JP5273455B2 - Photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method - Google Patents
Photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method Download PDFInfo
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- JP5273455B2 JP5273455B2 JP2008242462A JP2008242462A JP5273455B2 JP 5273455 B2 JP5273455 B2 JP 5273455B2 JP 2008242462 A JP2008242462 A JP 2008242462A JP 2008242462 A JP2008242462 A JP 2008242462A JP 5273455 B2 JP5273455 B2 JP 5273455B2
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- resin composition
- photosensitive resin
- carbon atoms
- general formula
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical class OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012964 benzotriazole Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 238000011161 development Methods 0.000 claims description 35
- -1 acrylic ester Chemical class 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 23
- 229940048053 acrylate Drugs 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000036211 photosensitivity Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229940114077 acrylic acid Drugs 0.000 description 4
- 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 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-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
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- CDUQMGQIHYISOP-RMKNXTFCSA-N (e)-2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C\C1=CC=CC=C1 CDUQMGQIHYISOP-RMKNXTFCSA-N 0.000 description 1
- FWUIHQFQLSWYED-ARJAWSKDSA-N (z)-4-oxo-4-propan-2-yloxybut-2-enoic acid Chemical compound CC(C)OC(=O)\C=C/C(O)=O FWUIHQFQLSWYED-ARJAWSKDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SCEFCWXRXJZWHE-UHFFFAOYSA-N 1,2,3-tribromo-4-(2,3,4-tribromophenyl)sulfonylbenzene Chemical compound BrC1=C(Br)C(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C(Br)=C1Br SCEFCWXRXJZWHE-UHFFFAOYSA-N 0.000 description 1
- PXKJUFVZGULJAA-UHFFFAOYSA-N 1-[[bis(2-ethylhexyl)amino]methyl]benzotriazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 PXKJUFVZGULJAA-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
- 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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- 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
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 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 1
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- 238000010521 absorption reaction Methods 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は、感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造法に関する。 The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for producing a printed wiring board.
従来、プリント配線板の製造分野において、エッチング及びめっき等に用いられるレジスト材料としては、感光性樹脂組成物及びそれに支持体と保護フィルムを用いて得られる感光性エレメントが広く用いられている。
プリント配線板は、通常(化学または物理)研磨を行った銅基板上に感光性エレメントをラミネートして、パターン露光した後、未露光部分を現像液で除去し、エッチング又はめっき処理を施して導体パターンを形成させた後、硬化部分を基板上からはく離除去する方法によって製造されている。
例えば、上記めっき処理を施して導体パターンを形成する場合、感光性エレメントには一般に感度、解像度及び密着性の他、耐めっき性も求められる。
また、上記はく離工程において、はく離片サイズ（はく離後のレジスト片のサイズ）が大きいと、はく離機の搬送ロールやスプレーノズル等に絡みつき、作業性や生産効率を低下させる、あるいは、基板上にはく離片が再付着し、結果としてプリント配線板に不具合が生じるという問題がある。従って、感光性エレメントに対しては、はく離片を細分化（はく離後のレジスト片のサイズを小さく）させることが要求されている。
レジストのはく離性を向上させるため、種々の感光性樹脂組成物が検討されている。例えば、バインダーポリマーのガラス転移温度、重量平均分子量、及び酸価を特定の範囲に調整することによりはく離速度及びはく離分散性を向上させた感光性樹脂組成物が開示されている（例えば、特許文献１参照）。また、特定の多官能エチレン性不飽和化合物を用いることによりレジストのはく離性を向上させた感光性樹脂組成物が開示されている（例えば、特許文献２参照）。
Conventionally, in the field of manufacturing printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film are widely used.
A printed wiring board is made by laminating a photosensitive element on a normal (chemical or physical) polished copper substrate, exposing the pattern, removing the unexposed portion with a developer, and performing etching or plating treatment on the conductor. After the pattern is formed, it is manufactured by a method in which the cured portion is peeled off from the substrate.
For example, when the conductor pattern is formed by performing the above plating treatment, the photosensitive element generally requires plating resistance as well as sensitivity, resolution and adhesion.
In the peeling process, if the peeling piece size (resist piece size after peeling) is large, it will be entangled with the transfer roll, spray nozzle, etc. of the peeling machine, reducing workability and production efficiency, or peeling on the substrate. There is a problem that the pieces are reattached, resulting in a failure in the printed wiring board. Therefore, it is required for the photosensitive element to subdivide the peeling piece (reducing the size of the resist piece after peeling).
In order to improve the peelability of the resist, various photosensitive resin compositions have been studied. For example, a photosensitive resin composition is disclosed in which the release rate and release dispersibility are improved by adjusting the glass transition temperature, weight average molecular weight, and acid value of the binder polymer to specific ranges (for example, patent documents). 1). Moreover, the photosensitive resin composition which improved the peelability of the resist by using a specific polyfunctional ethylenically unsaturated compound is disclosed (for example, refer patent document 2).
しかしながら、上記従来の感光性樹脂組成物では、剥離性を向上させることができても、はく離片を細分化（はく離後のレジスト片のサイズを小さく）させることが不十分であった。また、はく離性を向上させると耐めっき性は低下する傾向にあり、はく離片の細分化と耐めっき性を両立することは困難であった。
本発明は、上記問題に鑑みてなされたものであり、はく離片を細分化（はく離後のレジスト片のサイズを小さく）させることができ、且つ耐めっき性に優れ、感度、解像度及び密着性に優れる感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法を提供する。
However, in the conventional photosensitive resin composition described above, even if the peelability can be improved, it is not sufficient to subdivide the peeled pieces (reducing the size of the resist pieces after peeling). Further, when the peelability is improved, the plating resistance tends to decrease, and it is difficult to achieve both the fragmentation of the peeled piece and the plating resistance.
The present invention has been made in view of the above-mentioned problems, and can be used to subdivide the peeling pieces (reducing the size of the resist pieces after peeling), and is excellent in plating resistance, in sensitivity, resolution and adhesion. An excellent photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board are provided.
