KR20210038554A - Photosensitive resin composition, plating method, and manufacturing method of metal pattern - Google Patents
Photosensitive resin composition, plating method, and manufacturing method of metal pattern Download PDFInfo
- Publication number
- KR20210038554A KR20210038554A KR1020217002811A KR20217002811A KR20210038554A KR 20210038554 A KR20210038554 A KR 20210038554A KR 1020217002811 A KR1020217002811 A KR 1020217002811A KR 20217002811 A KR20217002811 A KR 20217002811A KR 20210038554 A KR20210038554 A KR 20210038554A
- Authority
- KR
- South Korea
- Prior art keywords
- photosensitive resin
- resin composition
- mass
- acrylate monomer
- acrylate
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000007747 plating Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 84
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 42
- -1 ethylene oxide-modified pentaerythritol tetraacrylate Chemical class 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 230000007261 regionalization Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000018109 developmental process Effects 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000011282 treatment Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 150000007514 bases Chemical class 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 125000004386 diacrylate group Chemical group 0.000 description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-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
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-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
- 238000010306 acid treatment Methods 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- LPYUENQFPVNPHY-UHFFFAOYSA-N 3-methoxycatechol Chemical compound COC1=CC=CC(O)=C1O LPYUENQFPVNPHY-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
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PRBBFHSSJFGXJS-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.C=CC(=O)OCC(C)(C)COC(=O)C=C PRBBFHSSJFGXJS-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ZMZHRHTZJDBLEX-UHFFFAOYSA-N (2-phenylphenyl) prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1C1=CC=CC=C1 ZMZHRHTZJDBLEX-UHFFFAOYSA-N 0.000 description 1
- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- UCSGWEMRGIONEW-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(2-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC=C1C1=C(C=2C(=CC=CC=2)OC)NC(C=2C(=CC=CC=2)Cl)=N1 UCSGWEMRGIONEW-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
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- 229940086559 methyl benzoin Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PKZWDLHLOBYXKV-UHFFFAOYSA-M oxazine-1 perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(N(CC)CC)=CC2=[O+]C3=CC(N(CC)CC)=CC=C3N=C21 PKZWDLHLOBYXKV-UHFFFAOYSA-M 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002991 phenoxazines Chemical class 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-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
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
협피치의 레지스트 패턴에 있어서도 레지스트 박리가 용이하고, 또한 패턴 형성이나 도금 공정에 있어서, 미세한 라인이나 도트가 기재 상에 안정적으로 유지되고, 높은 해상성을 갖는 감광성 수지 조성물 및 그 감광성 수지 조성물을 사용한 도금 방법을 제공하는 것을 과제로 하고, (A) 알칼리 가용성 수지, (B) 광중합 개시제 및 (C) 아크릴레이트 모노머를 함유하고, (C) 아크릴레이트 모노머에 대해, (D) 메타크릴레이트 모노머의 함유율이 0 ∼ 5 질량％ 이고, (C) 아크릴레이트 모노머로서 (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 를 함유하고, (C) 전체량에 대해, (C1) 의 함유율이 30 ∼ 70 질량％ 인 감광성 수지 조성물 및 그 감광성 수지 조성물을 사용한 도금 방법 및 금속 패턴의 제조 방법에 의해 상기 과제를 해결하였다.
Description
본 발명은, 감광성 수지 조성물, 그리고, 그 감광성 수지 조성물을 사용한 도금 방법 및 금속 패턴의 제조 방법에 관한 것이다.The present invention relates to a photosensitive resin composition, and a plating method using the photosensitive resin composition and a method for producing a metal pattern.
최근, 전자 기기의 소형화, 경량화에 수반하여, 프린트 배선판, 메탈 마스크 등에 있어서의 패턴의 미세화가 진행되고 있다. 그 때문에, 프린트 배선판의 도체 회로 제작 또는 메탈 마스크의 제작에 있어서, 감광성 수지 조성물과 전해 도금을 이용한 애디티브법에 의한 금속층의 제작이 실시되고 있다.In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization of patterns in printed wiring boards, metal masks, and the like has progressed. Therefore, in production of a conductor circuit of a printed wiring board or production of a metal mask, production of a metal layer by an additive method using a photosensitive resin composition and electrolytic plating is performed.
예를 들어, 프린트 배선판에 있어서의 (세미) 애디티브법은, 먼저 유리 에폭시 수지 등의 절연 수지의 표면에 무전해 도금에 의해 얇은 무전해 도금층을 형성하고, 다음으로 구리층 표면에 감광성 수지 조성물을 함유하는 감광성 수지층을 형성하고, 다음으로 노광, 현상을 실시하여 레지스트 패턴을 형성하고, 다음으로 전해 도금에 의해 전해 도금층을 두껍게 적층한 후, 레지스트 패턴을 박리하고, 박리 후에 나타난 무전해 도금층을 에칭하는 방법이다 (예를 들어, 특허문헌 1).For example, in the (semi) additive method in a printed wiring board, first, a thin electroless plated layer is formed on the surface of an insulating resin such as a glass epoxy resin by electroless plating, and then a photosensitive resin composition is applied to the surface of the copper layer. After forming a photosensitive resin layer containing, and then performing exposure and development to form a resist pattern, and then thickly laminating the electroplated layer by electroplating, the resist pattern was peeled off, and the electroless plated layer that appeared after the peeling It is a method of etching (for example, Patent Document 1).
또, 예를 들어, 메탈 마스크의 제작 방법으로서, 기판 상에 소정의 두께의 감광성 수지 조성물을 함유하는 감광성 수지층을 형성하는 제 1 공정과, 감광성 수지층 위에 메탈 마스크의 개구에 맞추어 패턴 노광하는 제 2 공정과, 현상하여 감광성 수지층의 비노광 부분만 제거하여 레지스트 패턴을 형성하고, 기판을 노출시키는 제 3 공정과, 이 제 3 공정에 의해 얻은 기판의 노출 부분에 전해 도금에 의해 메탈 마스크재층을 형성하는 제 4 공정을 실시한 후, 잔여의 감광성 수지층을 제거하는 제 5 공정과, 메탈 마스크재층을 기판으로부터 분리하는 제 6 공정을 실시하여 제작하는 방법이 있다 (예를 들어, 특허문헌 2).Further, for example, as a method of manufacturing a metal mask, a first step of forming a photosensitive resin layer containing a photosensitive resin composition having a predetermined thickness on a substrate, and pattern exposure on the photosensitive resin layer according to the opening of the metal mask. The second step, the third step of forming a resist pattern by removing only the unexposed portion of the photosensitive resin layer by developing, and exposing the substrate, and a metal mask by electrolytic plating on the exposed portion of the substrate obtained by the third step After performing the fourth step of forming a re-layer, there are a fifth step of removing the remaining photosensitive resin layer, and a method of producing by performing a sixth step of separating the metal mask material layer from the substrate (for example, Patent Document 2).
이들 방법에 있어서는, 협피치의 레지스트 패턴을 형성하고, 그 좁은 스페이스 사이에 전해 도금을 실시하여, 전해 도금층 또는 메탈 마스크재층이 되는 금속층을 두껍게 형성한다. 그러나, 이 후에 이어지는, 레지스트 패턴을 박리하거나 또는 잔여의 감광성 수지층을 제거하는 공정인 레지스트 박리의 공정에 있어서, 레지스트 패턴이 정상적으로 박리되지 않고, 프린트 배선판이나 메탈 마스크 상에 레지스트 박리편이 잔류해 버리는 문제가 있었다.In these methods, a narrow-pitch resist pattern is formed, and electroplating is performed between the narrow spaces to form a thick metal layer serving as an electroplating layer or a metal mask material layer. However, in the subsequent process of peeling the resist, which is a process of peeling off the resist pattern or removing the remaining photosensitive resin layer, the resist pattern is not normally peeled off, and the resist peeling piece remains on the printed wiring board or the metal mask. There was a problem.
이와 같은 레지스트 박리의 문제를 해결하기 위해, 기재에 대한 밀착성이 높고, 또한 레지스트 박리액에 용해되는 감광성 수지 조성물이 제안되어 있다 (예를 들어, 특허문헌 3 ∼ 6 참조). 레지스트 박리액에 대한 용해성이 양호하면, 좁은 스페이스 사이에 레지스트 박리편이 잔존하는 문제를 없앨 수 있다.In order to solve such a problem of resist peeling, a photosensitive resin composition having high adhesion to a substrate and dissolving in a resist stripping solution has been proposed (see, for example, Patent Documents 3 to 6). If the solubility in the resist stripping solution is good, the problem that the resist stripping pieces remain between narrow spaces can be eliminated.
특허문헌 3 ∼ 6 에서는, 감광성 수지 조성물의 레지스트 박리액에 대한 용해성을 높이기 위해서, 가교성 모노머로서, 메타크릴레이트 모노머의 함유량을 줄이고, 아크릴레이트 모노머의 함유량을 늘린 감광성 수지 조성물이 제안되어 있다. 그러나, 아크릴레이트 모노머의 함유량을 늘린 경우, 감광성 수지 조성물의 친수성이 높기 때문에, 알칼리 현상시에 감광성 수지층이 팽윤하고, 그 결과, 레지스트 두께가 50 ㎛ 이상으로 두꺼운 경우에, 50 ㎛ 이하와 같은 좁은 레지스트 스페이스를 해상하는 것이 곤란한 문제, 레지스트 패턴 형성 및 도금의 공정에서, 미세한 라인이나 도트가 기재 상으로부터 박리되기 쉬워지는 문제 등이 존재한다.In Patent Documents 3 to 6, in order to increase the solubility of the photosensitive resin composition in a resist stripper, as a crosslinkable monomer, a photosensitive resin composition in which the content of the methacrylate monomer is reduced and the content of the acrylate monomer is increased is proposed. However, when the content of the acrylate monomer is increased, since the photosensitive resin composition has high hydrophilicity, the photosensitive resin layer swells during alkaline development, and as a result, when the resist thickness is 50 μm or more, it is 50 μm or less. There exist a problem in which it is difficult to resolve a narrow resist space, a problem in that fine lines or dots are easily peeled off from the substrate in the process of forming a resist pattern and plating.
그 때문에, 레지스트 박리액에 용해되는 특성을 갖고, 미세한 라인이나 도트를 갖는 레지스트 패턴에 있어서도, 패턴 형성이나 도금 공정에 있어서 기재 상에 안정적으로 유지되고, 또한 높은 해상성을 갖는 감광성 수지 조성물이 요망되고 있다.Therefore, a photosensitive resin composition having a property of dissolving in a resist stripping solution and having a high resolution, which is stably maintained on the substrate in the pattern formation or plating process, even for a resist pattern having fine lines or dots is desired. Has become.
본 발명의 과제는, 협피치의 레지스트 패턴에 있어서도 레지스트 박리가 용이하고, 또한 패턴 형성이나 도금 공정에 있어서 미세한 라인이나 도트가 기재 상에 안정적으로 유지되고, 또한 높은 해상성을 갖는 감광성 수지 조성물, 그리고, 그 감광성 수지 조성물을 사용한 도금 방법 및 금속 패턴의 제조 방법을 제공하는 것이다.The subject of the present invention is a photosensitive resin composition having easy resist peeling even in a narrow-pitch resist pattern, in which fine lines and dots are stably maintained on the substrate in pattern formation and plating processes, and has high resolution, And it is to provide a plating method and a method for producing a metal pattern using the photosensitive resin composition.
상기 과제를 해결하기 위해서 예의 검토한 결과, 하기 수단을 알아냈다.In order to solve the said subject, as a result of intensive examination, the following means were found.
＜1＞<1>
(A) 알칼리 가용성 수지, (B) 광중합 개시제 및 (C) 아크릴레이트 모노머를 함유하고,(A) an alkali-soluble resin, (B) a photoinitiator and (C) an acrylate monomer,
(C) 아크릴레이트 모노머에 대해, (D) 메타크릴레이트 모노머의 함유율이 0 ∼ 5 질량％ 이고,(C) with respect to the acrylate monomer, the content rate of the (D) methacrylate monomer is 0 to 5% by mass,
(C) 아크릴레이트 모노머로서, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 를 함유하고,(C) As an acrylate monomer, (C1) ethylene oxide-modified pentaerythritol tetraacrylate (a compound represented by general formula (i), l+m+n+o=24-48) is contained,
(C) 아크릴레이트 모노머 전체량에 대해, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 의 함유율이 30 ∼ 70 질량％ 인 것을 특징으로 하는 감광성 수지 조성물.(C) The content rate of (C1) ethylene oxide-modified pentaerythritol tetraacrylate (a compound represented by the general formula (i), l+m+n+o=24 to 48) with respect to the total amount of the (C) acrylate monomer is 30 The photosensitive resin composition characterized in that it is-70 mass %.
