KR20210062016A - Photosensitive resin composition, method of forming a resist pattern, and method of manufacturing a plated article - Google Patents
Photosensitive resin composition, method of forming a resist pattern, and method of manufacturing a plated article Download PDFInfo
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- KR20210062016A KR20210062016A KR1020217008561A KR20217008561A KR20210062016A KR 20210062016 A KR20210062016 A KR 20210062016A KR 1020217008561 A KR1020217008561 A KR 1020217008561A KR 20217008561 A KR20217008561 A KR 20217008561A KR 20210062016 A KR20210062016 A KR 20210062016A
- Authority
- KR
- South Korea
- Prior art keywords
- resist pattern
- resin composition
- meth
- photosensitive resin
- acrylate
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- -1 thiol compound Chemical class 0.000 claims abstract description 81
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000011282 treatment Methods 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 25
- 238000007747 plating Methods 0.000 claims description 24
- 239000007870 radical polymerization initiator Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002923 oximes Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 74
- 239000000047 product Substances 0.000 description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 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
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- 240000008976 Pterocarpus marsupium Species 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 238000007772 electroless plating Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- UCUPUEARJPTGKU-UHFFFAOYSA-N octadecyl 3-sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCS UCUPUEARJPTGKU-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000010526 radical polymerization reaction Methods 0.000 description 2
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- 125000004079 stearyl 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])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
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
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- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
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- NKMOLEYVYVWWJC-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCN1C(=O)N(CCOC(=O)CC(C)S)C(=O)N(CCOC(=O)CC(C)S)C1=O NKMOLEYVYVWWJC-UHFFFAOYSA-N 0.000 description 1
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- G03F7/004—Photosensitive materials
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- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- 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
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- G03F7/004—Photosensitive materials
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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Abstract
본 발명은, 중합성 화합물 (A), 광 라디칼 중합 개시제 (B), 티올 화합물 (C) 및 중합 금지제 (D)를 함유하고, 상기 티올 화합물 (C)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 5 내지 50질량부, 상기 중합 금지제 (D)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 1 내지 10질량부인 것을 특징으로 하는 감광성 수지 조성물이다. 본 발명은, 브라이트 필드와 다크 필드의 양쪽에 있어서 노광량 여유도(EL)가 넓은 감광성 수지 조성물을 제공할 수 있다. 상기 감광성 수지 조성물을 사용하여, 브라이트 필드와 다크 필드의 양쪽에 있어서 고정밀도의 미세한 레지스트 패턴을 형성할 수 있는, 레지스트 패턴의 형성 방법을 제공할 수 있다. 상기 레지스트 패턴의 형성 방법에 의해 형성한 레지스트 패턴을 사용하여, 고정밀도의 미세한 도금 조형물을 제조할 수 있는, 도금 조형물의 제조 방법을 제공할 수 있다.The present invention contains a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C) and a polymerization inhibitor (D), and the content of the thiol compound (C) is the polymerizable compound ( A) 5 to 50 parts by mass per 100 parts by mass, and the content of the polymerization inhibitor (D) is 1 to 10 parts by mass per 100 parts by mass of the polymerizable compound (A). The present invention can provide a photosensitive resin composition having a wide exposure amount margin EL in both a bright field and a dark field. Using the photosensitive resin composition, it is possible to provide a method for forming a resist pattern capable of forming a fine resist pattern with high precision in both bright fields and dark fields. It is possible to provide a method for manufacturing a plated article, capable of producing a high-precision, fine plated article by using the resist pattern formed by the method of forming the resist pattern.
Description
본 발명은, 감광성 수지 조성물, 레지스트 패턴의 형성 방법, 및 도금 조형물의 제조 방법에 관한 것이다.The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and a method for producing a plated article.
근년, 반도체 소자나, 액정 디스플레이나 터치 패널 등의 표시 소자의 배선이나 범프 등의 접속 단자는, 고밀도로 실장하는 것에 대한 요구가 높아지고 있는 점에서, 미세화가 진행되고 있다.In recent years, the demand for high-density mounting of connection terminals such as wiring and bumps of semiconductor elements and display elements such as liquid crystal displays and touch panels is increasing, and thus, miniaturization has progressed.
일반적으로 배선이나 범프 등은 도금 조형물이며, 특허문헌 1에 기재된 바와 같이, 구리 등의 금속박을 갖는 기판 상에 감광성 수지 조성물을 도포하여 레지스트 도막을 형성하고, 그 레지스트 도막에 마스크를 사용하여 노광 및 현상을 행하여, 레지스트 패턴을 형성하고, 그 레지스트 패턴을 마스크로 하여, 기판 상에 도금을 행함으로써 제조된다.In general, wiring or bumps are plated products, and as described in Patent Document 1, a photosensitive resin composition is applied on a substrate having a metal foil such as copper to form a resist coating film, and exposure and exposure using a mask on the resist coating film are performed. It is manufactured by performing development, forming a resist pattern, and plating on a substrate using the resist pattern as a mask.
이 때문에, 배선이나 범프 등의 미세화에 수반하여, 그 제조에 사용되는 레지스트 패턴도 미세화가 필요해지고 있다.For this reason, along with the miniaturization of wirings and bumps, the resist pattern used for its production is also required to be miniaturized.
네가티브형의 레지스트 도막에 마스크를 사용하여 노광을 행할 때, 레지스트 도막에 있어서, 배선용의 레지스트가 밀하게 형성되는 부분은, 상대적으로 노광량이 많아지는 명 영역(브라이트 필드, Bright-Field)이 되고, 범프용의 레지스트가 성기게 형성되는 부분은, 상대적으로 노광량이 적어지는 암 영역(다크 필드, Dark-Field)이 된다.When exposure is performed using a mask on a negative resist coating film, a portion of the resist coating film in which the resist for wiring is densely formed becomes a bright area (bright field) in which the exposure amount is relatively increased, The portion where the bump resist is sparsely formed becomes a dark area (dark field) in which the exposure amount is relatively small.
레지스트 패턴이 미세화되면, 노광광의 회절, 누설광, 기판으로부터의 노광광의 반사 영향이 강해져, 브라이트 필드와 다크 필드에 있어서, 레지스트 도막에 대한 실질적인 노광량(실행 노광량)이 달라진다. 그것에서 기인하여, 브라이트 필드와 다크 필드에 있어서, 형성되는 레지스트 패턴의 정밀도에 차가 생기는 문제가 발생한다. 그 때문에, 브라이트 필드와 다크 필드에 있어서, 실행 노광량이 어느 정도 다르다고 해도, 브라이트 필드와 다크 필드의 양쪽에 있어서 레지스트 패턴이 고정밀도로 형성되는 성질이 레지스트 도막에 요구된다. 즉, 다크 필드 및 브라이트 필드의 양쪽에 있어서 양호한 레지스트 패턴을 형성할 수 있는 노광량의 범위가 중복되는, 넓은 공통의 노광량 여유도(Exposure Latitude, 약칭하여 「EL」이라고도 함)를 갖는 레지스트 조성물이 요구된다. 여기서, 노광량 여유도(EL)란, 레지스트 패턴이 고정밀도로 형성될 수 있는 노광량의 범위를 의미한다.When the resist pattern is made finer, the diffraction of exposure light, leakage light, and reflection of exposure light from the substrate become stronger, and the actual exposure amount (performed exposure amount) to the resist coating film varies in bright field and dark field. Due to this, in the bright field and the dark field, a problem arises in that a difference in the precision of the formed resist pattern occurs. Therefore, even if the amount of exposure performed in the bright field and the dark field differs to some extent, the resist coating film is required to have a property of forming a resist pattern with high precision in both the bright field and the dark field. That is, there is a need for a resist composition having a wide common exposure amount margin (Exposure Latitude, also referred to as ``EL'' for short), in which the range of exposure amounts capable of forming a good resist pattern in both the dark field and the bright field overlap. do. Here, the exposure amount margin EL refers to the range of the exposure amount in which the resist pattern can be formed with high precision.