本発明は、（Ａ）バインダーポリマー、（Ｂ）エチレン性不飽和基を有する光重合性化合物、及び（Ｃ）光重合開始剤を含有する感光性樹脂組成物であって、前記（Ａ）バインダーポリマーが、少なくとも（メタ）アクリル酸及びヒドロキシアルキル（メタ）アクリル酸エステルを共重合成分として含む感光性樹脂組成物を提供する。
本発明の感光性樹脂組成物は、上記構成を有することにより、感度、解像度及び密着性に優れ、さらにはく離片を細分化（はく離後のレジスト片のサイズを小さく）させることができ、且つ耐めっき性に優れたレジストを得ることが可能となる。
本発明の感光性樹脂組成物は、（Ｄ）密着性付与剤として、（Ｄ−１）ベンゾトリアゾール及び（Ｄ−２）下記一般式（Ｉ）で表されるカルボキシベンゾトリアゾール誘導体を含有することが好ましい。これらの密着性付与剤を組み合わせることにより、レジストの密着性及び耐めっき性を向上させることができ、さらに現像残渣を抑制することができる。
The present invention is a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a photopolymerization initiator, the (A) binder Provided is a photosensitive resin composition in which a polymer contains at least (meth) acrylic acid and a hydroxyalkyl (meth) acrylic acid ester as a copolymerization component.
The photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and adhesion by having the above-described configuration, and can further subdivide the peeled piece (reducing the size of the resist piece after peeling), and is resistant to damage. It becomes possible to obtain a resist having excellent plating properties.
The photosensitive resin composition of the present invention contains (D-1) benzotriazole and (D-2) a carboxybenzotriazole derivative represented by the following general formula (I) as (D) adhesion promoter. Is preferred. By combining these adhesion-imparting agents, the adhesion and plating resistance of the resist can be improved, and further development residues can be suppressed.
本発明の感光性樹脂組成物において、前記一般式（Ｉ）中のＲ１は、下記一般式（ＩＩ）で表される有機基であることが好ましい。
In the photosensitive resin composition of the present invention, R 1 in the general formula (I) is preferably an organic group represented by the following general formula (II).
本発明の感光性樹脂組成物において、前記一般式（ＩＩ）中のＲ２及びＲ３のうち少なくとも一方は、イミノ基及び炭素数１０〜３０のアルキル基を含む一価の有機基であることが好ましい。
本発明の感光性樹脂組成物において、前記一般式（ＩＩ）中のＲ２及びＲ３のうち少なくとも一方は、下記一般式（ＩＩＩ）で表される有機基であることが好ましい。
In the photosensitive resin composition of the present invention, at least one of R 2 and R 3 in the general formula (II) is a monovalent organic group containing an imino group and an alkyl group having 10 to 30 carbon atoms. Is preferred.
In the photosensitive resin composition of the present invention, at least one of R 2 and R 3 in the general formula (II) is preferably an organic group represented by the following general formula (III).
また、本発明は、支持体と、該支持体上に形成された前記感光性樹脂組成物からなる感光性樹脂組成物層と、を備える感光性エレメントを提供する。
また、本発明は、前記感光性エレメントを、回路形成用基板上に感光性樹脂組成物層が密着するようにして積層する積層工程と、前記感光性樹脂組成物層の所定部分に活性光線を照射して露光部を光硬化せしめる露光工程と、前記露光部以外の部分を除去してレジストパターンを形成する現像工程と、を有するレジストパターンの形成方法を提供する。
また、本発明は、前記レジストパターンの形成方法により、レジストパターンが形成された回路形成用基板をエッチング又はめっきして導体パターンを形成する工程を有するプリント配線板の製造法を提供する。
また、本発明のプリント配線板の製造法において、前記レジストパターンが形成された回路形成用基板を、スズめっきして前記導体パターンを形成することが好ましい。
また、本発明のプリント配線板の製造法は、前記導体パターンが形成された回路形成用基板から、前記レジストパターンをアルカリ水溶液によりはく離除去する工程を有することが好ましい。
Moreover, this invention provides a photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body.
In addition, the present invention provides a laminating step in which the photosensitive element is laminated so that the photosensitive resin composition layer is in close contact with the circuit forming substrate, and an active ray is applied to a predetermined portion of the photosensitive resin composition layer. There is provided a resist pattern forming method comprising an exposure step of irradiating and photocuring an exposed portion, and a developing step of removing a portion other than the exposed portion to form a resist pattern.
In addition, the present invention provides a method for manufacturing a printed wiring board, which includes a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern.
In the method for manufacturing a printed wiring board of the present invention, it is preferable that the circuit pattern substrate on which the resist pattern is formed is tin-plated to form the conductor pattern.
Moreover, it is preferable that the manufacturing method of the printed wiring board of this invention has the process of peeling and removing the said resist pattern with alkaline aqueous solution from the circuit formation board | substrate with which the said conductor pattern was formed.
本発明によれば、はく離片を細分化（はく離後のレジスト片のサイズを小さく）させることができ、且つ耐めっき性に優れ、感度、解像度及び密着性に優れる感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法を提供することが可能となる。 According to the present invention, a stripping piece can be subdivided (the size of a resist strip after peeling is small), and is excellent in plating resistance, and is excellent in sensitivity, resolution and adhesion, It is possible to provide a photosensitive element used, a method for producing a resist pattern, and a method for producing a printed wiring board.
以下、本発明について詳細に説明する。なお、本発明における（メタ）アクリル酸とはアクリル酸及びそれに対応するメタクリル酸を意味し、（メタ）アクリレートとはアクリレート及びそれに対応するメタクリレートを意味し、（メタ）アクリロイル基とはアクリロイル基及びそれに対応するメタクリロイル基を意味する。
本発明の感光性樹脂組成物は、（Ａ）バインダーポリマー、（Ｂ）エチレン性不飽和基を有する光重合性化合物、及び（Ｃ）光重合開始剤を含有する。以下、各成分について説明する。
Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.
The photosensitive resin composition of the present invention contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a photopolymerization initiator. Hereinafter, each component will be described.