[화학식 1][Formula 1]
＜2＞<2>
그 감광성 수지 조성물이, (C) 아크릴레이트 모노머로서, (C2) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 ∼ 8 인 화합물) 를 함유하고, (C) 아크릴레이트 모노머 전체량에 대해, (C2) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 ∼ 8 인 화합물) 의 함유율이 30 ∼ 70 질량％ 인 ＜1＞ 에 기재된 감광성 수지 조성물.The photosensitive resin composition, (C) as an acrylate monomer, (C2) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), l + m + n + o = 4 to 8 compound) Containing, (C) with respect to the total amount of the acrylate monomer, (C2) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), 1 + m + n + o = 4 to 8 compound) of The photosensitive resin composition as described in <1> whose content rate is 30-70 mass %.
＜3＞<3>
그 감광성 수지 조성물이 (E) 중합 금지제를 함유하고, (A) 알칼리 가용성 수지, (B) 광중합 개시제, (C) 아크릴레이트 모노머 및 (E) 중합 금지제의 총량에 대해, (E) 중합 금지제의 함유율이 400 ∼ 1000 ppm 인 ＜1＞ 에 기재된 감광성 수지 조성물.The photosensitive resin composition contains (E) a polymerization inhibitor, (E) polymerization with respect to the total amount of (A) alkali-soluble resin, (B) photoinitiator, (C) acrylate monomer and (E) polymerization inhibitor. The photosensitive resin composition according to <1>, wherein the content rate of the inhibitor is from 400 to 1000 ppm.
＜4＞<4>
그 감광성 수지 조성물이 (F) 광발색제를 함유하고, (A) 알칼리 가용성 수지, (B) 광중합 개시제, (C) 아크릴레이트 모노머 및 (F) 광발색제의 총량에 대해 (F) 광발색제의 함유율이 0.15 ∼ 1.5 질량％ 인 ＜1＞ 에 기재된 감광성 수지 조성물.The photosensitive resin composition contains (F) a photochromic agent, and (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) an acrylate monomer, and (F) the content of the photochromic agent relative to the total amount of the photochromic agent. The photosensitive resin composition according to <1>, which is 0.15 to 1.5% by mass.
＜5＞ <5>
＜1＞ 내지 ＜4＞ 중 어느 하나에 기재된 감광성 수지 조성물을 함유하는 감광성 수지층을 기재 상에 형성하고, 다음으로 패턴 노광을 실시하여 노광부를 경화시키고, 이어서 알칼리 현상을 실시하여 비노광부의 감광성 수지층을 제거하여, 경화된 감광성 수지층을 포함하는 레지스트 패턴을 형성한 후, 노출되어 있는 기재에 도금을 실시하는 것을 특징으로 하는 도금 방법.The photosensitive resin layer containing the photosensitive resin composition in any one of <1> to <4> was formed on the base material, and pattern exposure was performed next to harden the exposed part, and then alkali development was performed to the photosensitivity of the non-exposed part. A plating method comprising removing the resin layer to form a resist pattern including the cured photosensitive resin layer, and then plating the exposed substrate.
＜6＞<6>
＜5＞ 에 기재된 도금 방법을 이용하여 기재 상에 금속 패턴을 형성하는 것을 특징으로 하는 금속 패턴의 제조 방법.A method for producing a metal pattern, comprising forming a metal pattern on a substrate by using the plating method described in <5>.
본 발명에 의하면, 협피치의 레지스트 패턴에 있어서도 레지스트 박리가 용이하고, 또한 패턴 형성이나 도금 공정에 있어서 미세한 라인이나 도트가 기재 상에 안정적으로 유지되고, 또한 높은 해상성을 갖는 감광성 수지 조성물, 및 그 감광성 수지 조성물을 사용한 도금 방법을 제공할 수 있다.According to the present invention, resist peeling is easy even in a narrow-pitch resist pattern, and fine lines and dots are stably maintained on the substrate in the pattern formation or plating process, and a photosensitive resin composition having high resolution, and A plating method using the photosensitive resin composition can be provided.
또, 본 발명에 의하면, 패턴 형성 후의 레지스트 박리가 용이하고, 또한 레지스트 패턴이 기재 상에 안정적으로 유지되므로, 도금 공정에 있어서 미세한 라인이나 도트가 기재 상에 형성되고, 높은 해상성을 갖는 금속 패턴을 형성할 수 있다.Further, according to the present invention, since resist peeling after pattern formation is easy and the resist pattern is stably maintained on the substrate, fine lines or dots are formed on the substrate in the plating process, and a metal pattern having high resolution Can be formed.
이하, 본 발명의 감광성 수지 조성물 및 도금 방법에 대해 상세하게 설명한다.Hereinafter, the photosensitive resin composition and plating method of the present invention will be described in detail.
본 발명의 감광성 수지 조성물은, (A) 알칼리 가용성 수지, (B) 광중합 개시제 및 (C) 아크릴레이트 모노머를 함유하고, (C) 아크릴레이트 모노머에 대해, (D) 메타크릴레이트 모노머의 함유율이 0 ∼ 5 질량％ 이고, (C) 아크릴레이트 모노머로서 (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 를 함유하고, (C) 아크릴레이트 모노머 전체량에 대해, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 의 함유율이 30 ∼ 70 질량％ 인 것을 특징으로 한다.The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photoinitiator, and (C) an acrylate monomer, and the content rate of (D) a methacrylate monomer is relative to the (C) acrylate monomer. It is 0-5 mass%, and (C1) ethylene oxide-modified pentaerythritol tetraacrylate (a compound represented by general formula (i), 1+m+n+o=24-48) as an acrylate monomer Containing, (C) with respect to the total amount of the acrylate monomer, (C1) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), 1 + m + n + o = 24-48 compound) of It is characterized in that the content is 30 to 70% by mass.
[화학식 2][Formula 2]
일반식 (i) 에 있어서의 l 과 m 과 n 과 o 는, 모두 일반식 (i) 에 있어서의 반복 단위수이고, 모두 자연수이다.All of l and m and n and o in the general formula (i) are the number of repeating units in the general formula (i), and all are natural numbers.
본 발명에 있어서의 (A) 알칼리 가용성 수지에 있어서, 「알칼리 가용성」이란, 대상이 되는 수지를 피막으로 하고, 1 질량％ 의 탄산나트륨 수용액에 25 ℃ 에서 10 분간 침지했을 때, 막 두께 0.01 ㎛ 이상이 용해되는 성질을 말한다.In (A) alkali-soluble resin in the present invention, "alkali-soluble" means a target resin as a film, and when immersed in 1% by mass of sodium carbonate aqueous solution at 25°C for 10 minutes, the film thickness is 0.01 μm or more. It refers to the dissolving property.
(A) 알칼리 가용성 수지란, 구체적으로는, 산성기를 함유하는 수지이고, 산가가 40 mgKOH/g 이상인 수지를 들 수 있다. 그 산성기로는, 구체적으로는 카르복실기, 페놀성 수산기, 술폰산기, 인산기 등을 들 수 있다.(A) The alkali-soluble resin specifically is a resin containing an acidic group, and an acid value of 40 mgKOH/g or more is exemplified. Specific examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group.
(A) 알칼리 가용성 수지로는, 예를 들어, (메트)아크릴계 수지, 스티렌계 수지, 에폭시계 수지, 아미드계 수지, 아미드 에폭시계 수지, 알키드계 수지, 페놀계 수지 등의 유기 고분자를 들 수 있다. 이것들은, 1 종을 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.(A) Examples of alkali-soluble resins include organic polymers such as (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. have. These may be used individually by 1 type, and may be used in combination of 2 or more types.
그 중에서도, (메트)아크릴계 수지를 사용하는 것이 바람직하다. 그 (메트)아크릴계 수지로는, (메트)아크릴레이트를 주로 하고, 이것에 에틸렌성 불포화 카르복실산을 공중합시켜 이루어지는 (메트)아크릴계 중합체가 바람직하다. 또, 이것에는, 그 밖의 공중합 가능한 에틸렌성 불포화기를 갖는 모노머를 공중합 시킨 것이어도 된다.Among them, it is preferable to use a (meth)acrylic resin. As the (meth)acrylic resin, a (meth)acrylate is mainly used, and a (meth)acrylic polymer obtained by copolymerizing ethylenically unsaturated carboxylic acid with this is preferable. Moreover, you may copolymerize this with another monomer which has an ethylenically unsaturated group which can be copolymerized.
상기 (메트)아크릴레이트로는, 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, n-헥실(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 2-(디메틸아미노)에틸(메트)아크릴레이트, 2-(디에틸아미노)에틸(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트 등을 들 수 있다.As the (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth) Acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(dimethylamino) Ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl ( And meth)acrylate.
또한, 「(메트)아크릴계」, 「(메트)아크릴레이트」등으로 기재했을 때에는, 각각, 「아크릴계 혹은 메타크릴계」, 「아크릴레이트 혹은 메타크릴레이트」등을 의미한다.In addition, when it describes as "(meth)acrylic system", "(meth)acrylate", etc., it means "acrylic type or methacrylic type", "acrylate or methacrylate", etc., respectively.
상기 에틸렌성 불포화 카르복실산으로서, 아크릴산, 메타크릴산, 크로톤산 등의 모노카르복실산이 바람직하게 사용되고, 말레산, 푸마르산, 이타콘산 등의 디카르복실산이나, 그것들의 무수물이나 하프 에스테르를 사용할 수도 있다. 이것들 중에서도, 아크릴산, 메타크릴산이 특히 바람직하다.As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid are preferably used, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and anhydrides or half esters thereof are used. May be. Among these, acrylic acid and methacrylic acid are particularly preferred.
상기 그 밖의 공중합 가능한 에틸렌성 불포화기를 갖는 모노머로는, 예를 들어, 스티렌, α-메틸스티렌, p-메틸스티렌, p-에틸스티렌, p-메톡시스티렌, p-에톡시스티렌, p-클로로스티렌, p-브로모스티렌, (메트)아크릴로니트릴, (메트)아크릴아미드, 디아세톤아크릴아미드, 비닐톨루엔, 아세트산비닐, 비닐-n-부틸에테르 등을 들 수 있다.As the monomers having other copolymerizable ethylenically unsaturated groups, for example, styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chloro Styrene, p-bromostyrene, (meth)acrylonitrile, (meth)acrylamide, diacetoneacrylamide, vinyltoluene, vinyl acetate, vinyl-n-butyl ether, and the like.
(A) 알칼리 가용성 수지의 산가는, 알칼리 현상 속도, 레지스트 박리 속도, 노광 감도, 감광성 수지층의 유연함, 감광성 수지층과 기재의 밀착성 등에 영향을 미친다. (A) 알칼리 가용성 수지의 산가는, 40 ∼ 500 mgKOH/g 인 것이 바람직하고, 100 ∼ 300 mgKOH/g 인 것이 보다 바람직하다.(A) The acid value of the alkali-soluble resin affects the alkali development rate, resist peeling rate, exposure sensitivity, softness of the photosensitive resin layer, adhesion between the photosensitive resin layer and the substrate, and the like. (A) It is preferable that it is 40-500 mgKOH/g, and, as for the acid value of (A) alkali-soluble resin, it is more preferable that it is 100-300 mgKOH/g.
산가가 40 mgKOH/g 미만에서는, 알칼리 현상 시간이 길어지는 경우가 있고, 한편, 500 mgKOH/g 을 초과하면, 감광성 수지층과 기재의 밀착성이 나빠지는 경우가 있다. 상기 산가는, JIS K2501 : 2003 에 준거하여 측정한 값이다.When the acid value is less than 40 mgKOH/g, the alkali development time may be prolonged, while when it exceeds 500 mgKOH/g, the adhesion between the photosensitive resin layer and the substrate may be deteriorated. The acid value is a value measured according to JIS K2501:2003.
또, (A) 알칼리 가용성 수지의 질량 평균 분자량은, 5,000 ∼ 150,000 인 것이 바람직하고, 10,000 ∼ 100,000 인 것이 보다 바람직하다. (A) 알칼리 가용성 수지의 질량 평균 분자량이 5,000 미만에서는, 경화 전의 감광성 수지 조성물을 필름 상태로 형성하는 것이 곤란해지는 경우가 있다. 한편, (A) 알칼리 가용성 수지의 질량 평균 분자량이 150,000 을 초과하면, 알칼리 현상액에 대한 용해성이 악화되는 경우나, 레지스트 박리액에 용해되는 속도가 느려지는 경우가 있다.Moreover, it is preferable that it is 5,000-150,000, and, as for the mass average molecular weight of (A) alkali-soluble resin, it is more preferable that it is 10,000-100,000. (A) When the mass average molecular weight of the alkali-soluble resin is less than 5,000, it may become difficult to form the photosensitive resin composition before curing in a film state. On the other hand, when the mass average molecular weight of the (A) alkali-soluble resin exceeds 150,000, the solubility in an alkali developer may deteriorate, or the rate at which it dissolves in a resist stripping solution may be slowed.