본 발명은, 다크 필드 및 브라이트 필드에 있어서 넓은 공통의 노광량 여유도(EL)를 갖는 감광성 수지 조성물을 제공하는 것, 다크 필드 및 브라이트 필드의 양쪽에 있어서 고정밀도의 미세한 레지스트 패턴을 형성할 수 있는 레지스트 패턴의 형성 방법을 제공하는 것, 및 고정밀도의 미세한 도금 조형물을 제조할 수 있는 도금 조형물의 제조 방법을 제공하는 것을 목적으로 한다.The present invention provides a photosensitive resin composition having a wide common exposure amount margin (EL) in a dark field and a bright field, and capable of forming a high-precision, fine resist pattern in both the dark field and the bright field. An object of the present invention is to provide a method for forming a resist pattern, and to provide a method for manufacturing a plated article capable of producing a fine plated article with high precision.
상기 목적을 달성하는 본 발명은, 예를 들어 하기 [1] 내지 [8]에 관한 것이다.The present invention which achieves the above object relates to the following [1] to [8], for example.
[1] 중합성 화합물 (A), 광 라디칼 중합 개시제 (B), 티올 화합물 (C) 및 중합 금지제 (D)를 함유하고, 상기 티올 화합물 (C)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 5 내지 20질량부, 상기 중합 금지제 (D)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 1 내지 5질량부인 것을 특징으로 하는 감광성 수지 조성물.[1] A polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D) are contained, and the content of the thiol compound (C) is the polymerizable compound (A) ) 5 to 20 parts by mass per 100 parts by mass, and the content of the polymerization inhibitor (D) is 1 to 5 parts by mass per 100 parts by mass of the polymerizable compound (A).
[2] 상기 티올 화합물 (C)가 다관능 티올 화합물 (C-1)인, 상기 [1]에 기재된 감광성 수지 조성물.[2] The photosensitive resin composition according to [1], wherein the thiol compound (C) is a polyfunctional thiol compound (C-1).
[3] 상기 티올 화합물 (C) 100질량부에 대하여, 상기 중합 금지제 (D)의 함유량이 20 내지 80질량부인, 상기 [1] 또는 [2]에 기재된 감광성 수지 조성물.[3] The photosensitive resin composition according to [1] or [2], wherein the content of the polymerization inhibitor (D) is 20 to 80 parts by mass per 100 parts by mass of the thiol compound (C).
[4] 상기 중합 금지제 (D)가 페놀계 중합 금지제 (D-1)인, 상기 [1] 내지 [3] 중 어느 한 항에 기재된 감광성 수지 조성물.[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polymerization inhibitor (D) is a phenolic polymerization inhibitor (D-1).
[5] 상기 광 라디칼 중합 개시제 (B)가 옥심계 광 라디칼 중합 개시제 (B1)인, 상기 [1] 내지 [4] 중 어느 한 항에 기재된 감광성 수지 조성물.[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photo-radical polymerization initiator (B) is an oxime-based photo-radical polymerization initiator (B1).
[6] 추가로 알칼리 가용성 수지 (E)를 함유하는, 상기 [1] 내지 [5]에 기재된 감광성 수지 조성물.[6] The photosensitive resin composition according to [1] to [5], further containing an alkali-soluble resin (E).
[7] 상기 [1] 내지 [6] 중 어느 한 항에 기재된 감광성 수지 조성물을 기판 상에 도포하여 수지 도막을 형성하는 공정 (1), 상기 수지 도막을 노광하는 공정 (2), 노광 후의 수지 도막을 현상하는 공정 (3)을 갖는 것을 특징으로 하는 레지스트 패턴의 형성 방법.[7] Step (1) of forming a resin coating film by applying the photosensitive resin composition according to any one of the above [1] to [6] on a substrate (1), the step of exposing the resin coating film (2), and the resin after exposure A method for forming a resist pattern, comprising the step (3) of developing a coating film.
[8] 상기 [7]에 기재된 레지스트 패턴의 형성 방법에 의해 형성한 레지스트 패턴을 마스크로 하여, 상기 기판에 대하여 도금 처리를 행하는 공정을 갖는 것을 특징으로 하는 도금 조형물의 제조 방법.[8] A method for producing a plated article, comprising a step of performing a plating treatment on the substrate using the resist pattern formed by the method of forming the resist pattern according to [7] as a mask.
본 발명은, 다크 필드 및 브라이트 필드에 있어서 넓은 공통의 노광량 여유도(EL)를 갖는 감광성 수지 조성물을 제공할 수 있다. 상기 감광성 수지 조성물을 사용하여, 브라이트 필드와 다크 필드의 양쪽에 있어서 고정밀도의 미세한 레지스트 패턴을 형성할 수 있는, 레지스트 패턴의 형성 방법을 제공할 수 있다. 상기 레지스트 패턴의 형성 방법에 의해 형성한 레지스트 패턴을 사용하여, 고정밀도의 미세한 도금 조형물을 제조할 수 있는, 도금 조형물의 제조 방법을 제공할 수 있다.The present invention can provide a photosensitive resin composition having a wide common exposure amount margin (EL) in a dark field and a bright field. Using the photosensitive resin composition, it is possible to provide a method for forming a resist pattern capable of forming a fine resist pattern with high precision in both bright fields and dark fields. It is possible to provide a method for manufacturing a plated article, capable of producing a high-precision, fine plated article by using the resist pattern formed by the method of forming the resist pattern.
도 1은, 실시예 1B, 2B 및 비교예 3B의 레지스트 패턴의 전자 현미경의 사진이다.
도 2는, EOP에 있어서의 2㎛의 1L/1S 레지스트 패턴을 마스크로 한 도금 조형물의 전자 현미경의 사진이다.1 is an electron microscope photograph of the resist patterns of Examples 1B and 2B and Comparative Example 3B.
Fig. 2 is a photograph of an electron microscope of a plated sculpture in which a 2 µm 1L/1S resist pattern is used as a mask in EOP.
[감광성 수지 조성물][Photosensitive resin composition]
본 발명의 감광성 수지 조성물은, 중합성 화합물 (A), 광 라디칼 중합 개시제 (B), 티올 화합물 (C) 및 중합 금지제 (D)를 함유하고, 상기 티올 화합물 (C)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 5 내지 50질량부, 상기 중합 금지제 (D)의 함유량이, 상기 중합성 화합물 (A) 100질량부에 대하여 1 내지 10질량부이다.The photosensitive resin composition of the present invention contains a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D), and the content of the thiol compound (C) is The content of the polymerization inhibitor (D) is 5 to 50 parts by mass per 100 parts by mass of the polymerizable compound (A) and 1 to 10 parts by mass per 100 parts by mass of the polymerizable compound (A).
본 발명의 감광성 수지 조성물은, 다크 필드 및 브라이트 필드에 있어서 넓은 공통의 EL을 갖는다.The photosensitive resin composition of the present invention has a wide common EL in a dark field and a bright field.