前記（Ａ）バインダーポリマーは、例えば、重合性単量体をラジカル重合させることにより製造することができる。本発明の（Ａ）バインダーポリマーは、上記重合性単量体として、少なくとも（メタ）アクリル酸及びヒドロキシアルキル（メタ）アクリル酸エステルを含む。
上記（メタ）アクリル酸としては、メタクリル酸及びアクリル酸が挙げられる。現像性、はく離性及び可とう性を良好にする見地から、メタクリル酸及びアクリル酸の双方を含むことが好ましい。
上記（メタ）アクリル酸は、現像性、はく離性及び可とう性を良好にする見地から、全共重合成分の１０〜６０質量％含むことが好ましく、１５〜５５質量％含むことがより好ましく、２０〜５０質量％含むことがさらに好ましい。この含有量が１０質量％未満では現像性及びはく離性が劣る傾向があり、６０質量％を超えると可とう性及びレジストの耐水性が低下する傾向がある。
上記ヒドロキシアルキル（メタ）アクリル酸エステルとしては、例えば、下記一般式（ＩＶ）で表される化合物、及びこれらの化合物のヒドロキシアルキル基にエポキシ基、ハロゲン原子等が置換した化合物などが挙げられる。
The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. The (A) binder polymer of the present invention contains at least (meth) acrylic acid and hydroxyalkyl (meth) acrylic acid ester as the polymerizable monomer.
Examples of the (meth) acrylic acid include methacrylic acid and acrylic acid. It is preferable that both methacrylic acid and acrylic acid are included from the viewpoint of improving developability, peelability and flexibility.
The (meth) acrylic acid is preferably contained in an amount of 10 to 60% by mass, more preferably 15 to 55% by mass of the total copolymer components, from the viewpoint of improving developability, peelability and flexibility. More preferably, it contains 20-50 mass%. When the content is less than 10% by mass, the developability and the peelability tend to be inferior, and when it exceeds 60% by mass, the flexibility and the water resistance of the resist tend to be lowered.
Examples of the hydroxyalkyl (meth) acrylic acid ester include compounds represented by the following general formula (IV), and compounds obtained by substituting an epoxy group, a halogen atom, or the like on the hydroxyalkyl group of these compounds.
［一般式（ＩＶ）中、Ｒ６は水素原子又はメチル基を示し、Ｒ７はヒドロキシアルキル基を示す。］
前記ヒドロキシアルキル基としては、レジストのはく離片の細分化と密着性及び耐めっき性向上とのバランスを良好にする見地から、炭素数１〜１２のヒドロキシアルキル基が好ましく、炭素数１〜８のヒドロキシアルキル基がより好ましく、炭素数１〜４のヒドロキシアルキル基がさらに好ましく、炭素数１〜３のヒドロキシアルキル基が特に好ましい。
上記炭素数１〜１２のヒドロキシアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基及びこれらの構造異性体にヒドロキシル基が置換したものが挙げられる。
上記一般式（ＩＶ）で表される化合物としては、（メタ）アクリル酸メチルヒドロキシド、（メタ）アクリル酸エチルヒドロキシド、（メタ）アクリル酸プロピルヒドロキシド、（メタ）アクリル酸ブチルヒドロキシド等が挙げられる。これらは単独でまたは２種以上を組み合わせて用いることができる。
上記ヒドロキシアルキル（メタ）アクリル酸エステルは、レジストのはく離片の細分化と密着性及び耐めっき性向上とのバランスを良好にする見地から、全共重合成分の１〜３０質量％含むことが好ましく、２〜２０質量％含むことがより好ましく、５〜１５質量％含むことがさらに好ましい。この含有量が１質量％未満では、はく離片が大きくなる傾向があり、また、３０質量％を超えるとレジストの耐水性が低下し密着性及び耐めっき性が悪化する傾向がある。
[In General Formula (IV), R 6 represents a hydrogen atom or a methyl group, and R 7 represents a hydroxyalkyl group. ]
As the hydroxyalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms is preferable from the standpoint of improving the balance between resist fragmentation and adhesion and plating resistance improvement. A hydroxyalkyl group is more preferable, a hydroxyalkyl group having 1 to 4 carbon atoms is more preferable, and a hydroxyalkyl group having 1 to 3 carbon atoms is particularly preferable.
Examples of the C1-C12 hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. And those in which these structural isomers are substituted with a hydroxyl group.
Examples of the compound represented by the general formula (IV) include (meth) acrylic acid methyl hydroxide, (meth) acrylic acid ethyl hydroxide, (meth) acrylic acid propyl hydroxide, (meth) acrylic acid butyl hydroxide, and the like. Is mentioned. These can be used alone or in combination of two or more.
The hydroxyalkyl (meth) acrylate is preferably contained in an amount of 1 to 30% by mass of the total copolymer components from the viewpoint of improving the balance between resist fragmentation and improved adhesion and plating resistance. 2 to 20% by mass, more preferably 5 to 15% by mass. When the content is less than 1% by mass, the peeling pieces tend to be large. When the content exceeds 30% by mass, the water resistance of the resist is lowered and the adhesion and plating resistance tend to be deteriorated.
（Ａ）バインダーポリマーは、（メタ）アクリル酸及びヒドロキシアルキル（メタ）アクリル酸エステル以外の他の重合性単量体を含むことができる。その他の重合性単量体としては、例えば、スチレン、ビニルトルエン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−エチルスチレン、ｐ−メトキシスチレン、ｐ−エトキシスチレン、ｐ−クロロスチレン、ｐ−ブロモスチレン等の重合可能なスチレン誘導体、アクリルアミド、アクリロニトリル、ビニル−ｎ−ブチルエーテル等のビニルアルコールのエステル類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸テトラヒドロフルフリルエステル、（メタ）アクリル酸ジメチルアミノエチルエステル、（メタ）アクリル酸ジエチルアミノエチルエステル、（メタ）アクリル酸グリシジルエステル、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（メタ）アクリレート、（メタ）アクリル酸、α−ブロモ（メタ）アクリル酸、α−クロル（メタ）アクリル酸、β−フリル（メタ）アクリル酸、β−スチリル（メタ）アクリル酸、マレイン酸、マレイン酸無水物、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル等のマレイン酸モノエステル、フマール酸、ケイ皮酸、α−シアノケイ皮酸、イタコン酸、クロトン酸、プロピオール酸などが挙げられる。上記（メタ）アクリル酸アルキルエステルとしては、例えば、一般式（Ｖ）で表される化合物、及びこれらの化合物のアルキル基にエポキシ基、ハロゲン原子等が置換した化合物などが挙げられる。 (A) A binder polymer can contain other polymerizable monomers other than (meth) acrylic acid and hydroxyalkyl (meth) acrylic acid ester. Examples of other polymerizable monomers include styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, p-ethoxy styrene, p-chloro styrene, p-bromo. Polymerizable styrene derivatives such as styrene, esters of vinyl alcohol such as acrylamide, acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , (Me ) Acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, maleic acid Examples thereof include maleic acid monoesters such as monomethyl, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. As said (meth) acrylic-acid alkylester, the compound etc. which the epoxy group, the halogen atom, etc. substituted the compound represented by general formula (V) and the alkyl group of these compounds are mentioned, for example.