(B) 광중합 개시제로는, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1-온, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온 등의 방향족 케톤 ; 2-에틸안트라퀴논, 페난트렌퀴논, 2-tert-부틸안트라퀴논, 옥타메틸안트라퀴논, 1,2-벤즈안트라퀴논, 2,3-벤즈안트라퀴논, 2-페닐안트라퀴논, 2,3-디페닐안트라퀴논, 1-클로로안트라퀴논, 2-메틸안트라퀴논, 1,4-나프토퀴논, 9,10-페난트라퀴논, 2-메틸-1,4-나프토퀴논, 2,3-디메틸안트라퀴논 등의 퀴논류 ; 벤조인메틸에테르, 벤조인에틸에테르, 벤조인페닐에테르 등의 벤조인에테르 화합물 ; 벤조인, 메틸벤조인, 에틸벤조인 등의 벤조인 화합물 ; 벤질디메틸케탈, 1-하이드록시-시클로헥실-페닐-케톤, 2-하이드록시-2-메틸-1-페닐-프로판-1-온, 1-[4-(2-하이드록시에톡시)-페닐]-2-하이드록시-2-메틸-1-프로판-1-온, 2-하이드록시-1-｛4-[4-(2-하이드록시-2-메틸-프로피오닐)-벤질]페닐｝-2-메틸-프로판-1-온, 2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부타논 등의 알킬페논류 ; 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스핀옥사이드류 ; 1,2-옥탄디온,1-[4-(페닐티오)-,2-(o-벤조일옥심)], 에타논,1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-,1-(o-아세틸옥심) 등의 옥심에스테르류 ; 2-(o-클로로페닐)-4,5-디페닐이미다졸 이량체, 2-(o-클로로페닐)-4,5-비스(메톡시페닐)이미다졸 이량체, 2-(o-플루오로페닐)-4,5-디페닐이미다졸 이량체, 2-(o-메톡시페닐)-4,5-디페닐이미다졸 이량체, 2-(p-메톡시페닐)-4,5-디페닐이미다졸 이량체 등의 2,4,5-트리아릴이미다졸 이량체 ; 9-페닐아크리딘, 1,7-비스(9,9'-아크리디닐)헵탄 등의 아크리딘 유도체 ; N-페닐글리신, N-페닐글리신 유도체 ; 쿠마린계 화합물 ; 벤조페논, 벤조일벤조산, 벤조일벤조산메틸, 4-페닐벤조페논, 하이드록시벤조페논, 아크릴화벤조페논, 4-벤조일-4'-메틸디페닐설파이드, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논, 4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논 등의 벤조페논계 화합물 등을 들 수 있다.(B) As a photoinitiator, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]- Aromatic ketones such as 2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthra Quinones such as quinone; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; Benzyldimethylketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-｛4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl｝ -2-methyl-propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Alkylphenones; Acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 1,2-octanedione,1-[4-(phenylthio)-,2-(o-benzoyloxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Oxime esters such as bazol-3-yl]-,1-(o-acetyloxime); 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o- Fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4 2,4,5-triarylimidazole dimers, such as a ,5-diphenylimidazole dimer; Acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine and N-phenylglycine derivatives; Coumarin-based compounds; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t Benzophenone compounds, such as -butylperoxycarbonyl)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone, etc. are mentioned.
상기 2,4,5-트리아릴이미다졸 이량체에 있어서의 2 개의 2,4,5-트리아릴이미다졸의 아릴기의 치환기는, 동일하고 대칭인 화합물을 부여해도 되고, 상이하고 비대칭인 화합물을 부여해도 된다. 또, 디에틸티오크산톤과 디메틸아미노벤조산 의 조합과 같이, 티오크산톤계 화합물과 3 급 아민 화합물을 조합해도 된다.Substituents of the aryl groups of two 2,4,5-triarylimidazole in the 2,4,5-triarylimidazole dimer may be given the same and symmetrical compound, different and asymmetric You may give a phosphorus compound. Moreover, like the combination of diethyl thioxanthone and dimethylaminobenzoic acid, you may combine a thioxanthone type compound and a tertiary amine compound.
이것들은 단독으로 또는 2 종류 이상을 조합하여 사용된다. 그 중에서도, 이미다졸 이량체를, 고감도여서 바람직하게 사용할 수 있고, 또한, 2-(o-클로로페닐)-4,5-디페닐이미다졸 이량체를 유용하게 사용할 수 있다.These are used alone or in combination of two or more. Among them, an imidazole dimer can be preferably used because of its high sensitivity, and a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer can be usefully used.
본 발명의 감광성 수지 조성물은, (C) 아크릴레이트 모노머로서, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 를 함유한다. (C1) 을 함유하는 것에 의해, 레지스트 박리시에 레지스트편이 용해된다는 특성을 유지하면서, 알칼리 현상시에 경화된 감광성 수지층의 팽윤이 적어, 기재와의 밀착성이 우수하여, 패턴 형성이나 도금 공정에 있어서 미세한 라인이나 도트가 안정적으로 유지된다는 효과를 달성할 수 있다.The photosensitive resin composition of the present invention is (C) an acrylate monomer, a compound having (C1) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), l + m + n + o = 24 to 48) ). By containing (C1), the photosensitive resin layer cured during alkaline development is less swelled while maintaining the property that the resist pieces are dissolved during resist stripping, and has excellent adhesion to the substrate. Therefore, it is possible to achieve the effect of stably maintaining fine lines or dots.
(C1) 의 l ＋ m ＋ n ＋ o 의 값이 24 보다 작으면, 언더 커트 (레지스트 바닥부의 획선 (畵線) 폭이 가늘어짐) 가 커지는 경우가 있고, 또, l ＋ m ＋ n ＋ o 의 값이 48 보다 크면, 알칼리 현상으로 감광성 수지층이 팽윤하기 쉬워져, 파인 패턴을 형성할 수 없는 경우가 있다. 따라서, (C1) 의 l ＋ m ＋ n ＋ o 의 값은, 24 ∼ 48 이고, 보다 바람직하게는 30 ∼ 40 이다.If the value of l+m+n+o in (C1) is less than 24, the undercut (the width of the stroke at the bottom of the resist becomes thinner) sometimes increases, and in addition, l + m + n + o When the value of is greater than 48, the photosensitive resin layer is liable to swell due to alkali development, and a fine pattern may not be formed. Therefore, the value of l+m+n+o of (C1) is 24 to 48, More preferably, it is 30 to 40.
본 발명의 감광성 수지 조성물은, (C) 아크릴레이트 모노머로서, (C2) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 ∼ 8 인 화합물) 를 함유하는 것이 바람직하다. (C2) 를 함유하는 것에 의해, 레지스트 박리시에 레지스트 박리편이 용해된다는 특성을 유지하면서, 알칼리 현상시에 감광성 수지층의 팽윤이 적어, 기재와의 밀착성이 우수하다는 효과가 보다 높아진다.The photosensitive resin composition of the present invention is (C) an acrylate monomer, a compound having (C2) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), l + m + n + o = 4 to 8) ) Is preferably contained. By containing (C2), the photosensitive resin layer swells less during alkaline development while maintaining the characteristic that the resist peeling piece dissolves at the time of resist peeling, and the effect of excellent adhesion to the substrate is enhanced.
(C2) 의 l ＋ m ＋ n ＋ o 의 값이 4 보다 작으면, 언더 커트가 커지는 경우가 있고, 또, l ＋ m ＋ n ＋ o 의 값이 8 보다 크면, 알칼리 현상으로 감광성 수지층이 팽윤하기 쉬워져, 파인 패턴을 형성할 수 없는 경우가 있다. 따라서, (C2) 의 l ＋ m ＋ n ＋ o 의 값은 4 ∼ 8 이고, 보다 바람직하게는 4 이다.If the value of l+m+n+o of (C2) is less than 4, the undercut may be large, and if the value of l+m+n+o is greater than 8, the photosensitive resin layer is formed by alkali development. It becomes easy to swell, and a fine pattern may not be formed. Therefore, the value of l+m+n+o of (C2) is 4-8, More preferably, it is 4.
(C) 아크릴레이트 모노머로는, 「(C3) (C1) 및 (C2) 이외의 아크릴레이트 모노머」를 함유해도 된다. (C3) 으로는, 1 이상의 아크릴로일기를 갖는 화합물을 들 수 있다.(C) As an acrylate monomer, you may contain "(C3) acrylate monomers other than (C1) and (C2)". As (C3), the compound which has one or more acryloyl groups is mentioned.
1 개의 아크릴로일기를 가진 (C3) 으로는, 예를 들어, 메틸아크릴레이트, 에틸아크릴레이트, n-프로필아크릴레이트, 이소프로필아크릴레이트, n-부틸아크릴레이트, 이소부틸아크릴레이트, t-부틸아크릴레이트, n-헥실아크릴레이트, 2-에틸헥실아크릴레이트, 시클로헥실아크릴레이트, 벤질아크릴레이트, 이소미리스틸아크릴레이트, 스테아릴아크릴레이트, 노닐페녹시폴리에틸렌글리콜아크릴레이트 (에톡시기 수가 1 이상), 2-하이드록시에틸아크릴레이트, 2-하이드록시프로필아크릴레이트, 글리시딜아크릴레이트, 라우릴아크릴레이트, 테트라하이드로푸르푸릴아크릴레이트, 2-(디메틸아미노)에틸아크릴레이트, 2-(디에틸아미노)에틸아크릴레이트, 2,2,2-트리플루오로에틸아크릴레이트, 2,2,3,3-테트라플루오로프로필아크릴레이트, 글리세린모노아크릴레이트, 메톡시폴리에틸렌글리콜아크릴레이트 (에톡시기 수가 2 ∼ 30), 페녹시폴리에틸렌글리콜아크릴레이트 (에톡시기 수가 2 ∼ 30), 메톡시폴리프로필렌글리콜아크릴레이트 (프로폭시기 수가 2 ∼ 30), 페녹시폴리프로필렌글리콜아크릴레이트 (프로폭시기 수가 2 ∼ 30), 2-아크릴로일옥시에틸숙시네이트, 2-하이드록시-3-페녹시프로필아크릴레이트, 에톡시화 o-페닐페놀아크릴레이트 등을 들 수 있다.As (C3) having one acryloyl group, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, isomyristyl acrylate, stearyl acrylate, nonylphenoxy polyethylene glycol acrylate (the number of ethoxy groups is 1 or more) , 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethyl Amino) ethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, glycerin monoacrylate, methoxypolyethylene glycol acrylate (the number of ethoxy groups is 2 30), phenoxy polyethylene glycol acrylate (the number of ethoxy groups is 2 to 30), methoxy polypropylene glycol acrylate (the number of propoxy groups is 2 to 30), phenoxy polypropylene glycol acrylate (the number of propoxy groups is 2 to 30), 2-acryloyloxyethyl succinate, 2-hydroxy-3-phenoxypropyl acrylate, ethoxylated o-phenylphenol acrylate, etc. are mentioned.
「에톡시기」란, 「-CH2CH2O-」이다. 「프로폭시기」란, 「-C3H6O-」이고, 직사슬형이어도 되고, 분기형이어도 된다."Ethoxy group" is "-CH 2 CH 2 O-". The "propoxy group" is "-C 3 H 6 O-", and may be linear or branched.
또, 2 개의 아크릴로일기를 가진 (C3) 으로는, 예를 들어, 다가의 알코올에 2 개의 아크릴산을 반응시켜 얻어지는 화합물을 들 수 있다. 또, 예를 들어, 에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트 (에톡시기 수가 2 ∼ 30), 프로필렌글리콜디아크릴레이트, 폴리프로필렌글리콜디아크릴레이트 (프로폭시기 수가 2 ∼ 30), 폴리테트라메틸렌글리콜디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 3-메틸-1,5-펜탄디올디아크릴레이트, 1,6-헥산디올디아크릴레이트, 1,10-데칸디올디아크릴레이트, 1,9-노난디올디아크릴레이트, 디메틸올트리시클로데칸디아크릴레이트, 비스페놀 A 의 에틸렌옥사이드 부가물의 디아크릴레이트 (에톡시기 수가 2 ∼ 30), 비스페놀 A 의 프로필렌옥사이드 부가물의 디아크릴레이트 (프로폭시기 수가 2 ∼ 40), 비스페놀 A 의 에틸렌옥사이드 및 프로필렌옥사이드 부가물의 디아크릴레이트 (에톡시기 및 프로폭시기의 합이 2 ∼ 40), 하이드록시피발산네오펜틸글리콜디아크릴레이트, 9,9-비스[4-(2-아크릴로일옥시에스테르)페닐]플루오레인, 트리시클로데칸디메탄올디아크릴레이트 등을 들 수 있다.Moreover, as (C3) which has two acryloyl groups, a compound obtained by reacting two acrylic acids with a polyhydric alcohol is mentioned, for example. In addition, for example, ethylene glycol diacrylate, polyethylene glycol diacrylate (the number of ethoxy groups 2 to 30), propylene glycol diacrylate, polypropylene glycol diacrylate (the number of propoxy groups 2 to 30), polytetra Methylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 1,9 -Nonandiol diacrylate, dimethylol tricyclodecane diacrylate, the diacrylate of the ethylene oxide adduct of bisphenol A (the number of ethoxy groups is 2 to 30), the diacrylate of the propylene oxide adduct of bisphenol A (the number of propoxy groups 2 to 40), diacrylate of ethylene oxide and propylene oxide adduct of bisphenol A (sum of ethoxy group and propoxy group is 2 to 40), hydroxypivalate neopentyl glycol diacrylate, 9,9-bis[ 4-(2-acryloyloxyester)phenyl]fluorine, tricyclodecane dimethanol diacrylate, etc. are mentioned.