전술한 바와 같이, 감광성 수지 조성물이 공통의 EL이 좁으면, 브라이트 필드와 다크 필드에 있어서, 형성되는 레지스트 패턴의 정밀도에 차가 발생하기 쉬워진다. 감광성 수지 조성물이 공통의 EL이 좁아지는 이유로서, 몇 가지 생각할 수 있지만, 그 중에서도 본 발명자는, (1) 감광성 수지 조성물에 노광을 하였을 때에 발생하는 라디칼의 확산 길이가 너무 긴 것, 및 (2) 감광성 수지 조성물의 노광광에 대한 감도가 낮은 것에 착안하였다.As described above, when the common EL of the photosensitive resin composition is narrow, a difference is likely to occur in the accuracy of the formed resist pattern in the bright field and the dark field. As the reason why the common EL of the photosensitive resin composition becomes narrow, several can be considered. Among them, the inventors of the present invention include (1) that the diffusion length of radicals generated when exposed to the photosensitive resin composition is too long, and (2) ) Focused on the low sensitivity of the photosensitive resin composition to exposure light.
라디칼의 확산 길이가 길면, 감광성 수지 조성물로 형성된 레지스트 도막에 있어서의 노광광이 닿는 영역 이외에도, 노광에 의해 발생한 라디칼이 광범위하게 확산되고, 상정하였던 범위를 초과하여 라디칼 반응이 진행하게 되고, 레지스트 패턴의 정밀도가 저하된다. 이 때문에, 고정밀도의 레지스트 패턴을 형성할 수 있는 노광량 범위가 제한되어, 공통의 EL이 좁아진다고 생각된다. 라디칼 반응이 진행되는 범위 및 정도는, 라디칼의 발생량과 확산 길이에 의존한다. 라디칼의 발생량은 브라이트 필드와 다크 필드에서는 다르므로, 브라이트 필드와 다크 필드에서 레지스트 패턴의 정밀도에 차가 발생하게 된다.If the diffusion length of radicals is long, radicals generated by exposure are diffused extensively in addition to the regions exposed to exposure light in the resist coating film formed of the photosensitive resin composition, and the radical reaction proceeds beyond the expected range, and the resist pattern The precision of the is deteriorated. For this reason, it is thought that the range of the exposure amount in which a highly accurate resist pattern can be formed is limited, and the common EL is narrowed. The extent and degree to which the radical reaction proceeds depends on the amount and the diffusion length of the radical. Since the amount of radicals generated differs between the bright field and the dark field, a difference occurs in the accuracy of the resist pattern in the bright field and the dark field.
또한, 감광성 수지 조성물의 노광광에 대한 감도가 낮으면, 노광량을 증가시킬 필요가 있게 되므로, 누설광의 영향이 커진다. 이 때문에, 감도의 낮음이 공통의 EL에 영향을 미친다고 생각된다.In addition, when the sensitivity of the photosensitive resin composition to exposure light is low, it becomes necessary to increase the exposure amount, so that the influence of the leakage light increases. For this reason, it is thought that the low sensitivity affects the common EL.
그래서, 본 발명에 있어서는, 라디칼의 확산 길이를 억제하기 위해서, 감광성 수지 조성물에 중합 금지제를 일정량 첨가한다. 한편, 중합 금지제를 넣으면 감도가 대폭 내려가므로, 감도를 높이는 것이 가능한 티올 화합물, 특히 다관능 티올 화합물을 감광성 수지 조성물에 일정량 첨가한다. 즉, 중합 금지제에 의해, 라디칼의 긴 확산 길이에서 기인하는 폐해를 억제하고, 중합 금지제의 첨가에 의해 발생하는, 감도의 저하에서 기인하는 폐해를 티올 화합물에 의해 억제한다. 또한, 다관능 티올의 첨가에 의해, 기판과 레지스트 도막의 접착성이 강해지고, 레지스트 패턴의 정밀도가 보다 향상된다. 이상과 같이, 본 발명은, 중합 금지제와 티올 화합물의 복합적인 효과에 의해, 넓은 공통의 EL을 실현한 것이다.Therefore, in the present invention, in order to suppress the diffusion length of radicals, a certain amount of a polymerization inhibitor is added to the photosensitive resin composition. On the other hand, since the sensitivity is significantly lowered when a polymerization inhibitor is added, a thiol compound capable of increasing the sensitivity, particularly a polyfunctional thiol compound, is added in a certain amount to the photosensitive resin composition. That is, the polymerization inhibitor suppresses the harm caused by the long diffusion length of the radical, and the harm caused by the decrease in sensitivity caused by the addition of the polymerization inhibitor is suppressed by the thiol compound. Further, the addition of the polyfunctional thiol enhances the adhesion between the substrate and the resist coating film, and further improves the accuracy of the resist pattern. As described above, the present invention realizes a wide common EL by the complex effect of the polymerization inhibitor and the thiol compound.
본 발명의 감광성 수지 조성물이 갖는 공통의 EL은, 통상 8％ 이상, 바람직하게는 10％ 이상, 보다 바람직하게는 15％ 이상이다. 이 때문에, 본 발명의 감광성 수지 조성물을 사용하여 레지스트 패턴을 형성할 때에는, 미세한 레지스트 패턴이어도 선택할 수 있는 노광량 범위가 넓고, 레지스트 패턴의 형성이 간편하여, 목적에 따른 레지스트 패턴을 브라이트 필드 및 다크 필드의 양쪽에 있어서 용이하게 형성할 수 있다.The common EL of the photosensitive resin composition of the present invention is usually 8% or more, preferably 10% or more, and more preferably 15% or more. For this reason, when forming a resist pattern using the photosensitive resin composition of the present invention, even a fine resist pattern can be selected in a wide range of exposure doses, and formation of a resist pattern is easy, so that the resist pattern according to the purpose is bright field and dark field. It can be formed easily on both sides of.
또한, 본 명세서에서는, 2㎛ 치수의 1대1 라인 앤 스페이스(이하, 「2㎛의 1L/1S」라고 약칭함)의 레지스트 패턴의 형성에 대응하는 영역을 브라이트 필드, 2㎛ 치수의 1대3 라인 앤 스페이스(이하, 「2㎛의 1L/3S」라 약칭함)의 레지스트 패턴의 형성에 대응하는 영역을 다크 필드로 한다. 공통의 EL은, 2㎛의 1L/1S 레지스트 패턴이 최적으로 형성되는 노광량을 최적 노광량(이하, 「EOP」라고도 함)으로 하였을 때, 브라이트 필드에 있어서, 고정밀도의 미세한 레지스트 패턴을 형성할 수 있는 노광량 범위와, 다크 필드에 있어서, 고정밀도의 미세한 레지스트 패턴을 형성할 수 있는 노광량 범위가 중복되는 노광량 범위의, 상기 최적 노광량에 대한 비율을 나타낸다.In addition, in the present specification, the area corresponding to the formation of a resist pattern of a 2 μm size 1 to 1 line and space (hereinafter, abbreviated as “2 μm 1L/1S”) is a bright field, and a 2 μm size 1 unit 3 A region corresponding to the formation of a line and space (hereinafter abbreviated as "2 µm 1L/3S") resist pattern is set as a dark field. In the common EL, when the exposure amount at which the 2 μm 1L/1S resist pattern is optimally formed is the optimal exposure amount (hereinafter, also referred to as “EOP”), a high-precision, fine resist pattern can be formed in a bright field. The ratio of the exposure amount range in which there is an exposure amount range and the exposure amount range capable of forming a high-precision fine resist pattern in a dark field overlap with the optimum exposure amount.