上記一般式（Ｖ）中のＲ９で示される炭素数１〜１２のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基及びこれらの構造異性体が挙げられる。
上記一般式（Ｖ）で表される単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル等が挙げられる。これらは単独でまたは２種以上を組み合わせて用いることができる。
これらのバインダーポリマーは、単独でまたは２種類以上を組み合わせて使用される。２種類以上を組み合わせて使用する場合のバインダーポリマーとしては、例えば、異なる共重合成分からなる２種類以上のバインダーポリマー、異なる重量平均分子量の２種類以上のバインダーポリマー、異なる分散度の２種類以上のバインダーポリマーなどが挙げられる。また、特開平１１−３２７１３７号公報記載のマルチモード分子量分布を有するポリマーを使用するもできる。
Examples of the alkyl group having 1 to 12 carbon atoms represented by R 9 in the general formula (V) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.
Examples of the monomer represented by the general formula (V) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Examples include pentyl acid, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These can be used alone or in combination of two or more.
These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion Examples thereof include a binder polymer. In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can be used.
前記（Ｂ）エチレン性不飽和基を有する光重合性化合物として、多価アルコールにα，β−不飽和カルボン酸を反応させて得られる化合物、２，２−ビス（４−（（メタ）アクリロキシポリエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリブトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリエトキシポリプロポキシ）フェニル）プロパン等のビスフェノールＡ系（メタ）アクリレート化合物、グリシジル基含有化合物にα、β−不飽和カルボン酸を反応させで得られる化合物、分子内にウレタン結合を有する（メタ）アクリレート化合物等のウレタンモノマ、ノニルフェノキシポリエチレンオキシアクリレート、γ−クロロ−β−ヒドロキシプロピル−β′−（メタ）アクリロイルオキシエチル−ｏ−フタレート、β−ヒドロキシアルキル−β′−（メタ）アクリロイルオキシアルキル−ｏ−フタレート等のフタル酸系化合物、（メタ）アクリル酸アルキルエステル等が挙げられる。これらは単独でまたは２種類以上を組み合わせて使用される。
（Ｂ）成分は、レジストのはく離片の細分化と密着性及び耐めっき性向上とのバランスを良好にする見地から、分子内にエチレン性不飽和基を１つ有する光重合性化合物及び分子内にエチレン性不飽和基を２つ以上有する光重合性化合物を含むことが好ましい。
分子内にエチレン性不飽和基を１つ有する光重合性化合物としては、ノニルフェノキシポリエチレンオキシアクリレートが好ましく、分子内にエチレン性不飽和基を２つ以上有する光重合性化合物としては、ビスフェノールＡ系（メタ）アクリレート化合物又は分子内にウレタン結合を有する（メタ）アクリレート化合物が好ましい。
(B) As a photopolymerizable compound having an ethylenically unsaturated group, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2,2-bis (4-((meth) acrylic) Loxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, By reacting an α, β-unsaturated carboxylic acid with a bisphenol A-based (meth) acrylate compound such as 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane or a glycidyl group-containing compound. Compound obtained, urethane monomer such as (meth) acrylate compound having urethane bond in the molecule, nonylphenoxypolyethylene oxy Phthalic acid compounds such as acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate, Examples include (meth) acrylic acid alkyl esters. These may be used alone or in combination of two or more.
The component (B) is a photopolymerizable compound having one ethylenically unsaturated group in the molecule and the molecule from the viewpoint of improving the balance between the fragmentation of the resist strip and the improvement in adhesion and plating resistance. It is preferable to contain a photopolymerizable compound having two or more ethylenically unsaturated groups.
The photopolymerizable compound having one ethylenically unsaturated group in the molecule is preferably nonylphenoxypolyethyleneoxyacrylate, and the photopolymerizable compound having two or more ethylenically unsaturated groups in the molecule is a bisphenol A-based compound. A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule is preferred.
前記（Ｃ）光重合開始剤及び増感剤の例としては、アクリジンまたは分子内に少なくとも１つのアクリジニル基を有するアクリジン系化合物、ベンゾフェノン、Ｎ，Ｎ’−テトラメチル−４，４’−ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ’−テトラアルキル−４，４’−ジアミノベンゾフェノン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパノン−１等の芳香族ケトン、アルキルアントラキノン等のキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体等の２，４，５−トリアリールイミダゾール二量体、Ｎ−フェニルグリシン、Ｎ−フェニルグリシン誘導体、クマリン系化合物、オニウム塩などが挙げられる。これらは単独でまたは２種類以上を組み合わせて使用される。
（Ｃ）成分は、感度及び密着性の見地から、２，４，５−トリアリールイミダゾール二量体を含むことが好ましい。
Examples of the (C) photopolymerization initiator and sensitizer include acridine or an acridine compound having at least one acridinyl group in the molecule, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [ Aromatic ketone such as 4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyldimethyl ketal, etc. Benzyl derivative of 2- (o-chlorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer 2,4,5-triaryl such as 2-mer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Examples include imidazole dimer, N-phenylglycine, N-phenylglycine derivative, coumarin compound, onium salt and the like. These may be used alone or in combination of two or more.
The component (C) preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of sensitivity and adhesion.
本発明の感光性樹脂組成物は、レジストの密着性及び耐めっき性を向上させる見地から、（Ｄ）密着性付与剤として（Ｄ−１）ベンゾトリアゾール及び（Ｄ−２）下記一般式（Ｉ）で表されるカルボキシベンゾトリアゾール誘導体を含有することが好ましい。 From the standpoint of improving the adhesion and plating resistance of the resist, the photosensitive resin composition of the present invention comprises (D) benzotriazole and (D-2) the following general formula (I) as an adhesion imparting agent. It is preferable to contain the carboxybenzotriazole derivative represented by this.
レジストの密着性及び耐めっき性を一層向上させる見地から、上記一般式（Ｉ）中、Ｒ１は水素原子又は炭素数１〜３０のアルキル基であることが好ましい。
また、レジストの密着性及び耐めっき性を一層向上させる見地から、前記Ｒ１は、下記一般式（ＩＩ）で表される有機基であることが好ましい。
From the viewpoint of further improving the adhesion and plating resistance of the resist, in the general formula (I), R 1 is preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
Moreover, from the viewpoint of further improving the adhesion and plating resistance of the resist, R 1 is preferably an organic group represented by the following general formula (II).