또, 3 개 이상의 아크릴로일기를 가진 (C3) 으로는, 예를 들어, 다가의 알코올에 아크릴산을 반응시켜 얻어지는 화합물을 들 수 있다. 또, 예를 들어, 트리메틸올프로판트리아크릴레이트, 디트리메틸올프로판테트라아크릴레이트, 펜타에리트리톨트리아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨펜타아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 에틸렌옥사이드 변성 펜타에리트리톨트리아크릴레이트, 트리메틸올프로판트리글리시딜에테르트리아크릴레이트, 에틸렌옥사이드 변성 이소시아누르산트리아크릴레이트, ε-카프로락톤 변성 트리스-(2-아크릴옥시에틸)이소시아누레이트, 글리세린트리아크릴레이트, 에틸렌옥사이드 변성 글리세린트리아크릴레이트, 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o 가 4 미만, 8 초과 24 미만, 48 초과인 화합물) 등을 들 수 있다.Moreover, as (C3) which has 3 or more acryloyl groups, the compound obtained by making acrylic acid react with polyhydric alcohol is mentioned, for example. Further, for example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Ethylene oxide-modified pentaerythritol triacrylate, trimethylolpropane triglycidyl ether triacrylate, ethylene oxide-modified isocyanuric acid triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanu Rate, glycerin triacrylate, ethylene oxide-modified glycerin triacrylate, ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), l + m + n + o is less than 4, more than 8 and less than 24, 48 Excess compound), etc. are mentioned.
(D) 메타크릴레이트 모노머로는, 상기 (C) 아크릴레이트 모노머의 아크릴로일기를 메타크릴로일기로 치환한 화합물을 들 수 있다.As (D) a methacrylate monomer, the compound which substituted the acryloyl group of the said (C) acrylate monomer with a methacryloyl group is mentioned.
본 발명의 감광성 수지 조성물은, (D) 메타크릴레이트 모노머를 함유해도 되고, 그 함유율은, (C) 아크릴레이트 모노머에 대해 0 ∼ 5 질량％ 이다. (D) 메타크릴레이트 모노머의 함유율이 5 질량％ 초과인 경우, 레지스트 박리시에, 경화된 감광성 수지층의 박리편이 커져, 용해되지 않게 된다.The photosensitive resin composition of this invention may contain (D) a methacrylate monomer, and the content rate is 0-5 mass% with respect to (C) acrylate monomer. (D) When the content rate of the methacrylate monomer is more than 5% by mass, the peeling piece of the cured photosensitive resin layer becomes large and does not dissolve at the time of resist peeling.
본 발명에 있어서의 (C1) 의 함유율은, (C) 아크릴레이트 모노머 전체량에 대해 30 ∼ 70 질량％ 이고, 보다 바람직하게는 35 ∼ 65 질량％ 이고, 더욱 바람직하게는 40 ∼ 60 질량％ 이다.The content rate of (C1) in the present invention is 30 to 70% by mass, more preferably 35 to 65% by mass, and still more preferably 40 to 60% by mass with respect to the total amount of (C) acrylate monomer. .
함유율이 30 질량％ 보다 작으면, 또는 함유율이 지나치게 작으면, 언더 커트가 커지는 경우가 있고, 함유율이 70 질량％ 보다 크면, 또는 함유율이 지나치게 크면, 알칼리 현상으로 감광성 수지층이 팽윤하기 쉬워져, 밀착성이 악화되는 경우나 현상에 의해 미세한 라인이나 도트가 박리되는 경우가 있다.When the content rate is less than 30% by mass, or when the content rate is too small, the undercut may be large, and when the content rate is more than 70% by mass or when the content rate is too large, the photosensitive resin layer is liable to swell due to alkali development, There are cases where the adhesion is deteriorated or fine lines or dots are peeled off due to development.
또, 본 발명의 감광성 수지 조성물은, (C2) 를 함유하고 있는 것이 바람직하다. (C2) 의 함유율은, (C) 아크릴레이트 모노머 전체량에 대해 30 ∼ 70 질량％ 인 것이 바람직하고, 40 ∼ 60 질량％ 인 것이 보다 바람직하다. 함유율이 30 질량％ 보다 작으면, 알칼리 현상으로 감광성 수지층이 팽윤하기 쉬워져, 밀착성이 악화되는 경우가 있고, 함유율이 70 질량％ 보다 크면, 경화 피막이 단단하여 깨지기 쉬워지기 때문에, 반송 롤러 등의 접촉에 의해 레지스트에 결락이 발생하는 경우가 있다.Moreover, it is preferable that the photosensitive resin composition of this invention contains (C2). The content rate of (C2) is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass with respect to the total amount of the (C) acrylate monomer. If the content is less than 30% by mass, the photosensitive resin layer is liable to swell due to an alkali phenomenon, and the adhesion may deteriorate. If the content is greater than 70% by mass, the cured film is hard and fragile. The resist may fall off due to contact.
본 발명의 감광성 수지 조성물에 있어서, (A) 의 함유율은, (A), (B), (C) 및 (D) 의 총량에 대해 30 ∼ 75 질량％ 인 것이 바람직하고, 35 ∼ 70 질량％ 인 것이 보다 바람직하고, 40 ∼ 60 질량％ 인 것이 더욱 바람직하다. (A) 의 함유율이 30 질량％ 미만에서는, 피막성이 나빠지는 경우나, 알칼리 현상성이 저하되는 경우가 있다. (A) 의 함유율이 70 질량％ 를 초과하면, 레지스트 패턴의 해상성이 저하되는 경우가 있다.In the photosensitive resin composition of the present invention, the content rate of (A) is preferably 30 to 75 mass%, and 35 to 70 mass% with respect to the total amount of (A), (B), (C) and (D). It is more preferable that it is, and it is still more preferable that it is 40-60 mass %. When the content rate of (A) is less than 30% by mass, film properties may deteriorate or alkali developability may decrease. When the content rate of (A) exceeds 70% by mass, the resolution of the resist pattern may decrease.
(B) 의 함유율은, (A), (B), (C) 및 (D) 의 총량에 대해 0.1 ∼ 10 질량％ 인 것이 바람직하고, 0.2 ∼ 5 질량％ 인 것이 보다 바람직하다. (B) 의 함유율이 0.1 질량％ 미만에서는, 광중합성이 불충분해지는 경우가 있다. 한편, 10 질량％ 를 초과하면, 노광시에 감광성 수지층의 표면에서 흡수가 증대되어, 감광성 수지층 내부의 광가교가 불충분해지는 경우가 있다.The content rate of (B) is preferably 0.1 to 10 mass%, and more preferably 0.2 to 5 mass% with respect to the total amount of (A), (B), (C) and (D). When the content rate of (B) is less than 0.1% by mass, photopolymerization may become insufficient. On the other hand, when it exceeds 10 mass%, absorption at the surface of the photosensitive resin layer increases during exposure, and the photocrosslinking inside the photosensitive resin layer may become insufficient.
(C) 의 함유율은, (A), (B), (C) 및 (D) 의 총량에 대해 15 ∼ 60 질량％ 인 것이 바람직하고, 17 ∼ 55 질량％ 인 것이 보다 바람직하고, 20 ∼ 50 질량％ 인 것이 더욱 바람직하다. (C) 의 함유율이 15 질량％ 미만에서는, 가교성이 저하되는 경우가 있고, 또, 광감도가 불충분해지는 경우가 있다. 한편, 55 질량％ 를 초과하면, 막 표면의 점착성이 증가하는 경우가 있다.The content rate of (C) is preferably 15 to 60 mass%, more preferably 17 to 55 mass%, and 20 to 50 with respect to the total amount of (A), (B), (C) and (D). It is more preferable that it is mass %. When the content rate of (C) is less than 15% by mass, the crosslinking property may decrease, and the photosensitivity may be insufficient. On the other hand, when it exceeds 55 mass%, the adhesiveness of the film surface may increase.
본 발명의 감광성 수지 조성물은, (E) 중합 금지제를 함유하는 것이 바람직하고, (A), (B), (C) 및 (E) 의 총량에 대해, (E) 중합 금지제의 함유율이 400 ∼ 1000 ppm 인 것이 보다 바람직하다.The photosensitive resin composition of the present invention preferably contains (E) a polymerization inhibitor, and the content rate of the polymerization inhibitor (E) relative to the total amount of (A), (B), (C) and (E) is It is more preferably 400 to 1000 ppm.
(E) 중합 금지제는, 감광성 수지 조성물의 광경화능을 억제하는 작용을 갖는다.(E) The polymerization inhibitor has an action of suppressing the photocuring ability of the photosensitive resin composition.
(E) 중합 금지제는, 라디칼을 보충하여 감광성 수지 조성물의 광화학 반응을 정지시킬 수 있는 것이면 특별히 한정되지 않지만, 예를 들어, 하이드로퀴논, 메틸하이드로퀴논, 4-메톡시페놀, 2,5-디-tert-부틸하이드로퀴논, tert-부틸하이드로퀴논, 2,6-디-tert-부틸-p-크레졸, p-벤조퀴논, 메틸-p-벤조퀴논, tert-부틸-p-벤조퀴논, 카테콜, 4-tert-부틸카테콜, 3-메톡시카테콜, 피로갈롤, 피크르산 등의 하이드로퀴논류를 들 수 있다.(E) The polymerization inhibitor is not particularly limited as long as it is capable of stopping the photochemical reaction of the photosensitive resin composition by supplementing radicals. For example, hydroquinone, methylhydroquinone, 4-methoxyphenol, 2,5- Di-tert-butylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, cate And hydroquinones such as chol, 4-tert-butylcatechol, 3-methoxycatechol, pyrogallol, and picric acid.
또, 페녹사진, 3,7-비스(디에틸아미노)페녹사진-5-이움·퍼클로레이트, 5-아미노-9-(디메틸아미노)-10-메틸벤조[a]페녹사진-7-이움·클로라이드 등의 페녹사진 유도체를 들 수 있다.Further, phenoxazine, 3,7-bis(diethylamino)phenoxazine-5-ium perchlorate, 5-amino-9-(dimethylamino)-10-methylbenzo[a]phenoxazine-7-ium chloride And phenoxazine derivatives such as.
또, 염화구리, N-니트로소페닐하이드록실아민알루미늄염 등을 들 수 있다.Moreover, copper chloride, an N-nitrosophenyl hydroxylamine aluminum salt, etc. are mentioned.
(E) 중합 금지제는, 감광성 수지 조성물의 보존성을 향상시킬 뿐만 아니라, 레지스트 패턴의 해상성을 향상시킨다. 이것들은, 1 종을 단독으로 또는 2 종류 이상을 조합하여 사용할 수 있다. 그 중에서도, 4-메톡시페놀을, 보존 안정성, 용제에 대한 용해성 등으로부터 바람직하게 사용할 수 있다.(E) The polymerization inhibitor not only improves the storage property of the photosensitive resin composition, but also improves the resolution of the resist pattern. These can be used alone or in combination of two or more. Among them, 4-methoxyphenol can be preferably used from storage stability, solubility in a solvent, and the like.
(E) 의 함유율은, (A), (B), (C) 및 (E) 의 총량에 대해 400 ∼ 1000 ppm 인 것이 바람직하고, 500 ∼ 900 ppm 인 것이 보다 바람직하다. (E) 의 함유율이 400 ppm 미만에서는, 해상성 및 밀착성이 저하되는 경우가 있다. 한편, 1000 ppm 을 초과하면, 감도가 불충분해지는 경우가 있다.The content rate of (E) is preferably 400 to 1000 ppm, and more preferably 500 to 900 ppm with respect to the total amount of (A), (B), (C) and (E). When the content rate of (E) is less than 400 ppm, resolution and adhesiveness may decrease. On the other hand, when it exceeds 1000 ppm, the sensitivity may become insufficient.