중합성 화합물 (A)는, 노광에 의해 광 라디칼 중합 개시제로부터 발생하는 활성종에 의해 라디칼 중합하는 성분이며, 바람직하게는 1 분자 중에 적어도 1개의 에틸렌성 불포화 이중 결합을 갖는다.The polymerizable compound (A) is a component that undergoes radical polymerization by active species generated from a photoradical polymerization initiator by exposure, and preferably has at least one ethylenically unsaturated double bond per molecule.
중합성 화합물 (A)로서는, (메트)아크릴로일기를 갖는 (메트)아크릴레이트 화합물, 비닐기를 갖는 화합물이 바람직하다. 상기 (메트)아크릴레이트 화합물은 단관능성 (메트)아크릴레이트 화합물과 다관능성 (메트)아크릴레이트 화합물로 분류되지만, 어느 화합물이어도 된다.As the polymerizable compound (A), a (meth)acrylate compound having a (meth)acryloyl group and a compound having a vinyl group are preferable. The (meth)acrylate compound is classified into a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound, but any compound may be used.
상기 단관능성 (메트)아크릴레이트 화합물로서는, 예를 들어 2-히드록시에틸(메트)아크릴레이트, 2-히드록시프로필(메트)아크릴레이트, 2-히드록시부틸(메트)아크릴레이트, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, 부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 이소아밀(메트)아크릴레이트, 헥실(메트)아크릴레이트, 헵틸(메트)아크릴레이트, 옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 운데실(메트)아크릴레이트, 도데실아밀(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 옥타데실(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 테트라히드로푸르푸릴(메트)아크릴레이트, 벤질(메트)아크릴레이트, 페녹시에틸(메트)아크릴레이트, 에톡시에틸(메트)아크릴레이트, 부톡시에틸(메트)아크릴레이트, 글리세롤(메트)아크릴레이트, 에틸렌글리콜모노메틸에테르(메트)아크릴레이트, 에틸렌글리콜모노에틸에테르(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트, 메톡시에틸렌글리콜(메트)아크릴레이트, 에톡시 디에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 메톡시폴리프로필렌글리콜(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 페녹시폴리프로필렌글리콜(메트)아크릴레이트, 트리시클로[5.2.1.02,6]데카디에닐(메트)아크릴레이트, 트리시클로[5.2.1.02,6]데카닐(메트)아크릴레이트, 트리시클로[5.2.1.02,6]데세닐(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 보르닐(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 아크릴산아미드, 메타크릴산아미드, 디아세톤(메트)아크릴아미드, 이소부톡시메틸(메트)아크릴아미드, N,N-디메틸(메타)아크릴아미드, tert-옥틸(메트)아크릴아미드, 디메틸아미노에틸(메트)아크릴레이트, 디에틸아미노에틸(메트)아크릴레이트, 7-아미노-3,7-디메틸옥틸(메트)아크릴레이트 등을 들 수 있다.Examples of the monofunctional (meth)acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and methyl (meth)acrylate. )Acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, Pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth) )Acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecylamyl (meth)acrylate, lauryl (meth)acrylate , Octadecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylic Rate, butoxyethyl (meth)acrylate, glycerol (meth)acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Propylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate , Phenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, tricyclo[5.2.1.0 2,6 ] decadienyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]Decanyl(meth)acrylate, tricyclo[5.2.1.0 2,6 ]decenyl(meth)acrylate, isobornyl(meth)acrylate, bornyl(meth)acrylate, cyclohexyl(meth)acrylic Rate, acrylic acid amide, methacrylic acid amide, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N,N-dimethyl (meth) acrylamide, tert-jade Tyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, and the like.
상기 다관능성 (메트)아크릴레이트 화합물로서는, 예를 들어 트리메틸올프로판디(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 트리메틸올프로판 PO(propylene oxide) 변성 트리(메트)아크릴레이트, 테트라메틸올프로판테트라(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 부틸렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트디(메트)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트 트리(메트)아크릴레이트, 트리시클로데칸디메탄올 디(메트)아크릴레이트, 비스페놀 A의 디글리시딜에테르에 (메트)아크릴산을 부가시킨 에폭시(메트)아크릴레이트, 비스페놀 A 디(메트)아크릴로일옥시에틸에테르, 비스페놀 A 디(메트)아크릴로일옥시메틸에틸에테르, 비스페놀 A 디(메트)아크릴로일옥시에틸옥시에틸에테르, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 폴리에스테르(메트)아크릴레이트(3관능 이상), 프탈산과 에폭시아크릴레이트의 반응물 등을 들 수 있다.Examples of the polyfunctional (meth)acrylate compound include trimethylolpropanedi (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO (propylene oxide) modified tri(meth)acrylate, Tetramethylolpropane tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tris(2-hydroxyethyl) )Isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, diglycidyl of bisphenol A Epoxy (meth)acrylate obtained by adding (meth)acrylic acid to ether, bisphenol A di(meth)acryloyloxyethyl ether, bisphenol A di(meth)acryloyloxymethylethyl ether, bisphenol A di(meth)acrylic Royloxyethyloxyethyl ether, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Polyester (meth)acrylate (trifunctional or more), a reaction product of phthalic acid and epoxy acrylate, etc. are mentioned.
중합성 화합물 (A)로서, 시판되고 있는 화합물을 그대로 사용할 수 있다. 시판되고 있는 화합물로서는, 예를 들어 아로닉스 M-210, 동 M-309, 동 M-310, 동 M-320, 동 M-400, 동 M-7100, 동 M-8030, 동 M-8060, 동 M-8100, 동 M-9050, 동 M-240, 동 M-245, 동 M-6100, 동 M-6200, 동 M-6250, 동 M-6300, 동 M-6400, 동 M-6500(이상, 도아 고세(주)제), KAYARAD R-551, 동 R-712, 동 TMPTA, 동 HDDA, 동 TPGDA, 동 PEG400DA, 동 MANDA, 동 HX-220, 동 HX-620, 동 R-604, 동 DPCA-20, DPCA-30, 동 DPCA-60, 동 DPCA-120(이상, 닛폰 가야쿠(주)제), 비스코트 #295, 동 300, 동 260, 동 312, 동 335HP, 동 360, 동 GPT, 동 3PA, 동 400(이상, 오사까 유끼 가가꾸 고교(주)제) 등을 들 수 있다.As the polymerizable compound (A), a commercially available compound can be used as it is. As a commercially available compound, for example, Aronix M-210, Copper M-309, Copper M-310, Copper M-320, Copper M-400, Copper M-7100, Copper M-8030, Copper M-8060, East M-8100, East M-9050, East M-240, East M-245, East M-6100, East M-6200, East M-6250, East M-6300, East M-6400, East M-6500 ( Above, Doa Kose Co., Ltd.), KAYARAD R-551, East R-712, East TMPTA, East HDDA, East TPGDA, East PEG400DA, East MANDA, East HX-220, East HX-620, East R-604, East DPCA-20, DPCA-30, East DPCA-60, East DPCA-120 (above, manufactured by Nippon Kayaku Co., Ltd.), Viscot #295, East 300, East 260, East 312, East 335HP, East 360, The GPT, the 3PA, and the 400 (above, manufactured by Osaka Yuki Kagaku High School Co., Ltd.) are mentioned.
이들 중합성 화합물 (A)는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.These polymerizable compounds (A) may be used alone or in combination of two or more.