レジストの密着性及び耐めっき性を一層向上させる見地から、上記一般式（ＩＩ）中、前記Ｒ２及びＲ３のうち少なくとも一方は、炭素数１〜３０のアルキル基であることが好ましく、炭素数５〜２５のアルキル基であることがより好ましく、炭素数１０〜２０のアルキル基であることがさらに好ましい。
また、レジストの密着性及び耐めっき性を一層向上させる見地から、上記一般式（ＩＩ）中、前記Ｒ２及びＲ３のうち少なくとも一方は、イミノ基及び炭素数１０〜３０のアルキル基を含む一価の有機基であることが好ましい。
From the viewpoint of further improving the adhesion and plating resistance of the resist, in the general formula (II), at least one of R 2 and R 3 is preferably an alkyl group having 1 to 30 carbon atoms. It is more preferably an alkyl group having 5 to 25 carbon atoms, and further preferably an alkyl group having 10 to 20 carbon atoms.
Further, from the viewpoint of further improving the adhesion and plating resistance of the resist, in the general formula (II), at least one of the R 2 and R 3 contains an imino group and an alkyl group having 10 to 30 carbon atoms. A monovalent organic group is preferred.
本発明の感光性樹脂組成物において、前記一般式（ＩＩ）中のＲ２及びＲ３のうち少なくとも一方は、下記一般式（ＩＩＩ）で表される有機基であることが好ましい。 In the photosensitive resin composition of the present invention, at least one of R 2 and R 3 in the general formula (II) is preferably an organic group represented by the following general formula (III).
また、感光性樹脂組成物は上記（Ｄ−１）及び（Ｄ−２）成分以外の密着性付与剤を含んでいてもよい。
Moreover, the photosensitive resin composition may contain adhesiveness imparting agents other than the said (D-1) and (D-2) component.
前記（Ａ）バインダーポリマーの含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、４０〜８０質量部であることが好ましく、４５〜７０質量部であることがより好ましい。この含有量が４０質量部未満では光硬化物が脆くなり易く、感光性エレメントとして用いた場合に塗膜性が劣る傾向があり、８０質量部を超えると光感度が不充分となる傾向がある。
前記（Ｂ）エチレン性不飽和基を有する光重合性化合物の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、２０〜６０質量部であることが好ましく、３０〜５０質量部であることがより好ましい。この含有量が２０質量部未満では光感度が不充分となる傾向があり、６０質量部を超えると光硬化物が脆くなる傾向がある。
The content of the (A) binder polymer is preferably 40 to 80 parts by mass and more preferably 45 to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). preferable. If this content is less than 40 parts by mass, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be inferior, and if it exceeds 80 parts by mass, the photosensitivity tends to be insufficient. .
The content of the photopolymerizable compound (B) having an ethylenically unsaturated group is preferably 20 to 60 parts by mass with respect to 100 parts by mass as a total of the components (A) and (B), 30 More preferably, it is -50 mass parts. If this content is less than 20 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by mass, the photocured product tends to become brittle.
前記（Ｃ）光重合開始剤及び増感剤の含有量は、感光性樹脂組成物層の吸光度が０．２〜１．５になるように調整されることが好ましく、０．３〜１．０になるように調整されることがより好ましく、０．４〜０．８になるように調整されることが最も好ましい。この感光性樹脂組成物層の吸光度が０．２未満では光感度が不充分となる傾向があり、１．５を超えると露光の際に組成物の表面での吸収が増大して内部の光硬化が不充分となる傾向がある。 The content of the (C) photopolymerization initiator and sensitizer is preferably adjusted so that the absorbance of the photosensitive resin composition layer is 0.2 to 1.5, and 0.3 to 1. It is more preferable to adjust so that it may be set to 0, and it is most preferable to adjust so that it may become 0.4-0.8. If the absorbance of the photosensitive resin composition layer is less than 0.2, the photosensitivity tends to be insufficient, and if it exceeds 1.5, absorption on the surface of the composition increases during exposure, and the internal light is increased. There is a tendency for curing to be insufficient.
感光性樹脂組成物が（Ｄ）密着性付与剤を含む場合の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．０１〜１０質量部であることが好ましく、０．０１〜５質量部であることがより好ましく、０．０１〜１質量部であることがさらに好ましい。この含有量が０．０１質量部未満ではレジストの密着性及び耐めっき性が不十分となる傾向があり、２０質量部を超えるとはく離性の低下及び現像残渣を生じる傾向がある。
（Ｄ）密着性付与剤が（Ｄ−１）ベンゾトリアゾール及び（Ｄ−２）上記一般式（Ｉ）で表されるカルボキシベンゾトリアゾール誘導体を含有する場合の各々の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、（Ｄ−１）成分は０．０１〜１質量部であることが好ましく、０．０１〜０．１質量部であることがより好ましく、（Ｄ−２）成分は０．０１〜１質量部であることが好ましく、０．０５〜０．５質量部であることがより好ましい。（Ｄ−１）の含有量が０．０１質量部未満ではレジストの密着性及び耐めっき性が不十分となる傾向があり、１質量部を超えると現像残渣を生じる傾向があり、（Ｄ−２）の含有量が０．０１質量部未満ではレジストの密着性及び耐めっき性が不十分となる傾向があり、１質量部を超えるとはく離性が低下する傾向がある。
Content in case a photosensitive resin composition contains (D) adhesion imparting agent shall be 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. Preferably, it is 0.01-5 mass parts, More preferably, it is 0.01-1 mass part. If the content is less than 0.01 parts by mass, the adhesion and plating resistance of the resist tend to be insufficient, and if it exceeds 20 parts by mass, the peelability tends to deteriorate and a development residue tends to occur.
(D) When the adhesion-imparting agent contains (D-1) benzotriazole and (D-2) a carboxybenzotriazole derivative represented by the above general formula (I), each content is (A) component And with respect to 100 mass parts of total amounts of (B) component, it is preferable that (D-1) component is 0.01-1 mass part, It is more preferable that it is 0.01-0.1 mass part, The component (D-2) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 part by mass. If the content of (D-1) is less than 0.01 parts by mass, the adhesiveness and plating resistance of the resist tend to be insufficient, and if it exceeds 1 part by mass, a development residue tends to occur. If the content of 2) is less than 0.01 part by mass, the adhesion and plating resistance of the resist tend to be insufficient, and if it exceeds 1 part by mass, the peelability tends to decrease.