본 발명의 감광성 수지 조성물은, (F) 광발색제를 함유하는 것이 바람직하고, (A), (B), (C) 및 (F) 의 총량에 대해, (F) 광발색제의 함유율이 0.15 ∼ 1.5 질량％ 인 것이 보다 바람직하다.The photosensitive resin composition of the present invention preferably contains (F) a photochromic agent, and the content rate of the photochromic agent (F) is 0.15 to the total amount of (A), (B), (C) and (F). It is more preferable that it is 1.5 mass %.
(F) 광발색제로는, 특별히 한정되지 않지만, 예를 들어, 류코크리스탈 바이올렛, 류코빅토리아 블루 BH, 류코빅토리아퓨어 블루 BOH, 류코다이아몬드 그린, 류코애시드 바이올렛 5B, 류코솔라시아닌 6B, 류코브릴리언트 그린, 3,6-비스디에틸아미노-9-페닐잔텐 등의 류코 색소를 들 수 있다. 이것들 중에서도, 발색성, 변색, 색조 등의 관점에서, 류코크리스탈 바이올렛이 바람직하게 사용된다.(F) Although it does not specifically limit as a photochromic agent, For example, leucocrystal violet, leucovictoria blue BH, leucovictoria pure blue BOH, leuco diamond green, leuco acid violet 5B, leucosolacyanin 6B, leuco brilliant green And leuco dyes such as 3,6-bisdiethylamino-9-phenylxanthene. Among these, from the viewpoints of color development, discoloration, color tone, and the like, leucocrystal violet is preferably used.
(F) 의 함유율은, (A), (B), (C) 및 (F) 의 총량에 대해, 0.15 ∼ 1.5 질량％ 인 것이 바람직하고, 보다 바람직하게는 0.2 ∼ 1.0 질량％ 이다. 광발색제의 함유율이 0.15 질량％ 미만인 경우, 감광성 수지층을 노광시켰을 때에, 노광부와 미노광부의 콘트라스트가 저하되는 경우가 있다. 한편, (F) 의 함유율이 1.5 질량％ 를 초과하는 경우, (F) 가 완전히 용해되지 않고, 감광성 수지층의 내부에서 결정으로서 석출되는 경우나, 감광성 수지 조성물의 보존 안정성이 저하되는 경우가 있다.The content rate of (F) is preferably 0.15 to 1.5% by mass, more preferably 0.2 to 1.0% by mass with respect to the total amount of (A), (B), (C) and (F). When the content rate of the photochromic agent is less than 0.15% by mass, when the photosensitive resin layer is exposed, the contrast between the exposed portion and the unexposed portion may decrease. On the other hand, when the content rate of (F) exceeds 1.5% by mass, (F) is not completely dissolved, precipitates as crystals inside the photosensitive resin layer, or the storage stability of the photosensitive resin composition is sometimes deteriorated. .
본 발명의 감광성 수지 조성물에는, 필요에 따라, 상기 (A) ∼ (F) 이외의 성분을 함유시켜도 된다. 이와 같은 성분으로는, 용제, 가소제, 착색제 (색소, 염료, 안료), 광감색제, 열발색 방지제, 충전제, 소포제, 난연제, 밀착성 부여제, 레벨링제, 박리 촉진제, 산화 방지제, 향료, 열경화제, 발수제, 발유제 등을 들 수 있고, 각각, (A), (B), (C), (D), (E) 및 (F) 의 총량에 대해, 0.01 ∼ 20 질량％ 정도 함유할 수 있다. 이것들은, 1 종을 단독으로 또는 2 종류 이상을 조합하여 사용할 수 있다.The photosensitive resin composition of the present invention may contain components other than the above (A) to (F) as necessary. Examples of such components include solvents, plasticizers, colorants (colorants, dyes, pigments), photosensitizers, anti-thermal agents, fillers, antifoaming agents, flame retardants, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, and thermosetting agents. , A water repellent, an oil repellent, etc., respectively, with respect to the total amount of (A), (B), (C), (D), (E) and (F), it can contain about 0.01 to 20% by mass have. These can be used alone or in combination of two or more.
본 발명의 감광성 수지 조성물은, 지지체, 감광성 수지 조성물을 함유하는 감광성 수지층, 및 커버 필름이 적층된 드라이 필름 레지스트의 구성으로 해도 된다. 이하, 「드라이 필름 레지스트」를, 간단히 「DFR」로 약기하는 경우가 있다.The photosensitive resin composition of the present invention may be configured as a dry film resist in which a support, a photosensitive resin layer containing a photosensitive resin composition, and a cover film are laminated. Hereinafter, "dry film resist" may simply be abbreviated as "DFR".
지지체는, 미경화 또는 경화된 감광성 수지층으로부터 박리할 수 있으면 되고, 활성 광선을 투과시키는 투명 필름이 바람직하다. 그 지지체의 두께는 얇은 것이, 광의 굴절이 적기 때문에 바람직하고, 두꺼운 것이, 도공 안정성이 우수하기 때문에 바람직하지만, 5 ∼ 50 ㎛ 가 특히 바람직하다. 이와 같은 필름으로는, 폴리에틸렌테레프탈레이트, 폴리카보네이트 등의 필름을 들 수 있다.The support should just be peelable from the uncured or cured photosensitive resin layer, and a transparent film which transmits active light is preferable. The thickness of the support is preferably thin because it has little refraction of light, and thick one is preferable because it has excellent coating stability, but it is particularly preferably 5 to 50 µm. Examples of such a film include films such as polyethylene terephthalate and polycarbonate.
커버 필름은, 미경화의 감광성 수지층으로부터 박리할 수 있으면 되고, 이형 성이 높은 수지가 사용된다. 예를 들어, 폴리에틸렌 필름 ; 폴리프로필렌 필름 ; 실리콘 등의 이형제가 도공된 폴리알킬렌 필름 ; 등을 들 수 있다.The cover film should just be peelable from the uncured photosensitive resin layer, and resin with high mold release property is used. For example, a polyethylene film; Polypropylene film; Polyalkylene films coated with a release agent such as silicone; And the like.
그 감광성 수지층은, 본 발명의 감광성 수지 조성물로 이루어지는 층이다.The photosensitive resin layer is a layer made of the photosensitive resin composition of the present invention.
드라이 필름 레지스트의 구성의 경우에는, 감광성 수지층의 두께는, 10 ∼ 150 ㎛ 인 것이 바람직하고, 30 ∼ 120 ㎛ 인 것이 보다 바람직하다. 이 감광성 수지층의 두께가 지나치게 크면, 해상성의 저하, 고비용 등의 문제가 발생하기 쉬워진다. 반대로 지나치게 얇으면, 밀착성, 내산성이 저하되는 경우가 있다.In the case of the configuration of a dry film resist, the thickness of the photosensitive resin layer is preferably 10 to 150 µm, more preferably 30 to 120 µm. If the thickness of this photosensitive resin layer is too large, problems such as a decrease in resolution and high cost tend to occur. Conversely, when it is too thin, adhesiveness and acid resistance may fall.
다음으로 본 발명의 도금 방법에 대해 상세하게 설명한다. 본 발명의 도금 방법은, 구리 도금, 니켈 도금 등의 도금 가공을 실시할 때의 도금 방법으로서 적용할 수 있다. 구체적으로는, 금속 회로 형성의 애디티브법, 세미 애디티브법, 고정세한 메탈 마스크를 제작하는 애디티브법 등의 용도에 바람직하게 사용되고, 기재 상에 포토법으로 레지스트 패턴을 형성한 후, 레지스트 패턴부 이외의 노출된 기재에 도금을 실시하여, 금속 패턴·회로 패턴을 형성하는 방법이다.Next, the plating method of the present invention will be described in detail. The plating method of the present invention can be applied as a plating method for performing plating processing such as copper plating and nickel plating. Specifically, it is preferably used for applications such as an additive method for forming a metal circuit, a semi-additive method, and an additive method for producing a high-definition metal mask. After forming a resist pattern on a substrate by a photo method, the resist This is a method of forming a metal pattern/circuit pattern by plating an exposed substrate other than the pattern portion.
예를 들어, 프린트 배선판을 제조하는 경우의 세미 애디티브법에서는, 먼저, 절연성 기판에 얇은 금속층을 형성한 기판을 기재로서 준비한다. 다음으로, 회로 패턴을 형성하지 않는 부분에 레지스트 패턴을 형성한다. 이어서, 전해 도금을 실시하여, 노출되어 있는 얇은 금속층의 표면에 도금 금속층을 형성한다. 계속해서, 레지스트 박리 공정에 의해 레지스트 패턴이 제거된다. 그 후, 얇은 금속층을 (플래시) 에칭 제거함으로써, 금속 패턴·회로 패턴이 형성된다.For example, in the semi-additive method in the case of manufacturing a printed wiring board, first, a substrate in which a thin metal layer is formed on an insulating substrate is prepared as a substrate. Next, a resist pattern is formed in a portion where the circuit pattern is not formed. Next, electroplating is performed to form a plated metal layer on the exposed surface of the thin metal layer. Subsequently, the resist pattern is removed by a resist stripping process. Thereafter, a metal pattern/circuit pattern is formed by removing the thin metal layer by (flash) etching.
기재로는, 예를 들어, 구리, 구리계 합금 (티탄구리 합금, 구리니켈 합금등) ; 니켈 ; 크롬 ; 철 ; 텅스텐 ; 스테인리스, 42 알로이 등의 철계 합금 ; 알루미늄 ; 아모르퍼스 합금 ; 등의 금속 기재를 사용할 수 있다.Examples of the substrate include copper and copper-based alloys (titanium-copper alloy, copper-nickel alloy, etc.); Nickel; chrome ; Iron; Tungsten; Iron-based alloys such as stainless steel and 42 alloy; aluminum ; Amorphous alloy; Metal substrates such as can be used.
또, 프린트 배선판 제조 등에 사용되는, 구리 피복 적층판, 무전해 도금된 기판, 전해 도금된 기판, 무전해 도금용 촉매 부여 기판, 플렉시블 구리 피복 적층판, 플렉시블 스테인리스판, 다단 구조 기판 등을 사용할 수 있다.Further, a copper clad laminate, an electroless plated substrate, an electrolytic plated substrate, a catalyst imparting substrate for electroless plating, a flexible copper clad laminate, a flexible stainless steel plate, a multi-stage structure substrate, etc. used in the manufacture of printed wiring boards, etc. can be used.
기재 상에 레지스트 패턴을 형성하기 위해서는, 포토법이 이용된다. 포토법에서는, 먼저, 기재에 감광성 수지 조성물을 함유하는 도공액을 도공하고, 건조시켜, 감광성 수지 조성물을 함유하는 감광성 수지층을 형성한다. 미리, 지지체 (캐리어 필름) 에 감광성 수지층을 형성한 DFR 을 제작하고, 기재에 감광성 수지층을 전사해도 된다.In order to form a resist pattern on a substrate, a photo method is used. In the photo method, first, a coating liquid containing a photosensitive resin composition is applied to a substrate and dried to form a photosensitive resin layer containing a photosensitive resin composition. In advance, DFR in which a photosensitive resin layer was formed on a support (carrier film) may be prepared, and the photosensitive resin layer may be transferred to the substrate.
다음으로, 패턴 노광을 실시하고, 노광부를 경화시킨다. 이어서, 알칼리 현상을 실시하고, 레지스트 패턴으로서 불필요한 부분인 비노광부의 감광성 수지층을 제거하여, 경화된 감광성 수지층을 포함하는 레지스트 패턴을 형성한다. 알칼리 현상에 사용하는 알칼리 현상액으로는, 예를 들어, 무기 염기성 화합물의 수용액을 사용할 수 있다. 무기 염기성 화합물로는, 리튬, 나트륨, 칼륨 등의 탄산염, 수산화물을 들 수 있고, 0.1 ∼ 3 질량％ 의 탄산나트륨 수용액을 바람직하게 사용할 수 있다.Next, pattern exposure is performed and the exposed part is hardened. Next, alkali development is performed, and the photosensitive resin layer of the non-exposed portion, which is an unnecessary portion as a resist pattern, is removed to form a resist pattern including the cured photosensitive resin layer. As an alkali developer used for alkali development, for example, an aqueous solution of an inorganic basic compound can be used. Examples of the inorganic basic compound include carbonates and hydroxides such as lithium, sodium and potassium, and an aqueous solution of 0.1 to 3% by mass of sodium carbonate can be preferably used.
