.0gMalachite green 0.05gParamethoxyphenol 0.1gBenzimidazole 0.04gA photosensitive solution was prepared using a photosensitive resin composition consisting of the above components. Otherwise, a photosensitive layer was formed on a polyethylene terephthalate film in the same manner as in Example 1. Next, this photosensitive layer was prepared in Example 1.
Exposure was carried out at 100 mJ/cn in the same manner as above. At this time 6.4
r*J/ctl, 6.4% of light was transmitted through the photosensitive layer. The sensitivity was measured using a ST-7721 step tablet and was found to be 6 steps. Line/space=50am
The pattern of 15011 was sufficiently resolved.
次に、得られた露光ステンレス板を実施例１と同様にニ
ッケルメッキに供したところ、メツキもぐりを生じ、Ｌ
ｉｎｅ／５ｐａｃｅ−５０μｍ １５０ ｐｍのパター
ンは得られなかった。そこで、実施例１と同様にしてＬ
ｉｎｅ／５ｐａｃｅ＝１００ ｐｍ ／１００μｍのパ
ターンでメツキしたところ、メツキもぐりは見られなか
った。次いで、このものをグリーンシートに転写したと
ころ、ニッケルメッキ部は転写されず、逆にレジスト像
がステンレ板表面から剥離してグリーンシート上に転写
された。Next, when the obtained exposed stainless steel plate was subjected to nickel plating in the same manner as in Example 1, plating plating occurred and L
A pattern of ine/5 pace-50 μm 150 pm was not obtained. Therefore, as in Example 1, L
When plating was performed with a pattern of ine/5 pace=100 pm/100 μm, no plating was observed. When this was then transferred to a green sheet, the nickel plated portion was not transferred, and on the contrary, the resist image was peeled off from the stainless steel plate surface and transferred onto the green sheet.
裏施炭又
メタクリル酸メチル／アクリル酸２−エチルヘキシル／
アクリル酸（３８／３７／２５）共重合体（Ｍｗ）
６０ ｇ２．２′−ビス （４−アクリロキシジェトキ
シフェニル）プロパン １
５ｇテトラエチレングリコールジアクリレート １５ｇ
Ｎ、Ｎ、Ｎ’、Ｎ’ −ビス （ジエチルアミノ）ベ
ンゾフェノン
０．４ｇベンゾフェノン
３．０ｇクリスタルバイオレット ０．
０４ ｇバラメトキシフェノール ０．
１ｇ２−メルカプトベンズチアゾール ０．０５
ｇ上記各成分からなる感光性樹脂組成物を用いて感光液
を調製した他は実施例１と同様にしてポリエチレンテレ
フタレートフィルム上に感光層を形成した。次に、この
感光層を実施例１と同様にして１００ｍＪ／ｃｄ露光し
た。この時、６．４ｍＪ ／ ＣＴ１１．６．４％の光
が組成物を透過した。感度をスト−７７２１段ステップ
タブレットで測定したところ６段であった。Ｌｉｎｅ／
５ｐａｃｅ＝５０μｍ １５０ ｐｒｎのパターンは十
分に解像されていた。Backed carbon or methyl methacrylate/2-ethylhexyl acrylate/
Acrylic acid (38/37/25) copolymer (Mw)
60 g2.2'-bis(4-acryloxyjethoxyphenyl)propane 1
5g Tetraethylene glycol diacrylate 15g
N,N,N',N'-bis(diethylamino)benzophenone
0.4g benzophenone
3.0g crystal violet 0.
04 g Paramethoxyphenol 0.
1g 2-Mercaptobenzthiazole 0.05
g A photosensitive layer was formed on a polyethylene terephthalate film in the same manner as in Example 1, except that a photosensitive liquid was prepared using a photosensitive resin composition comprising the above-mentioned components. Next, this photosensitive layer was exposed to 100 mJ/cd in the same manner as in Example 1. At this time, 6.4 mJ/CT11.6.4% of light was transmitted through the composition. The sensitivity was measured using a ST-7721 step tablet and was found to be 6 steps. Line/
The pattern of 5 pace = 50 μm 150 prn was well resolved.
次に、このものを以下の■〜■の操作で銅メツキに供し
た。Next, this product was subjected to copper plating by the following operations (1) to (2).