본 감광성 수지 조성물에 있어서의 중합성 화합물 (A)의 함유 비율은, 고형분 중, 통상 5 내지 90질량％이며, 바람직하게는 10 내지 70질량％, 보다 바람직하게는 15 내지 50질량％이다. 또한, 본 발명에 있어서 「고형분」이란, 감광성 수지 조성물에 포함되는 용제 이외의 전체 성분을 말한다.The content ratio of the polymerizable compound (A) in the present photosensitive resin composition is usually 5 to 90% by mass, preferably 10 to 70% by mass, and more preferably 15 to 50% by mass in the solid content. In addition, in the present invention, "solid content" refers to all components other than the solvent contained in the photosensitive resin composition.
광 라디칼 중합 개시제 (B)는 노광광의 조사에 의해 라디칼을 발생하고, 중합성 화합물 (A)의 라디칼 중합을 개시시키는 화합물이다.The photoradical polymerization initiator (B) is a compound that generates a radical by irradiation with exposure light and initiates radical polymerization of the polymerizable compound (A).
광중합 개시제 (B)로서는, 예를 들어 옥심계 화합물, 유기 할로겐화 화합물, 옥시디아졸 화합물, 카르보닐 화합물, 케탈 화합물, 벤조인 화합물, 아크리딘 화합물, 유기 과산화 화합물, 아조 화합물, 쿠마린 화합물, 아지드 화합물, 메탈로센 화합물, 헥사아릴비이미다졸 화합물, 유기 붕산 화합물, 디술폰산 화합물, 오늄염 화합물, 아실포스핀(옥시드) 화합물을 들 수 있다. 이들 중에서도 감도의 점에서, 옥심계 광 라디칼 중합 개시제 (B1), 특히 옥심에스테르 구조를 갖는 광 라디칼 중합 개시제가 바람직하다.As the photoinitiator (B), for example, an oxime compound, an organic halogenated compound, an oxidiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, a A zide compound, a metallocene compound, a hexaarylbiimidazole compound, an organic boric acid compound, a disulfonic acid compound, an onium salt compound, and an acylphosphine (oxide) compound. Among these, from the viewpoint of sensitivity, an oxime-based photo-radical polymerization initiator (B1), particularly a photo-radical polymerization initiator having an oxime ester structure is preferred.
옥심에스테르 구조를 갖는 광 라디칼 중합 개시제에는 옥심의 이중 결합에서 기인하는 기하 이성체가 존재할 수 있지만, 이들은 구별되지 않고, 모두 광 라디칼 중합 개시제 (B)에 포함된다.In the photo-radical polymerization initiator having an oxime ester structure, geometric isomers resulting from double bonds of oxime may exist, but these are not distinguished, and all are included in the photo-radical polymerization initiator (B).
옥심에스테르 구조를 갖는 광 라디칼 중합 개시제로서는, 예를 들어 WO2010/146883호 공보, 일본 특허 공개 제2011-132215호 공보, 일본 특허 공표 제2008-506749호 공보, 일본 특허 공표 제2009-519904 및 일본 특허 공표 제2009-519991호 공보에 기재된 광 라디칼 중합 개시제를 들 수 있다.As a photo-radical polymerization initiator having an oxime ester structure, for example, WO2010/146883, Japanese Patent Publication No. 2011-132215, Japanese Patent Publication No. 2008-506749, Japanese Patent Publication No. 2009-519904 and Japanese Patent The photo-radical polymerization initiator described in Publication No. 2009-519991 is mentioned.
옥심에스테르 구조를 갖는 광 라디칼 중합 개시제의 구체예로서는, N-벤조일옥시-1-(4-페닐술파닐페닐)부탄-1-온-2-이민, N-에톡시카르보닐옥시-1-페닐프로판-1-온-2-이민, N-벤조일옥시-1-(4-페닐술파닐페닐)옥탄-1-온-2-이민, N-아세톡시-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄-1-이민, 및 N-아세톡시-1-[9-에틸-6-{2-메틸-4-(3,3-디메틸-2,4-디옥사시클로펜타닐메틸옥시)벤조일}-9H-카르바졸-3-일]에탄-1-이민, 에타논, 1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-, 1-(O-아세틸옥심)(이르가큐어 OXE-02) 등을 들 수 있다.As specific examples of the photo-radical polymerization initiator having an oxime ester structure, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2 -Methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2) ,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Bazol-3-yl]-, 1-(O-acetyloxime) (Irgacure OXE-02), etc. are mentioned.
이들 광중합 개시제 (B)는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.These photoinitiators (B) may be used individually by 1 type, and may use 2 or more types together.
본 감광성 수지 조성물에 있어서의 광중합 개시제 (B)의 함유량은, 중합성 화합물 (A) 100에 대하여 통상 1 내지 40질량부이며, 바람직하게는 3 내지 35 질량, 보다 바람직하게는 5 내지 30질량부이다. 광 라디칼 중합 개시제 (B)의 함유량이 상기 범위 내이면, 적합한 라디칼량이 얻어져, 우수한 해상도가 얻어진다.The content of the photopolymerization initiator (B) in the photosensitive resin composition is usually 1 to 40 parts by mass, preferably 3 to 35 parts by mass, more preferably 5 to 30 parts by mass based on 100 of the polymerizable compound (A). to be. When the content of the photo-radical polymerization initiator (B) is within the above range, a suitable amount of radicals is obtained, and excellent resolution is obtained.
티올 화합물 (C)는 전술한 바와 같이, 감광성 수지 조성물의 감도를 향상시키고, 중합 금지제 (D)와의 복합적인 효과에 의해, 브라이트 필드 및 다크 필드의 양쪽에 있어서의 넓은 공통의 EL의 실현에 기여하는 성분이다.As described above, the thiol compound (C) improves the sensitivity of the photosensitive resin composition, and by the combined effect with the polymerization inhibitor (D), it is possible to realize a wide common EL in both the bright field and the dark field. It is a contributing ingredient.
티올 화합물 (C)는 단관능 티올 화합물 및 다관능 티올 화합물 중 어느 것이어도 되지만, 감광성 수지 조성물의 노광광에 대한 감도를 의해 높이는 관점에서, 다관능 티올 화합물 (C-1)인 것이 바람직하다.The thiol compound (C) may be a monofunctional thiol compound and a polyfunctional thiol compound, but from the viewpoint of increasing the sensitivity of the photosensitive resin composition to exposure light, it is preferably a polyfunctional thiol compound (C-1).
단관능 티올 화합물이란, 티올기(머캅토기)를 분자 내에 1개 갖는 화합물이다. 단관능 티올 화합물로서는, 예를 들어 스테아릴-3-머캅토프로피오네이트 등을 들 수 있다.The monofunctional thiol compound is a compound having one thiol group (mercapto group) in a molecule. As a monofunctional thiol compound, stearyl-3-mercaptopropionate etc. are mentioned, for example.
다관능 티올 화합물 (C-1)이란, 티올기(머캅토기)를 분자 내에 2개 이상 갖는 화합물이다. 다관능 티올 화합물로서는, 분자량 100 이상의 저분자 화합물이 바람직하고, 구체적으로는 분자량 100 내지 1,500인 것이 보다 바람직하고, 150 내지 1,000이 더욱 바람직하다.The polyfunctional thiol compound (C-1) is a compound having two or more thiol groups (mercapto groups) in a molecule. As the polyfunctional thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 are still more preferable.