현상액에는, 계면 활성제, 소포제, 용제 등을, 적절히 소량 혼입할 수도 있다. 현상 처리 방법으로는, 딥 방식, 패들 방식, 스프레이 방식, 브러싱, 스크레이핑 등이 있고, 스프레이 방식이 제거 속도의 점에서는 가장 적합하다. 현상 처리의 온도는, 15 ∼ 35 ℃ 가 바람직하고, 또, 스프레이압은, 0.02 ∼ 0.3 ㎫ 이 바람직하다.In the developing solution, a surfactant, an antifoaming agent, a solvent, and the like may be appropriately mixed in a small amount. As a developing treatment method, there are a dip method, a paddle method, a spray method, brushing, scraping, and the like, and the spray method is most suitable in terms of removal speed. The temperature of the developing treatment is preferably 15 to 35°C, and the spray pressure is preferably 0.02 to 0.3 MPa.
본 발명에서는, 알칼리 현상 후의 레지스트 패턴에 베이크 처리를 실시해도 된다. 베이크 처리에 의해, 감광성 수지층과 기재의 밀착을 향상시키는 효과나 내도금성을 향상시키는 효과 등이 얻어진다. 베이크 처리의 온도는 80 ℃ 이상이 바람직하고, 시간은 5 분 이상이 바람직하다. 또, 기재가 구리 등으로서, 산화 등에 의해 변색되기 쉬운 재질이면, 80 ℃ 정도에서 베이크 처리를 실시한다. 기재가 스테인리스 등으로서, 잘 산화되지 않는 재질이면, 베이크 처리의 온도는 100 ℃ 이상이어도 되고, 또, 30 분 이상의 장시간 처리를 실시해도 된다. 또, 베이크 처리 전에 감광성 수지층의 열에 의한 변형을 방지하는 것을 목적으로 하여, 자외선 등의 활성 광선 조사 처리를 실시해도 된다.In the present invention, a bake treatment may be performed on the resist pattern after alkali development. By the bake treatment, an effect of improving the adhesion between the photosensitive resin layer and the substrate, an effect of improving plating resistance, and the like are obtained. The temperature of the bake treatment is preferably 80° C. or more, and the time is preferably 5 minutes or more. Moreover, if the base material is copper or the like and is a material that is liable to discolor due to oxidation or the like, a bake treatment is performed at about 80°C. If the base material is stainless steel or the like and is a material that is not easily oxidized, the temperature of the bake treatment may be 100° C. or higher, or may be subjected to a long time treatment of 30 minutes or more. Further, for the purpose of preventing deformation of the photosensitive resin layer due to heat before the baking treatment, an actinic ray irradiation treatment such as ultraviolet rays may be performed.
이어서, 레지스트 패턴이 형성되어 있지 않은 기재의 노출 부분에, 도금을 실시하여 금속 패턴·회로 패턴을 형성한다. 그 도금 방법은, 상기 서술한 바와 같고, 전해 도금이어도 되고, 치환형 혹은 환원형의 무전해 도금이어도 된다. 또, 도금하는 금속 (합금) (도금 금속 (합금)) 은 특별히 한정되지 않는다.Subsequently, plating is applied to the exposed portion of the substrate on which the resist pattern is not formed to form a metal pattern/circuit pattern. The plating method is as described above, electrolytic plating may be used, or substitution type or reduction type electroless plating may be used. In addition, the metal to be plated (alloy) (plated metal (alloy)) is not particularly limited.
레지스트 박리 공정에서는, 레지스트 박리액으로서 알칼리 수용액이 유용하게 사용된다. 레지스트 박리액에 사용되는 염기성 화합물로는, 예를 들어, 규산 알칼리 금속염, 알칼리 금속 수산화물, 인산 알칼리 금속염, 탄산 알칼리 금속염, 인산암모늄, 탄산암모늄염 등의 무기 염기성 화합물 ; 에탄올아민, 에틸렌디아민, 프로판디아민, 트리에틸렌테트라민, 모르폴린, 수산화테트라메틸암모늄 등의 유기 염기성 화합물을 들 수 있다.In the resist stripping step, an alkaline aqueous solution is usefully used as a resist stripping liquid. Examples of the basic compound used in the resist stripping solution include inorganic basic compounds such as alkali metal silicate, alkali metal hydroxide, alkali metal phosphate, alkali metal carbonate, ammonium phosphate, and ammonium carbonate; And organic basic compounds such as ethanolamine, ethylenediamine, propanediamine, triethylenetetramine, morpholine, and tetramethylammonium hydroxide.
레지스트 박리 공정에 있어서, 경화된 감광성 수지층에 대한 용해성을 제어하기 위해, 레지스트 박리액의 농도, 온도, 스프레이압, 초음파 조건 등을 조정할 필요가 있다. 레지스트 박리액의 온도가 높을수록, 경화된 감광성 수지층이 용해되는 속도가 빨라져, 40 ℃ 이상의 온도가 바람직하다. 레지스트 박리액에 있어서의 염기성 화합물의 농도로는, 용해성에 적합한 농도가 좋고, 염기성 화합물이 수산화나트륨인 경우, 1 ∼ 4 질량％ 인 것이 바람직하다. 장치로는, 딥 처리 장치, 초음파 장치, 샤워 스프레이 장치 등을 이용할 수 있다.In the resist stripping process, in order to control the solubility of the cured photosensitive resin layer, it is necessary to adjust the concentration, temperature, spray pressure, ultrasonic conditions, and the like of the resist stripping solution. The higher the temperature of the resist stripping solution, the faster the rate at which the cured photosensitive resin layer dissolves, and a temperature of 40° C. or higher is preferable. As the concentration of the basic compound in the resist stripper, a concentration suitable for solubility is good, and when the basic compound is sodium hydroxide, it is preferably 1 to 4% by mass. As the device, a dip treatment device, an ultrasonic device, a shower spray device, or the like can be used.
본 발명에 있어서, 패턴 노광에 의해 경화되고, 경우에 따라, 베이크 처리가 실시된 후의 감광성 수지층은, 레지스트 박리 공정에 있어서, 레지스트 박리액에 의해 제거될 때에, 레지스트 박리액에 용해된다. 본 발명에 있어서, 경화된 감광성 수지층의 「용해」란, 감광성 수지층이 레지스트 박리액에 용해되어 있거나, 또는 육안으로 확인할 수 없을 만큼의 크기까지 레지스트 박리편이 매우 미세해져 있는 상태인 것을 말한다. 레지스트 박리편이 매우 미세해져 있는 상태로는, 분자 집합체 레벨로 분산되어 있는 상태, 100 ㎛ 이하의 미립자로서 분산되어 있는 상태 등이 포함된다.In the present invention, the photosensitive resin layer after curing by pattern exposure and optionally subjected to a bake treatment is dissolved in a resist stripping solution when removed by a resist stripping solution in a resist stripping step. In the present invention, "dissolution" of the cured photosensitive resin layer refers to a state in which the photosensitive resin layer is dissolved in a resist stripping solution, or that the resist stripping piece is very fine to a size that cannot be seen with the naked eye. The state in which the resist peeling piece is very fine includes a state dispersed at the molecular aggregate level, a state dispersed as fine particles of 100 µm or less, and the like.
본 발명은, 상기한 도금 방법을 이용하여 기재 상에 금속 패턴을 형성하는 것을 특징으로 하는 금속 패턴의 제조 방법이기도 하다.The present invention is also a method of manufacturing a metal pattern, characterized in that a metal pattern is formed on a substrate by using the above-described plating method.
금속 패턴의 형성에는, 각 공정에 있어서 상기한 방법을 사용하는 것이 바람직하다.In forming a metal pattern, it is preferable to use the above-described method in each step.
실시예Example
이하, 실시예에 의해 본 발명을 더욱 상세하게 설명하지만, 본 발명은 이 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
표 1 ∼ 표 3 에 있어서, 각 성분은 이하와 같다.In Tables 1-3, each component is as follows.
(A-1) 메틸메타크릴레이트/n-부틸아크릴레이트/메타크릴산을 질량비 64/15/21 로 공중합시킨 공중합 수지 (질량 평균 분자량 40,000)(A-1) Copolymer resin obtained by copolymerizing methyl methacrylate/n-butyl acrylate/methacrylic acid at a mass ratio of 64/15/21 (mass average molecular weight 40,000)
(B-1) 2-(o-클로로페닐)-4,5-디페닐이미다졸 이량체(B-1) 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer
(B-2) 4,4'-비스(디에틸아미노)벤조페논(B-2) 4,4'-bis(diethylamino)benzophenone
(C1-1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 35 인 화합물)(C1-1) Ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), a compound of l+m+n+o=35)
(C2-1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 인 화합물)(C2-1) Ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), a compound of l+m+n+o=4)
(C3-1) 펜타에리트리톨트리아크릴레이트(C3-1) pentaerythritol triacrylate
(C3-2) 폴리에틸렌글리콜 ＃600 디아크릴레이트 (에틸렌옥사이드의 반복수가 14)(C3-2) Polyethylene glycol #600 diacrylate (the number of repetitions of ethylene oxide is 14)
(D-1) 비스페놀 A 의 에틸렌옥사이드 부가물의 디메타크릴레이트 (에틸렌옥사이드의 반복수가 합계로 10)(D-1) Dimethacrylate of ethylene oxide adduct of bisphenol A (the total number of repeating ethylene oxide is 10)
(E-1) 4-메톡시페놀(E-1) 4-methoxyphenol
(F-1) 류코크리스탈 바이올렛(F-1) Leuco Crystal Violet
실시예 1-1 ∼ 1-6, 비교예 1-1 ∼ 1-4Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-4
표 1 에 나타내는 각 성분을 혼합하고, 감광성 수지 조성물 및 도공액을 얻었다. 또한, 표 1 에 있어서의 각 성분의 배합량의 단위는, 질량부를 나타낸다.Each component shown in Table 1 was mixed, and the photosensitive resin composition and the coating liquid were obtained. In addition, the unit of the compounding quantity of each component in Table 1 represents a mass part.
얻어진 도공액을, 어플리케이터를 사용하여, 폴리에틸렌테레프탈레이트 (PET) 필름 (상품명 : R310, 16 ㎛ 두께, 미츠비시 케미컬사 제조) 상에 도공하고, 80 ℃ 에서 8 분간 건조시켜, 용제를 제거하고, PET 필름의 편면 상에, 실시예 1-1 ∼ 1-6, 비교예 1-1 ∼ 1-4 의 감광성 수지 조성물로 이루어지는 감광성 수지층 (건조 막 두께 : 30 ㎛) 을 형성한 DFR 을 얻었다.The obtained coating liquid was coated on a polyethylene terephthalate (PET) film (trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical) using an applicator, and dried at 80° C. for 8 minutes to remove the solvent, and PET On one side of the film, DFR was obtained in which a photosensitive resin layer (dry film thickness: 30 µm) formed of the photosensitive resin composition of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 was formed.
표면 조도 Ra 가 0.01 ㎛ ∼ 1 ㎛ 인 스테인리스 강판에, 알칼리 탈지, 산 처리 등의 표면 처리를 실시하고, 실시예 1-1 ∼ 1-6, 비교예 1-1 ∼ 1-4 의 감광성 수지층을 첩부하였다. 다음으로, 50 ㎛ 라인 ＆ 스페이스의 패턴을 갖는 포토마스크를 개재하여 노광하고, 이어서, PET 필름을 박리하고, 1.0 질량％ 탄산나트륨 수용액으로 알칼리 현상을 실시하고, 비노광부의 감광성 수지층을 제거하여, 레지스트 패턴을 형성하였다.A stainless steel sheet having a surface roughness Ra of 0.01 µm to 1 µm was subjected to surface treatment such as alkali degreasing and acid treatment, and the photosensitive resin layer of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 Was attached. Next, exposure was performed through a photomask having a pattern of 50 µm line & space, and then the PET film was peeled off, alkali development was performed with a 1.0 mass% sodium carbonate aqueous solution, and the photosensitive resin layer of the non-exposed portion was removed, A resist pattern was formed.
그 때, (C) 아크릴레이트 모노머 전체량에 대해, (C1) 의 함유율이 70 질량％ 초과인 비교예 1-1 의 감광성 수지층에 있어서는, 경화된 감광성 수지층으로 이루어지는 레지스트 패턴이 팽윤하여, 50 ㎛ 라인 ＆ 스페이스의 패턴이 탈리되었다.At that time, in the photosensitive resin layer of Comparative Example 1-1 in which the content of (C1) is more than 70% by mass relative to the total amount of (C) the acrylate monomer, the resist pattern composed of the cured photosensitive resin layer swells, The pattern of 50 μm line & space was removed.
한편, 실시예 1-1 ∼ 1-6 에서는, 모두 양호한 50 ㎛ 라인 ＆ 스페이스의 패턴을 제작할 수 있었다.On the other hand, in Examples 1-1 to 1-6, a good 50 µm line & space pattern could be produced.