■酸性脱脂処理・・・シューリング■製酸性りリーナー
ＦＲＩＯ重量％、硫酸２０重量％水溶液を用いて、４０
”Ｃで５分間浸漬
■ソフトエツチング処理・・・過硫酸ナトリウム２５重
量％水溶液にて室温で９０秒間浸漬■酸洗処理・・・２
０重量％硫酸にて室温で６０秒間浸漬
■硫酸銅メツキ処理・・・硫酸銅メツキ浴にて２０°Ｃ
１電流密度３八／ｄｍ２で３０分間処理
その結果、ステンレス板の表面には厚み２５μｍの銅メ
ツキが形成され、メツキ部分の表面を顕微鏡で観察した
ところ、レジスト像下部へのメツキもぐりは見られなか
った。■ Acidic degreasing treatment: Using Acid Reiner FRIO manufactured by Schuling ■ and a 20% by weight aqueous solution of sulfuric acid,
Soft etching treatment: Soaking in 25% sodium persulfate aqueous solution for 90 seconds at room temperature ■Pickling treatment: 2
Immersed in 0% by weight sulfuric acid at room temperature for 60 seconds ■Copper sulfate plating treatment...at 20°C in a copper sulfate plating bath
As a result, copper plating with a thickness of 25 μm was formed on the surface of the stainless steel plate, and when the surface of the plating area was observed under a microscope, no plating was observed at the bottom of the resist image. There wasn't.
次に、この銅メツキによる画線が描かれたステンレス板
を、ガラスエポキシプリプレグにメツキ部と接するよう
に圧着し、１５ｋｇ／ｃ＋１１の圧力で１分間放置した
後、ステンレス板をガラスエポキシプリプレグから剥が
したところ、ガラスエポキシプリプレグ上に銅メツキの
みが転写された。このガラスエポキシプリプレグを熱処
理することにより、ガラスエポキシ回路板が得られた。Next, the stainless steel plate with the copper plating lines drawn on it was crimped onto the glass epoxy prepreg so that it was in contact with the plating area, and after being left at a pressure of 15 kg/c+11 for 1 minute, the stainless steel plate was peeled off from the glass epoxy prepreg. However, only the copper plating was transferred onto the glass epoxy prepreg. A glass epoxy circuit board was obtained by heat-treating this glass epoxy prepreg.
このような操作の後、ステンレス板のレジスト像には、
全く欠損は見られなかった。このメツキ転写を１０回繰
り返したところ、レジスト像に異常は見られなかった。After such operations, the resist image on the stainless steel plate has
No defects were observed. When this plating transfer was repeated 10 times, no abnormality was observed in the resist image.
実衡斑主
アクリル酸エチル／メタクリル酸メチル／アクリル酸（
３５／４０／２５）共重合体（Ｍ−８万）６０ｇ２．２
”−ビス（４−メアクリロキシジエトキシフェニル）プ
ロパン ２０ｇトリメチロール
プロパントリアクリレート０ｇ
２．４−ジエチルチオキサントン １．０ｇｐ−
ジメチルアミノ安息香酸エチル ２．０ｇマラカイト
グリーン ０．０５ ｇバラメトキシ
フェノール ０．１ｇ２−メルカプトベ
ンズキサゾール ０．０５ｇ上記各成分からなる感
光性樹脂組成物を用いて感光液を調製した他は、実施例
１と同様にしてポリエチレンテレフタレートフィルム上
に感光層ヲ形成した。次に、この感光層を実施例１と同
様にして１００ｍＪ／ｃ＋ａ露光した。この時２５ｍＪ
／ ｃ＋ｆｌ、 ２５％の光が組成物を透過した。Mainly ethyl acrylate/methyl methacrylate/acrylic acid (
35/40/25) copolymer (M-80,000) 60g2.2
"-Bis(4-meacryloxydiethoxyphenyl)propane 20g trimethylolpropane triacrylate 0g 2.4-diethylthioxanthone 1.0gp-
Ethyl dimethylaminobenzoate 2.0 g Malachite green 0.05 g Paramethoxyphenol 0.1 g 2-mercaptobenzuxazole 0.05 g Other than preparing a photosensitive solution using a photosensitive resin composition consisting of each of the above components, the following steps were carried out. A photosensitive layer was formed on a polyethylene terephthalate film in the same manner as in Example 1. Next, this photosensitive layer was exposed to 100 mJ/c+a in the same manner as in Example 1. At this time 25mJ
/c+fl, 25% of the light was transmitted through the composition.