다관능 티올 화합물 (C-1)의 관능기수로서는, 2 내지 10관능이 바람직하고, 2 내지 8관능이 보다 바람직하고, 2 내지 4관능이 더욱 바람직하다. 관능기수가 커지면 막 강도가 우수한 한편, 관능기수가 작으면 보존 안정성이 우수하다. 상기 범위의 경우, 이들을 양립시킬 수 있다.As the number of functional groups of the polyfunctional thiol compound (C-1), 2 to 10 functions are preferable, 2 to 8 functions are more preferable, and 2 to 4 functions are still more preferable. When the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the above range, these can be made compatible.
다관능 티올 화합물 (C-1)로서는, 지방족 다관능 티올 화합물이 바람직하다. 지방족 다관능 티올 화합물의 바람직한 예로서는, 지방족 탄화수소기와, -O-, -C(=O)-의 조합을 포함하는 화합물이며, 지방족 탄화수소기의 수소 원자의 적어도 2개가 티올기로 치환된 화합물이 예시된다.As the polyfunctional thiol compound (C-1), an aliphatic polyfunctional thiol compound is preferable. Preferred examples of the aliphatic polyfunctional thiol compound include a compound containing an aliphatic hydrocarbon group and a combination of -O-, -C(=O)-, and a compound in which at least two hydrogen atoms of the aliphatic hydrocarbon group are substituted with a thiol group is exemplified. .
다관능 티올 화합물 (C-1)에 있어서의 티올기는, 제1급 티올기여도, 제2급 티올기여도, 제3급 티올기여도 되지만, 감도 및 내약품성의 관점에서, 제1급 또는 제2급 티올기인 것이 바람직하고, 제2급 티올기인 것이 보다 바람직하다. 또한, 보존 안정성의 관점에서는, 제2급 또는 제3급 티올기인 것이 바람직하고, 제2급 티올기인 것이 보다 바람직하다.The thiol group in the polyfunctional thiol compound (C-1) may be a primary thiol group, a secondary thiol group, or a tertiary thiol group, but from the viewpoint of sensitivity and chemical resistance, the first or secondary thiol It is preferable that it is a group, and it is more preferable that it is a secondary thiol group. Moreover, from a viewpoint of storage stability, it is preferable that it is a secondary or tertiary thiol group, and it is more preferable that it is a secondary thiol group.
지방족 다관능 티올 화합물로서는, 펜타에리트리톨테트라키스(3-머캅토부티레이트), 1,4-비스(3-머캅토부티릴옥시)부탄, 1,3,5-트리스(3-머캅토부티릴옥시에틸)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 트리메틸올프로판트리스(3-머캅토부티레이트), 트리메틸올에탄트리스(3-머캅토부티레이트), 트리메틸올프로판트리스(3-머캅토프로피오네이트), 트리스[(3-머캅토프로피오닐옥시)에틸]이소시아누레이트, 펜타에리트리톨테트라키스(3-머캅토프로피오네이트), 테트라에틸렌글리콜비스(3-머캅토프로피오네이트) 및 디펜타에리트리톨헥사키스(3-머캅토프로피오네이트) 등을 들 수 있고, 이들 중에서도, 펜타에리트리톨테트라키스(3-머캅토부티레이트), 1,4-비스(3-머캅토부티릴옥시)부탄 및 1,3,5-트리스(3-머캅토부티릴옥시에틸)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온 등이 보다 바람직하다.As aliphatic polyfunctional thiol compounds, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl) Oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptobutyrate), trimethylolethantris(3-mercapto) Butyrate), trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), Tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto propionate), and the like. Among these, pentaerythritol tetrakis (3-mercapto butyrate) , 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6( 1H, 3H, 5H)-trione and the like are more preferable.
지방족 다관능 티올 화합물 (C-1)의 시판품으로서는, 예를 들어 카렌즈 MT-PE-1, 카렌즈 MT-BD-1, 카렌즈 MT-NR-1, TPMB, TEMB(이상, 쇼와 덴코(주)제), TMMP, TEMPIC, PEMP, EGMP-4 및 DPMP(이상, 사까이 가가꾸 고교(주)제) 등을 들 수 있다.As commercially available products of the aliphatic polyfunctional thiol compound (C-1), for example, Carens MT-PE-1, Carens MT-BD-1, Carens MT-NR-1, TPMB, TEMB (above, Showa Denko Co., Ltd.), TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (above, manufactured by Sakai Chemical Co., Ltd.), etc. are mentioned.
이들 티올 화합물 (C)는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.These thiol compounds (C) may be used alone or in combination of two or more.
중합 금지제 (D)와의 복합적인 효과에 의해, 넓은 공통의 EL을 실현하는 관점에서, 티올 화합물 (C)의 함유량은 전술한 바와 같이, 중합성 화합물 (A) 100질량부에 대하여 5 내지 50질량부이며, 바람직하게는 5 내지 35 질량, 보다 바람직하게는 5 내지 25질량부이다.From the viewpoint of realizing a wide common EL due to the complex effect with the polymerization inhibitor (D), the content of the thiol compound (C) is 5 to 50 per 100 parts by mass of the polymerizable compound (A), as described above. It is a mass part, Preferably it is 5 to 35 mass, More preferably, it is 5 to 25 mass parts.
중합 금지제 (D)는 전술한 바와 같이, 라디칼의 확산 길이를 억제하고, 티올 화합물 (C)와의 복합적인 효과에 의해, 넓은 공통의 EL의 실현에 기여하는 성분이다. 또한, 중합 금지제 (D)는 감광성 수지 조성물의 보존 안정성의 향상에도 기여할 수 있다.As described above, the polymerization inhibitor (D) is a component that suppresses the diffusion length of radicals and contributes to the realization of a wide common EL by a complex effect with the thiol compound (C). Moreover, the polymerization inhibitor (D) can also contribute to the improvement of the storage stability of a photosensitive resin composition.
중합 금지제 (D)로서는, 예를 들어 히드로퀴논, 히드로퀴논의 모노에스테르화물, N-니트로소디페닐아민, 벤조퀴논, 페노티아진, p-메톡시페놀, p-t-부틸카테콜, N-페닐나프틸아민, 2,6-디-t-부틸-p-메틸페놀, 클로라닐, 피로갈롤을 들 수 있다.As a polymerization inhibitor (D), for example, hydroquinone, monoester product of hydroquinone, N-nitrosodiphenylamine, benzoquinone, phenothiazine, p-methoxyphenol, pt-butylcatechol, N-phenylnaphthyl Amine, 2,6-di-t-butyl-p-methylphenol, chloranyl, and pyrogallol.
중합 금지제 (D)로서는, 히드로퀴논, p-메톡시페놀, 카테콜 등의 페놀계 중합 금지제 (D-1)이 바람직하다.As the polymerization inhibitor (D), a phenolic polymerization inhibitor (D-1) such as hydroquinone, p-methoxyphenol, and catechol is preferable.
중합 금지제 (D)의 시판품으로서는, 예를 들어 Irganox 1010(BASF사제), 키노 파워 QS20(가와사키 가세이 고교(주)제) 등을 들 수 있다.As a commercial item of the polymerization inhibitor (D), Irganox 1010 (manufactured by BASF), Kino Power QS20 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), etc. are mentioned, for example.
이들 중합 금지제 (D)는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.These polymerization inhibitors (D) may be used alone or in combination of two or more.