다음으로, 술팜산니켈 (Ni) 욕을 사용한 전해 도금에 의해, 스테인리스 강판 상의 레지스트 패턴에 의해 피복되어 있지 않은 부분 위에 도금막을 성장시켜, 두께가 25 ㎛ 가 되도록 Ni 금속층을 형성하였다.Next, by electrolytic plating using a nickel sulfamate (Ni) bath, a plated film was grown on the portion not covered by the resist pattern on the stainless steel sheet, and a Ni metal layer was formed so that the thickness became 25 µm.
그 때, (C) 아크릴레이트 모노머 전체량에 대해, (C1) 의 함유율이 30 질량％ 미만인 감광성 수지 조성물을 사용한 비교예 1-2 및 1-3 에서는, 레지스트 패턴의 라인 바닥부에 도금액의 스며듦이 발생하여, 레지스트 바닥부에 획선 가늘어짐이 있는 것을 알 수 있었다. 따라서, Ni 금속층이 레지스트 바닥부에 들어가, 양호한 Ni 패턴을 제작할 수 없었다.In that case, in Comparative Examples 1-2 and 1-3 using the photosensitive resin composition in which the content of (C1) was less than 30% by mass relative to the total amount of (C) acrylate monomer, the plating solution was soaked into the bottom of the line of the resist pattern. This occurred, and it was found that there was a thinning of a stroke at the bottom of the resist. Therefore, the Ni metal layer entered the resist bottom, and a good Ni pattern could not be produced.
한편, 실시예 1-1 ∼ 1-6 에서는, 모두 양호한 Ni 패턴을 제작할 수 있었다.On the other hand, in Examples 1-1 to 1-6, all favorable Ni patterns were able to be produced.
다음으로, 실시예 1-1 ∼ 1-6 및 비교예 1-4 에 있어서, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 침지하여, 레지스트 패턴의 박리를 실시하였다.Next, in Examples 1-1 to 1-6 and Comparative Example 1-4, the resist pattern was peeled off by immersing in a 3% by mass aqueous sodium hydroxide solution (liquid temperature of 50°C).
실시예 1-1 ∼ 1-6 의 감광성 수지 조성물에 의한 레지스트 패턴의 박리는, 양호하게 실시할 수 있었다.The peeling of the resist pattern by the photosensitive resin composition of Examples 1-1 to 1-6 could be performed favorably.
한편, (C) 아크릴레이트 모노머 전체량에 대해, (D) 의 함유율이 8.8 질량％ 이고 5 질량％ 초과인 감광성 수지 조성물을 사용한 비교예 1-4 에서는, 50 ㎛ 의 스페이스 사이에 레지스트 패턴의 잔류물이 잔존한다는 문제가 발생하였다.On the other hand, in Comparative Example 1-4 using a photosensitive resin composition having a content of (D) of 8.8% by mass and more than 5% by mass relative to the total amount of (C) acrylate monomer, the resist pattern remains between 50 μm spaces. There was a problem that water remained.
또, 실시예 1-1 ∼ 1-6 의 감광성 수지층의 박리편을, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 3 시간 침지한 결과, 박리편을 육안으로 확인할 수 없게 되었다. 이로써, 다음의 워크를 처리할 때, Ni 패턴 사이에 대한 레지스트 박리편의 「얽힘」의 우려가 없어졌다.Moreover, as a result of immersing the peeling piece of the photosensitive resin layer of Examples 1-1 to 1-6 in a 3% by mass aqueous sodium hydroxide solution (liquid temperature of 50°C) for 3 hours, the peeling piece could not be visually confirmed. Thereby, the fear of "entanglement" of the resist peeling piece between Ni patterns when processing the next work|work was eliminated.
실시예 2-1 ∼ 2-7, 비교예 2-1Examples 2-1 to 2-7, Comparative Example 2-1
표 2 에 나타내는 각 성분을 혼합하고, 감광성 수지 조성물 및 도공액을 얻었다. 또한, 표 2 에 있어서의 각 성분의 배합량의 단위는, 질량부를 나타낸다. 또, (E) 의 함유율은, (A), (B), (C) 및 (E) 의 총량에 대한 (E) 의 함유율이고, 그 단위는 질량ppm 이다.Each component shown in Table 2 was mixed, and the photosensitive resin composition and the coating liquid were obtained. In addition, the unit of the compounding quantity of each component in Table 2 represents a mass part. In addition, the content rate of (E) is the content rate of (E) with respect to the total amount of (A), (B), (C) and (E), and the unit is ppm by mass.
얻어진 도공액을, 어플리케이터를 사용하여, 폴리에틸렌테레프탈레이트 (PET) 필름 (상품명 : R310, 16 ㎛ 두께, 미츠비시 케미컬사 제조) 상에 도공하고, 80 ℃ 에서 8 분간 건조시켜, 용제를 제거하고, PET 필름의 편면 상에 실시예 2-1 ∼ 2-7, 비교예 2-1 의 감광성 수지 조성물을 함유하는 감광성 수지층 (건조 막 두께 : 30 ㎛) 을 형성한 DFR 을 얻었다.The obtained coating liquid was coated on a polyethylene terephthalate (PET) film (trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical) using an applicator, and dried at 80° C. for 8 minutes to remove the solvent, and PET DFR was obtained in which a photosensitive resin layer (dry film thickness: 30 µm) containing the photosensitive resin composition of Examples 2-1 to 2-7 and Comparative Example 2-1 was formed on one side of the film.
표면 조도 Ra 가 0.01 ㎛ ∼ 1 ㎛ 인 스테인리스 강판에, 알칼리 탈지, 산 처리 등의 표면 처리를 실시하고, 실시예 2-1 ∼ 2-7, 비교예 2-1 의 감광성 수지층을 첩부하였다.Surface treatments such as alkali degreasing and acid treatment were performed on a stainless steel sheet having a surface roughness Ra of 0.01 µm to 1 µm, and the photosensitive resin layers of Examples 2-1 to 2-7 and Comparative Example 2-1 were affixed.
다음으로, 직경이 200, 150, 100, 80 ㎛ 인 원형의 도트 패턴을 갖는 포토마스크를 개재하여 노광하고, 이어서, PET 필름을 박리하고, 1.0 질량％ 탄산나트륨 수용액으로 알칼리 현상을 실시하고, 비노광부의 감광성 수지층을 제거하여, 레지스트 패턴을 형성하였다.Next, exposure was performed through a photomask having a circular dot pattern having a diameter of 200, 150, 100, and 80 µm, and then the PET film was peeled off, and alkali development was performed with a 1.0 mass% sodium carbonate aqueous solution, and the non-exposed portion The photosensitive resin layer was removed to form a resist pattern.
이 때, (C) 아크릴레이트 모노머로서 (C1) 을 함유하고 있지 않은 비교예 2-1 에서는, 현상 공정에 의해, 직경 150 ㎛ 이하의 도트 패턴이 절반 이상 없어져 있었다.At this time, in Comparative Example 2-1 which did not contain (C1) as (C) an acrylate monomer, a dot pattern having a diameter of 150 µm or less was lost by half or more by a developing step.
또, (E) 의 함유율이 400 ppm 미만인 실시예 2-7 에서는, 현상 공정에 의해, 직경 100 ㎛ 이상의 도트 패턴은 기판 상에 잔존했지만, 직경 80 ㎛ 의 도트 패턴은 약간 없어져 있었다.Moreover, in Example 2-7 in which the content rate of (E) was less than 400 ppm, the dot pattern of 100 micrometers or more in diameter remained on the board|substrate by a developing process, but the dot pattern of 80 micrometers in diameter was slightly missing.
한편, 실시예 2-1 ∼ 2-6 에서는, 현상 후에도, 직경이 200, 150, 100, 80 ㎛ 인 원형의 도트 패턴이 모두 기판 상에 잔존하고, 높은 밀착성을 나타냈다.On the other hand, in Examples 2-1 to 2-6, even after development, circular dot patterns having a diameter of 200, 150, 100, and 80 µm all remained on the substrate, and high adhesion was exhibited.
다음으로, 술팜산니켈 (Ni) 욕을 사용한 전해 도금에 의해, 스테인리스 강판 상의 레지스트 패턴에 의해 피복되어 있지 않은 부분 위에 도금막을 성장시켜, 두께가 25 ㎛ 가 되도록 Ni 금속층을 형성하였다.Next, by electrolytic plating using a nickel sulfamate (Ni) bath, a plated film was grown on the portion not covered by the resist pattern on the stainless steel sheet, and a Ni metal layer was formed so that the thickness became 25 µm.
이 때, 비교예 2-1 에서는, 직경이 200 ㎛ 인 원형의 도트 패턴에 있어서, 도금액이 스며들어, 레지스트 바닥부에 획선 가늘어짐이 있는 것을 알 수 있었다. 그 때문에, Ni 금속층이 레지스트의 아래로 들어가 있어, 양호한 Ni 금속층을 형성할 수 없었다.At this time, in Comparative Example 2-1, it was found that in a circular dot pattern having a diameter of 200 µm, the plating solution soaked in, and there was a thinning of a stroke at the bottom of the resist. For this reason, the Ni metal layer entered under the resist, and a satisfactory Ni metal layer could not be formed.
한편, 실시예 2-1 ∼ 2-7 에서는, 도금액의 스며듦은 없고, 양호한 Ni 금속층이 형성되어 있었다.On the other hand, in Examples 2-1 to 2-7, there was no permeation of the plating solution, and a good Ni metal layer was formed.
다음으로, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 침지하여, 레지스트 패턴의 박리를 실시하였다. 실시예 2-1 ∼ 2-7 및 비교예 2-1 의 감광성 수지 조성물에 의한 레지스트 패턴은 양호하게 박리를 실시할 수 있었다.Next, it was immersed in 3 mass% sodium hydroxide aqueous solution (liquid temperature 50 degreeC), and the resist pattern was peeled. The resist patterns of Examples 2-1 to 2-7 and the photosensitive resin composition of Comparative Example 2-1 were able to be removed satisfactorily.
또, 실시예 2-1 ∼ 2-7 및 비교예 2-1 의 감광성 수지층의 박리편을, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 3 시간 침지한 결과, 박리편을 육안으로 확인할 수 없게 되었다. 그것에 의해, 다음의 워크를 처리할 때, Ni 패턴 사이에 대한 레지스트 박리편의 얽힘의 우려가 없어졌다.Moreover, as a result of immersing the peeling piece of the photosensitive resin layer of Examples 2-1 to 2-7 and the photosensitive resin layer of Comparative Example 2-1 for 3 hours in a 3% by mass aqueous sodium hydroxide solution (liquid temperature of 50° C.), the peeling piece was visually confirmed. I couldn't. Thereby, the fear of entanglement of the resist peeling piece between Ni patterns when processing the next work|work was eliminated.
실시예 3-1 ∼ 3-7, 비교예 3-1 ∼ 3-2Examples 3-1 to 3-7, Comparative Examples 3-1 to 3-2
표 3 에 나타내는 각 성분을 혼합하고, 감광성 수지 조성물 및 도공액을 얻었다. 또한, 표 3 에 있어서의 각 성분의 배합량의 단위는 질량부이다. 얻어진 도공액을, 어플리케이터를 사용하여, 폴리에틸렌테레프탈레이트 (PET) 필름 (상품명 : R310, 16 ㎛ 두께, 미츠비시 케미컬사 제조) 상에 도공하고, 80 ℃ 에서 8 분간 건조시켜, 용제를 제거하고, PET 필름의 편면 상에 실시예 3-1 ∼ 3-7, 비교예 3-1 ∼ 3-2 의 감광성 수지 조성물로 이루어지는 감광성 수지층 (건조 막 두께 : 50 ㎛) 을 형성한 DFR 을 얻었다.Each component shown in Table 3 was mixed, and the photosensitive resin composition and the coating liquid were obtained. In addition, the unit of the compounding quantity of each component in Table 3 is a mass part. The obtained coating liquid was coated on a polyethylene terephthalate (PET) film (trade name: R310, 16 μm thick, manufactured by Mitsubishi Chemical) using an applicator, and dried at 80° C. for 8 minutes to remove the solvent, and PET DFR was obtained in which a photosensitive resin layer (dry film thickness: 50 µm) formed of the photosensitive resin composition of Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-2 was formed on one side of the film.
표면 조도 Ra 가 0.01 ㎛ ∼ 1 ㎛ 인 스테인리스 강판에, 알칼리 탈지, 산 처리 등의 표면 처리를 실시하고, 실시예 3-1 ∼ 3-7, 비교예 3-1 ∼ 3-2 의 감광성 수지층을 첩부하였다.A stainless steel sheet having a surface roughness Ra of 0.01 µm to 1 µm was subjected to surface treatment such as alkali degreasing and acid treatment, and the photosensitive resin layer of Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-2 Was attached.