次に、得られた露光ステンレス板を実施例１と同様にニ
ッケルメッキに供したところ、メツキもぐりは見られな
かった。さらに、グリーンシートに転写したところ、ニ
ッケルメッキのみが転写され、このグリーンシートを焼
結することにより、セラミックス回路板が得られた。こ
のような操作の後、ステンレス板上のレジスト像には全
く欠損は見られなかった。このメツキ転写を５０回繰り
返してたところ、レジスト像に異常な見られなかった。Next, when the obtained exposed stainless steel plate was subjected to nickel plating in the same manner as in Example 1, no plating was observed. Furthermore, when it was transferred to a green sheet, only the nickel plating was transferred, and by sintering this green sheet, a ceramic circuit board was obtained. After such an operation, no defects were observed in the resist image on the stainless steel plate. When this plating transfer was repeated 50 times, no abnormality was found in the resist image.
（発明の効果）
このように、本発明の感光性樹脂組成物は上記のような
構成であるので、例えば、この感光性樹脂組成物を導体
画線形成材料として使用すると、感光層と金属との密着
性が良くてメツキもぐりを生じるようなことがなく、ま
た細線パターンを絶縁板へ転写する際には、細線パター
ンを容易に剥離させて転写させることができる。従って
、本発明の感光性樹脂組成物は、配線板など細線パター
ン転写用材料として好適に用いることができる。(Effects of the Invention) As described above, since the photosensitive resin composition of the present invention has the above-mentioned structure, for example, when this photosensitive resin composition is used as a material for forming conductive lines, the photosensitive layer and the metal The adhesion is good and no plating occurs, and when transferring a thin line pattern to an insulating plate, the thin line pattern can be easily peeled off and transferred. Therefore, the photosensitive resin composition of the present invention can be suitably used as a material for transferring fine line patterns such as wiring boards.
４、゛ の″ なｉ′Ｉ
第１図（ａ）はＩ。／Ｉの値が０．１〜０．５の場合の
レジスト像部分の断面図、第１図（ｂ）は■。／■の値
が０．１〜０．５の場合のレジスト像部分の断面図、第
１図（Ｃ）はＩ。／■の値が０．５を越える場合のレジ
スト像部分の断面図である。4. "i'I" Figure 1(a) is a cross-sectional view of the resist image portion when the value of I./I is 0.1 to 0.5, and Figure 1(b) is ■./ Figure 1 (C) is a cross-sectional view of the resist image portion when the value of I./■ exceeds 0.5. .
■・・・レジスト像、２・・・メツキ部、３金属板。■...Resist image, 2...Platched part, 3 Metal plate.
以上that's all
Claims (1)
位とし、そのうちカルボン酸を有する単量体を１０〜４
０重量％含有するアルカリ溶液に可溶な樹脂と、 （ｂ）下記式〔 I 〕で示される付加重合性物質と、▲
数式、化学式、表等があります▼〔 I 〕 （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４はＨ又はＣＨ
＿３であり、これらは同一であっても相異してもよく、
ｎ及びｍはｎ＋ｍ＝２〜４となる正の整数である） （ｃ）活性光線に増感する光重合開始剤と、（ｄ）下記
式〔II〕で示される化合物と、 ▲数式、化学式、表等があります▼〔II〕 （式中、Ｒ＿５はオルト芳香族炭化水素、ＺはＮＨ、Ｏ
又はＳである） を含有し、樹脂（ａ）１００重量部に対して、付加重合
性物質（ｂ）が５〜１５０重量部配合され、光重合開始
剤（ｃ）が０．０１〜１０重量部配合され、式〔II〕で
示される化合物（ｄ）が０．０１〜１重量部配合されて
いることを特徴とする感光性樹脂組成物。[Claims] 1. (a) α,β-unsaturated ethylenic monomers are used as structural units, among which 10 to 4 monomers having carboxylic acid are used.