前記感光性樹脂組成物には、必要に応じて、分子内に少なくとも１つのカチオン重合可能な環状エーテル基を有する光重合性化合物、カチオン重合開始剤、マラカイトグリーン等の染料、トリブロモフェニルスルホン、ロイコクリスタルバイオレット等の光発色剤、熱発色防止剤、ｐ−トルエンスルホンアミド等の可塑剤、顔料、充填剤、消泡剤、難燃剤、安定剤、レベリング剤、はく離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤などを（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して各々０．０１〜２０質量部程度含有することができる。これらは単独でまたは２種類以上を組み合わせて使用される。 In the photosensitive resin composition, if necessary, a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, tribromophenylsulfone, Photochromic agents such as leuco crystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, leveling agents, peeling accelerators, antioxidants, A fragrance | flavor, an imaging agent, a thermal crosslinking agent, etc. can be contained about 0.01-20 mass parts, respectively with respect to 100 mass parts of total amounts of (A) component and (B) component. These may be used alone or in combination of two or more.
前記感光性樹脂組成物は、必要に応じて、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、Ｎ，Ｎ−ジメチルホルムアミド、プロピレングリコールモノメチルエーテル等の溶剤またはこれらの混合溶剤に溶解して固形分３０〜６０質量％程度の溶液として塗布することができる。
前記感光性樹脂組成物は、特に制限はないが、銅、銅系合金、鉄、鉄系合金等の金属面上に、液状レジストとして塗布して乾燥後、必要に応じて保護フィルムを被覆して用いるか、感光性エレメントの形態で用いられることが好ましい。
また、感光性樹脂組成物層の厚みは、用途により異なるが、乾燥後の厚みで１〜１００μｍ程度であることが好ましい。液状レジストに保護フィルムを被覆して用いる場合は、保護フィルムとして、ポリエチレン、ポリプロピレン等の重合体フィルムなどが挙げられる。
The photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or a mixed solvent thereof as necessary. And can be applied as a solution having a solid content of about 30 to 60% by mass.
The photosensitive resin composition is not particularly limited, but is coated as a liquid resist on a metal surface such as copper, a copper-based alloy, iron, and an iron-based alloy, dried, and then covered with a protective film as necessary. Or used in the form of a photosensitive element.
Moreover, although the thickness of the photosensitive resin composition layer changes with uses, it is preferable that it is about 1-100 micrometers by the thickness after drying. In the case of using a liquid resist coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.
上記感光性エレメントは、例えば、支持体として、ポリエチレンテレフタレート、ポリプロピレン、ポリエチレン、ポリエステル等の重合体フィルム上に感光性樹脂組成物を塗布、乾燥することにより得ることができる。上記塗布は、例えば、ロールコータ、コンマコータ、グラビアコータ、エアーナイフコータ、ダイコータ、バーコータ等の公知の方法で行うことができる。また、乾燥は、４０〜１５０℃、１〜３０分間程度で行うことができる。また、感光性樹脂組成物層中の残存有機溶剤量は、後の工程での有機溶剤の拡散を防止する点から、２質量％以下とすることが好ましい。
これらの重合体フィルムの厚みは、１〜１００μｍとすることが好ましい。これらの重合体フィルムの一つは感光性樹脂組成物層の支持体として、他の一つは感光性樹脂組成物の保護フィルムとして感光性樹脂組成物層の両面に積層してもよい。保護フィルムとしては、感光性樹脂組成物層及び支持体の接着力よりも、感光性樹脂組成物層及び保護フィルムの接着力の方が小さいものが好ましく、また、低フィッシュアイのフィルムが好ましい。
また、前記感光性エレメントは、感光性樹脂組成物層、支持体及び保護フィルムの他に、クッション層、接着層、光吸収層、ガスバリア層等の中間層や保護層を有していてもよい。
前記感光性エレメントは、例えば、そのまままたは感光性樹脂組成物層の他の面に保護フィルムをさらに積層して円筒状の巻芯に巻きとって貯蔵される。なお、この際支持体が１番外側になるように巻き取られることが好ましい。上記ロール状の感光性エレメントロールの端面には、端面保護の見地から端面セパレータを設置することが好ましく、耐エッジフュージョンの見地から防湿端面セパレータを設置することが好ましい。また、梱包方法として、透湿性の小さいブラックシートに包んで包装することが好ましい。
上記巻芯としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体）等のプラスチックなどが挙げられる。
The photosensitive element can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester as a support. The application can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Moreover, drying can be performed at 40 to 150 ° C. for about 1 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
The thickness of these polymer films is preferably 1 to 100 μm. One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition. As the protective film, those having a smaller adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable.
In addition to the photosensitive resin composition layer, the support and the protective film, the photosensitive element may have an intermediate layer or protective layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer. .
The photosensitive element is stored, for example, as it is or by further laminating a protective film on the other surface of the photosensitive resin composition layer and winding it around a cylindrical core. In addition, it is preferable to wind up so that a support body may become the 1st outer side at this time. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.
Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
上記感光性エレメントを用いてレジストパターンを製造するに際しては、前記の保護フィルムが存在している場合には、保護フィルムを除去後、感光性樹脂組成物層を７０〜１３０℃程度に加熱しながら回路形成用基板に０．１〜１ＭＰａ程度（１〜１０ｋｇｆ／ｃｍ２程度）の圧力で圧着することにより積層する方法などが挙げられ、減圧下で積層することも可能である。積層される表面は、通常金属面であるが、特に制限はない。
このようにして積層が完了した感光性樹脂組成物層は、ネガまたはポジマスクパターンを通して活性光線が画像状に照射される。上記活性光線の光源としては、公知の光源、例えば、カーボンアーク灯、水銀蒸気アーク灯、高圧水銀灯、キセノンランプ等の紫外線、可視光などを有効に放射するものが用いられる。
次いで、露光後、感光性樹脂組成物層上に支持体が存在している場合には、支持体を除去した後、アルカリ性水溶液、水系現像液、有機溶剤等の現像液によるウエット現像、ドライ現像等で未露光部を除去して現像し、レジストパターンを製造することができる。上記アルカリ性水溶液としては、例えば、０．１〜５質量％炭酸ナトリウムの希薄溶液、０．１〜５質量％炭酸カリウムの希薄溶液、０．１〜５質量％水酸化ナトリウムの希薄溶液等が挙げられる。上記アルカリ性水溶液のｐＨは９〜１１の範囲とすることが好ましく、その温度は、感光性樹脂組成物層の現像性に合わせて調節される。また、アルカリ性水溶液中には、表面活性剤、消泡剤、有機溶剤等を混入させてもよい。上記現像の方式としては、例えば、ディップ方式、スプレー方式、ブラッシング、スラッピング等が挙げられる。
In producing a resist pattern using the photosensitive element, when the protective film is present, the protective film is removed and then the photosensitive resin composition layer is heated to about 70 to 130 ° C. For example, a method of laminating by pressure bonding to a circuit forming substrate at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm 2 ) may be mentioned, and the lamination may be performed under reduced pressure. The surface to be laminated is usually a metal surface, but is not particularly limited.
The photosensitive resin composition layer thus laminated is irradiated with actinic rays in an image form through a negative or positive mask pattern. As the light source of the actinic light, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used.
Next, after exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then wet development or dry development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. The resist pattern can be manufactured by removing the unexposed portion with development or the like and developing. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, and the like. It is done. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.
現像後の処理として、必要に応じて６０〜２５０℃程度の加熱または０．２〜１０Ｊ／ｃｍ２程度の露光を行うことによりレジストパターンをさらに硬化して用いてもよい。
現像後に行われる金属面のエッチングには、例えば、塩化第二銅溶液、塩化第二鉄溶液、アルカリエッチング溶液等を用いることができる。
本発明の感光性エレメントを用いてプリント配線板を製造する場合、現像されたレジストパターンをマスクとして、回路形成用基板の表面を、エッチング、めっき等の公知の方法で処理する。上記めっき法としては、例えば、銅めっき、はんだめっき、ニッケルめっき、金めっきなどがある。次いで、レジストパターンは、例えば、現像に用いたアルカリ性水溶液よりさらに強アルカリ性の水溶液ではく離することができる。上記強アルカリ性の水溶液としては、例えば、１〜１０質量％水酸化ナトリウム水溶液、１〜１０質量％水酸化カリウム水溶液、またはアミンはく離液等が用いられる。上記はく離液は単独でまたは２種類以上を組み合わせて使用される。上記はく離方式としては、例えば、浸漬方式、スプレ-方式等が挙げられる。また、レジストパターンが形成されたプリント配線板は、多層プリント配線板でもよく、小径スルーホールを有していてもよい。
As the treatment after development, the resist pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm 2 as necessary.
For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.
When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating. Next, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As said strong alkaline aqueous solution, 1-10 mass% sodium hydroxide aqueous solution, 1-10 mass% potassium hydroxide aqueous solution, or an amine peeling liquid etc. are used, for example. The said peeling liquid is used individually or in combination of 2 or more types. Examples of the peeling method include an immersion method and a spray method. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.
以下、本発明を実施例により説明する。
表１及び表２に示す材料を配合し、感光性樹脂組成物の溶液を得た（実施例１〜３及び比較例１〜３）。
Hereinafter, the present invention will be described with reference to examples.
The material shown in Table 1 and Table 2 was mix | blended, and the solution of the photosensitive resin composition was obtained (Examples 1-3 and Comparative Examples 1-3).
Ｆ−８０４Ｓ：下記式（ＶＩ）で示される1-[N,N-ビス(2-エチルヘキシル)アミノメチル]-5-カルボキシベンゾトリアゾール(千代田ケミカル株式会社製、商品名）
F-804S: 1- [N, N-bis (2-ethylhexyl) aminomethyl] -5-carboxybenzotriazole represented by the following formula (VI) (trade name, manufactured by Chiyoda Chemical Co., Ltd.)
次いで、銅箔（厚み３５μｍ）を両面に積層したガラスエポキシ材である銅張積層板（日立化成工業株式会社製、商品名ＭＣＬ−Ｅ−６７）の銅表面を＃６００相当のブラシを持つ研磨機（三啓株式会社製）を用いて研磨し、水洗後、空気流で乾燥し、得られた銅張積層板を８０℃に加温し、その銅表面上に保護フィルムを剥がしながら前記感光性樹脂組成物層を１２０℃のヒートロールを用い１．５ｍ／分の速度でラミネートした。
次に、高圧水銀灯ランプを有する露光機（株式会社オーク製作所製、商品名ＨＭＷ−２０１ＧＸ）を用いて、ネガとしてストーファー２１段ステップタブレットを試験片の上に置いて露光した。
次に、ポリエチレンテレフタレートフィルムをはく離し、３０℃で１質量％炭酸ナトリウム水溶液を最少現像時間の２倍の時間でスプレーし、未露光部分を除去した後、銅張積層板上に形成された光硬化膜のステップタブレットの段数を測定することにより、感光性樹脂組成物の光感度を評価した。
最少現像時間は未露光部のレジストが現像処理によって完全に除去された時間を測定した。
Next, the copper surface of a copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name MCL-E-67), which is a glass epoxy material laminated with copper foil (thickness 35 μm) on both sides, is polished with a brush equivalent to # 600 Polishing using a machine (manufactured by Sankei Co., Ltd.), washing with water, drying with air flow, heating the obtained copper-clad laminate to 80 ° C., and peeling off the protective film on the copper surface. The conductive resin composition layer was laminated at a speed of 1.5 m / min using a 120 ° C. heat roll.
Next, using a light exposure machine (trade name HMW-201GX, manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, a stove 21-step tablet was placed on the test piece as a negative and exposed.
Next, the polyethylene terephthalate film is peeled off, and a 1% by mass sodium carbonate aqueous solution is sprayed at 30 ° C. for twice the minimum development time to remove unexposed portions, and then the light formed on the copper clad laminate The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the cured film.
The minimum development time was measured as the time when the unexposed resist was completely removed by the development process.