티올 화합물 (C)와의 복합적인 효과에 의해, 넓은 공통의 EL을 실현하는 관점에서, 중합 금지제 (D)의 함유량은 전술한 바와 같이, 중합성 화합물 (A) 100질량부에 대하여 1 내지 10질량부이며, 바람직하게는 3 내지 8질량부, 보다 바람직하게는 4 내지 6질량부이다.From the viewpoint of realizing a wide common EL due to the complex effect with the thiol compound (C), the content of the polymerization inhibitor (D) is 1 to 10 per 100 parts by mass of the polymerizable compound (A), as described above. It is a mass part, Preferably it is 3-8 mass parts, More preferably, it is 4-6 mass parts.
본 발명의 감광성 수지 조성물은, 알칼리 가용성 수지 (E)를 함유하는 것이 바람직하다. 감광성 수지 조성물이 알칼리 가용성 수지 (E)를 함유하면, 레지스트에 도금액에 대한 내성을 부여할 수 있고, 또한 현상을 알칼리 현상액으로 행할 수 있다.It is preferable that the photosensitive resin composition of this invention contains an alkali-soluble resin (E). When the photosensitive resin composition contains an alkali-soluble resin (E), resistance to a plating solution can be imparted to the resist, and further development can be performed with an alkali developer.
알칼리 가용성 수지 (E)는, 목적으로 하는 현상 처리가 가능한 정도로 알칼리성의 현상액에 용해되는 성질을 갖는 수지이다. 알칼리 가용성 수지 (E)로서는, 예를 들어 일본 특허 공개 제2008-276194호 공보, 일본 특허 공개 제2003-241372호 공보, 일본 특허 공표 제2009-531730호 공보, WO2010/001691호 공보, 일본 특허 공개 제2011-123225호 공보, 일본 특허 공개 제2009-222923호 공보 및 일본 특허 공개 제2006-243161호 공보 등에 기재된 공지된 알칼리 가용성 수지를 들 수 있다. 보다 구체적으로는, 알칼리 가용성 수지 (E)로서는, 예를 들어 (메트)아크릴산, 말레산, p-히드록시스티렌, 이소프로페닐페놀 및 히드록시페닐(메트)아크릴레이트 등의 산성 관능기를 갖는 단량체 유래의 구조 단위, 그리고 스티렌, N-페닐말레이미드, n-부틸(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트 및 이소보르닐비닐에테르 등의 기타 단량체 유래의 구조 단위를 갖는 수지를 들 수 있다.The alkali-soluble resin (E) is a resin having a property of dissolving in an alkaline developing solution to the extent that a target development treatment is possible. As the alkali-soluble resin (E), for example, Japanese Patent Laid-Open No. 2008-276194, Japanese Patent Laid-Open No. 2003-241372, Japanese Patent Laid-Open No. 2009-531730, WO2010/001691, Japanese Patent Laid-Open The known alkali-soluble resins described in 2011-123225 A, JP 2009-222923 A, JP 2006-243161 A, and the like are mentioned. More specifically, examples of the alkali-soluble resin (E) include monomers having acidic functional groups such as (meth)acrylic acid, maleic acid, p-hydroxystyrene, isopropenylphenol, and hydroxyphenyl (meth)acrylate. And resins having structural units derived from other monomers such as styrene, N-phenylmaleimide, n-butyl (meth)acrylate, isobornyl (meth)acrylate and isobornyl vinyl ether. I can.
알칼리 가용성 수지 (E)의 겔 투과 크로마토그래피에 의해 측정된 폴리스티렌 환산의 중량 평균 분자량(Mw)은, 통상 1,000 내지 1,000,000, 바람직하게는 2,000 내지 50,000, 보다 바람직하게는 3,000 내지 20,000의 범위에 있다.The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the alkali-soluble resin (E) is usually in the range of 1,000 to 1,000,000, preferably 2,000 to 50,000, and more preferably 3,000 to 20,000.
알칼리 가용성 수지 (E)는, 레지스트의 도금액 내성이 향상되는 점에서, 페놀성 수산기를 갖는 것이 바람직하다.It is preferable that the alkali-soluble resin (E) has a phenolic hydroxyl group from the viewpoint of improving the resistance of the resist to the plating solution.
알칼리 가용성 수지 (E)는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.Alkali-soluble resin (E) may be used individually by 1 type, and may use 2 or more types together.
알칼리 가용성 수지 (E)의 함유량은, 중합성 화합물 (A) 100질량부에 대하여 통상 50 내지 300질량부, 바람직하게는 100 내지 250질량부이다. 알칼리 가용성 수지의 함유량이 상기 범위에 있으면, 도금액 내성이 우수한 레지스트의 형성이 가능해진다.The content of the alkali-soluble resin (E) is usually 50 to 300 parts by mass, preferably 100 to 250 parts by mass per 100 parts by mass of the polymerizable compound (A). When the content of the alkali-soluble resin is in the above range, it becomes possible to form a resist having excellent resistance to plating solution.
본 발명의 감광성 수지 조성물은, 그 밖의 성분으로서, 용제, 계면 활성제, 접착 보조제, 증감제, 무기 필러 등을, 본 발명의 목적 및 특성을 손상시키지 않는 범위에서 함유해도 된다.The photosensitive resin composition of the present invention may contain, as other components, a solvent, a surfactant, an adhesion aid, a sensitizer, an inorganic filler, and the like within a range that does not impair the object and properties of the present invention.
본 발명의 감광성 수지 조성물은 용제를 함유함으로써, 취급성이 향상되거나, 점도의 조절이 용이해지거나, 보존 안정성이 향상되거나 한다.When the photosensitive resin composition of the present invention contains a solvent, the handling property is improved, the viscosity is easily adjusted, or the storage stability is improved.
용제로서는,As a solvent,
메탄올, 에탄올, 프로필렌글리콜 등의 알코올류;Alcohols such as methanol, ethanol, and propylene glycol;
테트라히드로푸란, 디옥산 등의 환상 에테르류;Cyclic ethers such as tetrahydrofuran and dioxane;
에틸렌글리콜, 프로필렌글리콜 등의 글리콜류;Glycols such as ethylene glycol and propylene glycol;
에틸렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르 등의 알킬렌글리콜모노알킬에테르류;Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether;
에틸렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트 등의 알킬렌글리콜모노알킬에테르아세테이트류;Alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;
톨루엔, 크실렌 등의 방향족 탄화수소류;Aromatic hydrocarbons such as toluene and xylene;
아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논, 4-히드록시-4-메틸-2-펜타논 등의 케톤류;Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;
아세트산에틸, 아세트산부틸, 에톡시아세트산에틸, 히드록시아세트산에틸, 2-히드록시프로피온산에틸, 2-히드록시-2-메틸프로피온산에틸, 2-히드록시-3-메틸부탄산메틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산메틸, 락트산에틸 등의 에스테르류;Ethyl acetate, butyl acetate, ethyl ethoxy acetate, ethyl hydroxyacetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy Esters such as methyl propionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl lactate;
N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸포름아닐리드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 디메틸술폭시드, 벤질에틸에테르, 디헥실에테르, 아세토닐아세톤, 이소포론, 카프로산, 카프릴산, 1-옥탄올, 1-노난올, 벤질알코올, 아세트산벤질, 벤조산에틸, 옥살산디에틸, γ-부티로락톤, 탄산에틸렌, 탄산프로필렌, 페닐셀로솔브아세테이트 등을 들 수 있다.N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, di Hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, γ-butyrolactone, ethylene carbonate, carbonic acid Propylene, phenyl cellosolve acetate, and the like.
용제는 1종 단독으로 사용해도 되고, 2종 이상을 병용해도 된다.Solvents may be used alone or in combination of two or more.