A resin soluble in an alkaline solution containing 0% by weight, (b) an addition polymerizable substance represented by the following formula [I], and ▲
There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (In the formula, R_1, R_2, R_3, R_4 are H or CH
_3, which may be the same or different;
(n and m are positive integers such that n+m=2 to 4) (c) a photopolymerization initiator that sensitizes to actinic rays; (d) a compound represented by the following formula [II]; ▲Mathematical formula, chemical formula , tables, etc. ▼ [II] (In the formula, R_5 is an ortho aromatic hydrocarbon, Z is NH, O
or S), the addition polymerizable substance (b) is blended in an amount of 5 to 150 parts by weight with respect to 100 parts by weight of the resin (a), and the photopolymerization initiator (c) is blended in an amount of 0.01 to 10 parts by weight. 1 part by weight of a compound (d) represented by formula [II].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18648388A JPH0235454A (en) | 1988-07-25 | 1988-07-25 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18648388A JPH0235454A (en) | 1988-07-25 | 1988-07-25 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0235454A true JPH0235454A (en) | 1990-02-06 |
Family
ID=16189276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18648388A Pending JPH0235454A (en) | 1988-07-25 | 1988-07-25 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0235454A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0511439A (en) * | 1990-09-13 | 1993-01-22 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPH10274853A (en) * | 1997-03-27 | 1998-10-13 | Tokyo Ohka Kogyo Co Ltd | Pattern forming method and negative photoresist composition used for that method |
| WO2005029188A1 (en) * | 2003-09-24 | 2005-03-31 | Hitachi Chemical Co., Ltd. | Photosensitive element, method of forming resist pattern, and process for producing printed wiring board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53702A (en) * | 1975-12-23 | 1978-01-06 | Dynachem Corp | Adhesion promoting agent for polymerized film |
| JPS57192946A (en) * | 1981-05-11 | 1982-11-27 | Hitachi Chem Co Ltd | Photosensitive resin composition |
| JPS5888741A (en) * | 1981-11-20 | 1983-05-26 | Hitachi Chem Co Ltd | Photosensitive resin composition and its laminate |
| JPS60240715A (en) * | 1984-05-14 | 1985-11-29 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive resin composition laminate |
| JPS614038A (en) * | 1984-06-18 | 1986-01-09 | Asahi Chem Ind Co Ltd | Novel photosensitive material |
| JPS616644A (en) * | 1984-06-20 | 1986-01-13 | Asahi Chem Ind Co Ltd | Novel photosensitive composition |
-
1988
- 1988-07-25 JP JP18648388A patent/JPH0235454A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53702A (en) * | 1975-12-23 | 1978-01-06 | Dynachem Corp | Adhesion promoting agent for polymerized film |
| JPS57192946A (en) * | 1981-05-11 | 1982-11-27 | Hitachi Chem Co Ltd | Photosensitive resin composition |
| JPS5888741A (en) * | 1981-11-20 | 1983-05-26 | Hitachi Chem Co Ltd | Photosensitive resin composition and its laminate |
| JPS60240715A (en) * | 1984-05-14 | 1985-11-29 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive resin composition laminate |
| JPS614038A (en) * | 1984-06-18 | 1986-01-09 | Asahi Chem Ind Co Ltd | Novel photosensitive material |
| JPS616644A (en) * | 1984-06-20 | 1986-01-13 | Asahi Chem Ind Co Ltd | Novel photosensitive composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0511439A (en) * | 1990-09-13 | 1993-01-22 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPH10274853A (en) * | 1997-03-27 | 1998-10-13 | Tokyo Ohka Kogyo Co Ltd | Pattern forming method and negative photoresist composition used for that method |
| WO2005029188A1 (en) * | 2003-09-24 | 2005-03-31 | Hitachi Chemical Co., Ltd. | Photosensitive element, method of forming resist pattern, and process for producing printed wiring board |
| JPWO2005029188A1 (en) * | 2003-09-24 | 2007-11-15 | 日立化成工業株式会社 | Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method |
| KR100907368B1 (en) * | 2003-09-24 | 2009-07-10 | 히다치 가세고교 가부시끼가이샤 | Photosensitive element, method of forming resist pattern, and process for producing printed wiring board |
| US7622243B2 (en) | 2003-09-24 | 2009-11-24 | Hitachi Chemical Company, Ltd. | Photosensitive element, resist pattern formation method and printed wiring board production method |
| JP4640177B2 (en) * | 2003-09-24 | 2011-03-02 | 日立化成工業株式会社 | Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method |
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