光感度は、ストーファーの２１段ステップタブレットにおいて、現像後(現像時間＝最少現像時間×２)の残存ステップ段数が８．０となる露光エネルギー量(ｍＪ／ｃｍ２)で評価した。この露光エネルギー量が少ないほど光感度が高いことを示す。
解像度は、ストーファーの２１段ステップタブレットを有するフォトツールと解像度評価用ネガとしてスペース幅／ライン幅が８／４００〜４７／４００（単位：μｍ）の配線パターンを有するフォトツールを密着させ、ストーファーの２１段ステップタブレットにおいて、現像後(現像時間＝最少現像時間×２)の残存ステップ段数が８．０となるエネルギー量で露光を行った。ここで、解像度は、現像(現像時間＝最少現像時間×２)処理によって未露光部をきれいに除去することができたライン幅間のスペース幅の最も小さい値により評価した。解像度の評価は数値が小さいほど良好な値である。
Photosensitivity was evaluated by an exposure energy amount (mJ / cm 2 ) at which the number of remaining steps after development (development time = minimum development time × 2) was 8.0 in a stove 21 step tablet. The smaller the exposure energy amount, the higher the photosensitivity.
As for resolution, a photo tool having a stove 21-step tablet and a photo tool having a wiring pattern with a space width / line width of 8/400 to 47/400 (unit: μm) are closely attached as a negative for resolution evaluation. In a fur 21-step tablet, exposure was carried out with an energy amount such that the number of remaining step steps after development (development time = minimum development time × 2) was 8.0. Here, the resolution was evaluated based on the smallest value of the space width between the line widths in which the unexposed portion could be removed cleanly by the development (development time = minimum development time × 2) process. The smaller the numerical value, the better the resolution evaluation.
密着性は、ストーファーの２１段ステップタブレットを有するフォトツールと密着性評価用ネガとしてライン幅／スペース幅が８／４００〜４７／４００（単位：μｍ）の配線パターンを有するフォトツールを密着させ、ストーファーの２１段ステップタブレットにおいて、現像後(現像時間＝最少現像時間×２)の残存ステップ段数が８．０となるエネルギー量で露光を行った。ここで密着性は、現像後(現像時間＝最少現像時間×２)、ラインを形成しているレジストが基板にしっかりと密着していて剥がれている箇所が無く、また、ラインが蛇行していたり、曲がったりしていないライン幅の最も小さい値により評価した。密着性の評価は数値が小さいほど良好な値である。 Adhesion is achieved by adhering a phototool having a stove 21-step tablet and a phototool having a wiring pattern with a line width / space width of 8/400 to 47/400 (unit: μm) as a negative for adhesion evaluation. Then, in a 21-step tablet of Stöffer, exposure was performed with an energy amount that the number of remaining step steps after development (development time = minimum development time × 2) was 8.0. Here, the adhesion is that after development (development time = minimum development time × 2), there is no part where the resist forming the line is firmly adhered to the substrate, and the line is meandering. Evaluation was based on the smallest value of the line width that was not bent. The smaller the numerical value, the better the evaluation of adhesion.
はく離片形状（サイズ）は、はく離評価用ネガ(ＰＥＴネガ：６０×４５ｍｍ角(ベタ：パターン無し))を用いて、ストーファーの２１段ステップタブレットにおいて、現像後(現像時間＝最少現像時間×２)の残存ステップ段数が８．０となる露光エネルギー量で露光を行い、現像(現像時間＝最少現像時間×２)した。このようにして作製したはく離評価基板（６０×４５ｍｍ角)をビーカーに浸漬（はく離液：３．０質量％ ＮａＯＨ水溶液、５０℃）させ、はく離終了後攪拌子での攪拌を３０秒間行った後のはく離片形状（サイズ）を観測することで評価した（このはく離片形状（サイズ）は、用いたネガの種類やはく離機のスプレー圧などによって異なる）。 The shape (size) of the peeled piece was determined after development (development time = minimum development time ×) on a stove 21-step tablet using a peel evaluation negative (PET negative: 60 × 45 mm square (solid: no pattern)). The exposure was carried out with an exposure energy amount of 2) where the number of remaining steps was 8.0, and development (development time = minimum development time × 2) was performed. The separation evaluation substrate (60 × 45 mm square) produced in this manner was immersed in a beaker (peeling solution: 3.0% by mass NaOH aqueous solution, 50 ° C.), and after stirring, stirring with a stirrer was performed for 30 seconds. Evaluation was made by observing the shape (size) of the peeling piece (this peeling piece shape (size) varies depending on the type of negative used and the spray pressure of the peeling machine).
耐めっき性は、表３の条件でスズめっきを行い、表４の基準により評価した。 The plating resistance was evaluated based on the criteria shown in Table 4 by performing tin plating under the conditions shown in Table 3.
以上の結果をまとめて表５に示した。
The results are summarized in Table 5.
表５から明らかなように、実施例１、２及び３は、はく離片を細分化（はく離後のレジスト片のサイズを小さく）させる効果があり、且つ、耐めっき性が良好である。また、感度、解像度及び密着性にも優れる。これに対し、比較例１は耐めっき性及び密着性は良好であるものの、はく離片形状（サイズ）が大きく、比較例２及び３は、はく離片形状（サイズ）は小さくなるが、耐めっき性及び密着性が不十分である。 As is apparent from Table 5, Examples 1, 2 and 3 have the effect of subdividing the peeled pieces (reducing the size of the resist pieces after peeling) and having good plating resistance. Moreover, it is excellent also in a sensitivity, resolution, and adhesiveness. On the other hand, although Comparative Example 1 has good plating resistance and adhesion, the peel piece shape (size) is large. In Comparative Examples 2 and 3, the peel piece shape (size) is small, but the plating resistance is high. Insufficient adhesion.
Claims (9)
前記（Ａ）バインダーポリマーが、少なくとも（メタ）アクリル酸及びヒドロキシアルキル（メタ）アクリル酸エステルを共重合成分として含む感光性樹脂組成物。
The photosensitive resin composition in which the (A) binder polymer contains at least (meth) acrylic acid and a hydroxyalkyl (meth) acrylic ester as a copolymerization component.
前記感光性樹脂組成物層の所定部分に活性光線を照射して露光部を光硬化せしめる露光工程と、
前記露光部以外の部分を除去してレジストパターンを形成する現像工程と、
を有するレジストパターンの形成方法。 A lamination step of laminating the photosensitive element according to claim 5 so that the photosensitive resin composition layer is in close contact with the circuit forming substrate;
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; and
A development step of removing a portion other than the exposed portion to form a resist pattern;
A method for forming a resist pattern having
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