다음으로, 직경이 100, 80, 70, 60 ㎛ 인 원형의 도트 패턴을 갖는 포토마스크를 개재하여 노광하고, 이어서, PFT 필름을 박리하고, 1.0 질량％ 탄산나트륨 수용액으로 알칼리 현상을 실시하고, 비노광부의 감광성 수지층을 제거하여, 레지스트 패턴을 형성하였다.Next, exposure is performed through a photomask having a circular dot pattern having a diameter of 100, 80, 70, and 60 µm, and then the PFT film is peeled off, and alkali development is performed with a 1.0 mass% sodium carbonate aqueous solution, and the non-exposed part The photosensitive resin layer was removed to form a resist pattern.
이 때, (F) 의 함유율이 0.15 질량％ 미만인 실시예 3-7 의 감광성 수지층은, 노광에 대한 감도가 낮아, 실시예 3-1 ∼ 3-6 과 동일한 노광량에서는 레지스트의 경화가 충분히 진행되지 않았다. 그 때문에, 레지스트 화상을 관찰한 결과, 직경 80 ㎛ 이하의 도트 패턴이 절반 이상 없어져 있었지만, 직경 100 ㎛ 의 도트 패턴은 잔존하고 있었다.At this time, the photosensitive resin layer of Example 3-7 in which the content of (F) is less than 0.15% by mass has low sensitivity to exposure, and curing of the resist sufficiently proceeds at the same exposure amount as in Examples 3-1 to 3-6. Didn't. Therefore, as a result of observing the resist image, half or more of the dot patterns having a diameter of 80 µm or less were missing, but a dot pattern having a diameter of 100 µm remained.
또, (C) 아크릴레이트 모노머로서 (C1) 을 함유하지 않는 비교예 3-1 ∼ 3-2 의 감광성 수지층은, 기재에 대한 밀착이 약하여, 현상 공정에 의해, 모든 직경에 있어서, 도트 패턴이 절반 이상 없어져 있었다.In addition, (C) the photosensitive resin layers of Comparative Examples 3-1 to 3-2 that do not contain (C1) as an acrylate monomer have poor adhesion to the substrate, and according to the development step, dot patterns in all diameters More than half of this was missing.
한편, 실시예 3-1 ∼ 3-6 에서는, 현상 후에도, 모든 직경에 있어서, 도트 패턴이 기판 상에 잔존하고, 높은 밀착성을 나타냈다.On the other hand, in Examples 3-1 to 3-6, even after development, the dot pattern remained on the substrate in all diameters, and high adhesion was exhibited.
다음으로, 실시예 3-1 ∼ 3-7 에 있어서, 술팜산니켈 (Ni) 욕을 사용한 전해 도금에 의해, 스테인리스 강판 상의 레지스트 패턴에 의해 피복되어 있지 않은 부분 위에 도금막을 성장시켜, 두께가 25 ㎛ 가 되도록 Ni 금속층을 형성하였다.Next, in Examples 3-1 to 3-7, by electroplating using a nickel sulfamate (Ni) bath, a plated film was grown on the portion not covered by the resist pattern on the stainless steel sheet, and the thickness was 25. The Ni metal layer was formed so that it might become micrometer.
이 때, 실시예 3-1 ∼ 3-7 에서는, 도금액의 스며듦은 없고, 양호한 Ni 금속층이 형성되어 있었다.At this time, in Examples 3-1 to 3-7, there was no impregnation of the plating solution, and a good Ni metal layer was formed.
다음으로, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 침지하여, 레지스트 패턴 박리를 실시하였다. 실시예 3-1 ∼ 3-7 의 감광성 수지 조성물에 의한 레지스트 패턴은 양호하게 박리를 실시할 수 있었다.Next, it was immersed in 3 mass% sodium hydroxide aqueous solution (liquid temperature 50 degreeC), and resist pattern peeling was performed. The resist patterns of the photosensitive resin compositions of Examples 3-1 to 3-7 were able to be removed satisfactorily.
또, 실시예 3-1 ∼ 3-7 의 감광성 수지층의 박리편을, 3 질량％ 수산화나트륨 수용액 (액온 50 ℃) 에 3 시간 침지한 결과, 박리편을 육안으로 확인할 수 없게 되었다. 이로써, 다음의 워크를 처리할 때, Ni 패턴 사이에 대한 레지스트 박리편의 얽힘의 우려가 없어졌다.Moreover, as a result of immersing the peeling piece of the photosensitive resin layer of Examples 3-1 to 3-7 for 3 hours in a 3% by mass aqueous sodium hydroxide solution (liquid temperature of 50°C), the peeling piece could not be visually confirmed. Thereby, the fear of entanglement of the resist peeling piece between Ni patterns when processing the next work|work was eliminated.
산업상 이용가능성Industrial applicability
본 발명은, 감광성 수지 조성물의 제조나 사용 분야에 널리 이용할 수 있다. 특히, 프린트 배선판, 리드 프레임, 메탈 마스크, 쉐도우 마스크, 반도체 패키지, 전극 부재, 전자파 실드 등의 제조에 있어서, 도금 가공시에 사용되는 레지스트 패턴 형성용의 감광성 수지 조성물의 제조·사용 분야에 널리 이용할 수 있다.The present invention can be widely used in the field of manufacture or use of a photosensitive resin composition. In particular, in the manufacture of printed wiring boards, lead frames, metal masks, shadow masks, semiconductor packages, electrode members, electromagnetic shields, etc., it is widely used in the production and use of photosensitive resin compositions for forming resist patterns used during plating processing. I can.
Claims (6)
(C) 아크릴레이트 모노머에 대해, (D) 메타크릴레이트 모노머의 함유율이 0 ∼ 5 질량％ 이고,
(C) 아크릴레이트 모노머로서, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 를 함유하고,
(C) 아크릴레이트 모노머 전체량에 대해, (C1) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 24 ∼ 48 인 화합물) 의 함유율이 30 ∼ 70 질량％ 인 것을 특징으로 하는 감광성 수지 조성물.
(C) with respect to the acrylate monomer, the content rate of the (D) methacrylate monomer is 0 to 5% by mass,
(C) As an acrylate monomer, (C1) ethylene oxide-modified pentaerythritol tetraacrylate (a compound represented by general formula (i), l+m+n+o=24-48) is contained,
(C) The content rate of (C1) ethylene oxide-modified pentaerythritol tetraacrylate (a compound represented by the general formula (i), l+m+n+o=24 to 48) with respect to the total amount of the (C) acrylate monomer is 30 The photosensitive resin composition characterized in that it is-70 mass %.
그 감광성 수지 조성물이, (C) 아크릴레이트 모노머로서, (C2) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 ∼ 8 인 화합물) 를 함유하고, (C) 아크릴레이트 모노머 전체량에 대해, (C2) 에틸렌옥사이드 변성 펜타에리트리톨테트라아크릴레이트 (일반식 (i) 로 나타내고, l ＋ m ＋ n ＋ o = 4 ∼ 8 인 화합물) 의 함유율이 30 ∼ 70 질량％ 인 감광성 수지 조성물.The method of claim 1,
The photosensitive resin composition, (C) as an acrylate monomer, (C2) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), l + m + n + o = 4 to 8 compound) Containing, (C) with respect to the total amount of the acrylate monomer, (C2) ethylene oxide-modified pentaerythritol tetraacrylate (represented by the general formula (i), 1 + m + n + o = 4 to 8 compound) of A photosensitive resin composition having a content of 30 to 70% by mass.
그 감광성 수지 조성물이 (E) 중합 금지제를 함유하고, (A) 알칼리 가용성 수지, (B) 광중합 개시제, (C) 아크릴레이트 모노머 및 (E) 중합 금지제의 총량에 대해, (E) 중합 금지제의 함유율이 400 ∼ 1000 ppm 인 감광성 수지 조성물.The method of claim 1,
The photosensitive resin composition contains (E) a polymerization inhibitor, (E) polymerization with respect to the total amount of (A) alkali-soluble resin, (B) photoinitiator, (C) acrylate monomer and (E) polymerization inhibitor. The photosensitive resin composition in which the content rate of an inhibitor is 400-1000 ppm.
그 감광성 수지 조성물이 (F) 광발색제를 함유하고, (A) 알칼리 가용성 수지, (B) 광중합 개시제, (C) 아크릴레이트 모노머 및 (F) 광발색제의 총량에 대해, (F) 광발색제의 함유율이 0.15 ∼ 1.5 질량％ 인 감광성 수지 조성물.The method of claim 1,
The photosensitive resin composition contains (F) a photochromic agent, (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) an acrylate monomer, and (F) with respect to the total amount of the photochromic agent, A photosensitive resin composition having a content of 0.15 to 1.5% by mass.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| JPJP-P-2018-171510 | 2018-09-13 | ||
| JP2018209917 | 2018-11-07 | ||
| JPJP-P-2018-209917 | 2018-11-07 | ||
| PCT/JP2019/029588 WO2020027024A1 (en) | 2018-08-02 | 2019-07-29 | Photosensitive resin composition, plating method, and method for producing metal pattern |
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| JP (2) | JP7268028B2 (en) |
| KR (1) | KR20210038554A (en) |
| CN (1) | CN112470075A (en) |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04166844A (en) | 1990-10-30 | 1992-06-12 | Matsushita Electric Ind Co Ltd | Manufacture of metal mask for screen printing |
| JPH09265180A (en) | 1996-03-27 | 1997-10-07 | Mitsubishi Rayon Co Ltd | Laminate of photosensitive resin composition for metal processing |
| JP2004101617A (en) | 2002-09-05 | 2004-04-02 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and its laminate |
| JP2010113349A (en) | 2008-10-10 | 2010-05-20 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
| JP2011081031A (en) | 2009-10-02 | 2011-04-21 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
| JP2013037272A (en) | 2011-08-10 | 2013-02-21 | Mitsubishi Paper Mills Ltd | Photosensitive resin composition and photosensitive film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007452B (en) * | 2008-04-14 | 2012-10-31 | 旭化成电子材料株式会社 | Photosensitive resin composition and layered object obtained therewith |
| JP2010211095A (en) * | 2009-03-12 | 2010-09-24 | Toray Ind Inc | Photosensitive coverlay |
| EP2472330B1 (en) * | 2010-12-28 | 2017-01-25 | Fujifilm Corporation | Black radiation-sensitive composition, black cured film, solid-state imaging element, and method of producing black cured film |
| JP2012220837A (en) | 2011-04-12 | 2012-11-12 | Asahi Kasei E-Materials Corp | Photosensitive resin composition and laminate of the same |
| JP5899798B2 (en) * | 2011-10-26 | 2016-04-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
| JP5948539B2 (en) * | 2012-01-27 | 2016-07-06 | 旭化成株式会社 | Photosensitive resin composition |
| WO2014196546A1 (en) * | 2013-06-04 | 2014-12-11 | 日立化成株式会社 | Method of manufacturing transparent substrate provided with cured film, photosensitive resin composition, photosensitive element, and electrical component |
| CN106662812B (en) * | 2014-09-05 | 2020-10-02 | 日产化学工业株式会社 | Photosensitive electroless plating base agent |
| JP2017167395A (en) | 2016-03-17 | 2017-09-21 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for manufacturing printed wiring board |
-
2019
- 2019-07-29 WO PCT/JP2019/029588 patent/WO2020027024A1/en active Application Filing
- 2019-07-29 JP JP2020533521A patent/JP7268028B2/en active Active
- 2019-07-29 CN CN201980048740.3A patent/CN112470075A/en active Pending
- 2019-07-29 KR KR1020217002811A patent/KR20210038554A/en not_active Application Discontinuation
- 2019-08-01 TW TW108127315A patent/TW202012452A/en unknown
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- 2022-08-10 JP JP2022127539A patent/JP7392061B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04166844A (en) | 1990-10-30 | 1992-06-12 | Matsushita Electric Ind Co Ltd | Manufacture of metal mask for screen printing |
| JPH09265180A (en) | 1996-03-27 | 1997-10-07 | Mitsubishi Rayon Co Ltd | Laminate of photosensitive resin composition for metal processing |
| JP2004101617A (en) | 2002-09-05 | 2004-04-02 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and its laminate |
| JP2010113349A (en) | 2008-10-10 | 2010-05-20 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
| JP2011081031A (en) | 2009-10-02 | 2011-04-21 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
| JP2013037272A (en) | 2011-08-10 | 2013-02-21 | Mitsubishi Paper Mills Ltd | Photosensitive resin composition and photosensitive film |
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| Publication number | Publication date |
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| JP7268028B2 (en) | 2023-05-02 |
| WO2020027024A1 (en) | 2020-02-06 |
| JP2022169628A (en) | 2022-11-09 |
| JPWO2020027024A1 (en) | 2021-08-02 |
| CN112470075A (en) | 2021-03-09 |
| TW202012452A (en) | 2020-04-01 |
| JP7392061B2 (en) | 2023-12-05 |
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