용제의 함유량은, 막 두께 0.1 내지 100㎛의 레지스트 패턴을 형성하는 경우, 본 감광성 수지 조성물의 고형분이 5 내지 80질량％가 되는 양으로 할 수 있다.The content of the solvent may be an amount such that the solid content of the photosensitive resin composition is 5 to 80% by mass when forming a resist pattern having a film thickness of 0.1 to 100 µm.
본 발명의 감광성 수지 조성물은, 상기 성분을 균일하게 혼합함으로써 제조할 수 있다.The photosensitive resin composition of the present invention can be produced by uniformly mixing the above components.
[레지스트 패턴의 형성 방법][Method of forming resist pattern]
본 발명의 레지스트 패턴 형성 방법은, 전술한 감광성 수지 조성물을 기판 상에 도포하여 수지 도막을 형성하는 공정 (1), 상기 수지 도막을 노광하는 공정 (2), 노광 후의 수지 도막을 현상하는 공정 (3)을 갖는 것을 특징으로 한다.The resist pattern formation method of the present invention includes a step (1) of applying the above-described photosensitive resin composition on a substrate to form a resin coating film, a step of exposing the resin coating film (2), and a step of developing the exposed resin coating film ( It is characterized by having 3).
공정 (1)에서는, 상기 감광성 수지 조성물을 기판 상에 도포하여 수지 도막을 형성한다.In step (1), the photosensitive resin composition is applied on a substrate to form a resin coating film.
기판으로서는, 상기 수지 도막을 형성할 수 있는 기판이면 특별히 제한은 없고, 예를 들어 반도체 기판, 유리 기판, 실리콘 기판 및 반도체판, 유리판, 실리콘판의 표면에 각종 금속막 등을 마련하여 형성되는 기판 등을 들 수 있다. 기판의 형상에는 특별히 제한은 없다. 평판상이어도 실리콘 웨이퍼와 같이 평판에 오목부(구멍)를 마련하여 이루어지는 형상이어도 된다. 오목부를 구비하고, 또한 표면에 구리막을 갖는 기판의 경우, TSV 구조와 같이, 그 오목부의 저부에 구리막이 마련되어도 된다.The substrate is not particularly limited as long as it is a substrate on which the resin coating film can be formed, and for example, a semiconductor substrate, a glass substrate, a silicon substrate, and a substrate formed by providing various metal films on the surface of a semiconductor plate, a glass plate, or a silicon plate. And the like. There is no particular limitation on the shape of the substrate. It may be a flat plate shape or a shape formed by providing recesses (holes) in the flat plate like a silicon wafer. In the case of a substrate having a concave portion and a copper film on its surface, a copper film may be provided at the bottom of the concave portion, as in the TSV structure.
감광성 수지 조성물의 도포 방법으로서는, 특별히 한정되지 않고, 예를 들어, 스프레이법, 롤 코팅법, 스핀 코팅법, 슬릿 다이 도포법, 바 도포법, 잉크젯법을 채용할 수 있고, 특히 스핀 코팅법이 바람직하다. 스핀 코팅법의 경우, 회전 속도는 통상은 800 내지 3000rpm, 바람직하게는 800 내지 2000rpm이며, 회전 시간은 통상은 1 내지 300초간, 바람직하게는 5 내지 200초이다. 감광성 수지 조성물을 스핀 코팅한 후에는, 예를 들어 50 내지 250℃에서 1 내지 30분간 정도, 얻어진 도막을 가열 건조시킨다.The method of applying the photosensitive resin composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet method can be employed. In particular, the spin coating method is desirable. In the case of the spin coating method, the rotation speed is usually 800 to 3000 rpm, preferably 800 to 2000 rpm, and the rotation time is usually 1 to 300 seconds, preferably 5 to 200 seconds. After spin-coating the photosensitive resin composition, for example, at 50 to 250° C. for about 1 to 30 minutes, the obtained coating film is heated and dried.
수지 도막의 막 두께는 일반적으로는 0.1 내지 300㎛, 바람직하게는 1 내지 100㎛이며, 도금 조형물이 배선일 경우에는, 통상 0.1 내지 50㎛, 도금 조형물이 범프 전극일 경우에는, 통상 1 내지 300㎛이다. 수지 도막의 막 두께는 박막일수록, 산소 저해의 영향이 현저하게 나타나므로, 도금 조형물을 제조하는 경우, 막 두께는 상술한 범위로 하는 것이 바람직하다.The film thickness of the resin coating film is generally 0.1 to 300 μm, preferably 1 to 100 μm, and when the plated object is a wiring, usually 0.1 to 50 μm, and when the plated object is a bump electrode, it is usually 1 to 300 μm to be. As the film thickness of the resin coating film is thinner, the influence of oxygen inhibition is remarkably exhibited. Therefore, in the case of manufacturing a plated article, the film thickness is preferably within the above-described range.
공정 (2)에서는, 상기 수지 도막을 노광한다. 즉, 공정 (3)에 있어서 레지스트 패턴이 얻어지도록 상기 수지 도막을 선택적으로 노광한다.In step (2), the resin coating film is exposed. That is, in step (3), the resin coating film is selectively exposed so that a resist pattern is obtained.
선택적인 노광은 통상, 원하는 포토마스크를 통해, 예를 들어 콘택트 얼라이너, 스테퍼 또는 스캐너를 사용하여, 상기 도막에 대하여 노광을 행한다. 노광광으로서는, 통상 파장 200 내지 500nm의 광(예: i선(365nm))을 사용한다. 노광량은 도막 내의 성분의 종류, 배합량, 도막의 두께 등에 따라서 다르지만, 노광광에 i선을 사용하는 경우, 통상 1 내지 10,000mJ/cm2이다.In the selective exposure, exposure is usually performed on the coating film through a desired photomask, for example, using a contact aligner, a stepper or a scanner. As the exposure light, light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used. The exposure amount differs depending on the type of component in the coating film, the compounding amount, the thickness of the coating film, and the like, but when an i-line is used for exposure light, it is usually 1 to 10,000 mJ/cm 2 .
수지 도막의 형성에 사용된 감광성 수지 조성물은, 전술한 바와 같이, 다크 필드 및 브라이트 필드의 양쪽에 있어서 넓은 공통의 EL을 갖는 점에서, 공정 (2)에 있어서 브라이트 필드 및 다크 필드를 갖는 미세한 레지스트 패턴을 형성하는 경우에도, 목적을 따른 레지스트 패턴을 양호하게 형성할 수 있다.As described above, the photosensitive resin composition used for forming the resin coating film has a wide common EL in both the dark field and the bright field, and thus a fine resist having a bright field and a dark field in the step (2). Even in the case of forming a pattern, a resist pattern according to the purpose can be formed satisfactorily.
또한, 노광 후에 가열 처리를 행할 수도 있다. 노광 후의 가열 처리의 조건은, 수지 도막 내의 성분의 종류, 배합량, 도막의 두께 등에 의해 적절히 결정되지만, 통상 70 내지 180℃, 1 내지 60분이다.Moreover, heat treatment can also be performed after exposure. The conditions of the heat treatment after exposure are appropriately determined depending on the type, amount of the components in the resin coating film, the thickness of the coating film, and the like, but are usually 70 to 180°C and 1 to 60 minutes.
공정 (3)에서는, 노광 후의 수지 도막을 현상한다. 이에 의해 레지스트 패턴이 형성된다.In step (3), the resin coating film after exposure is developed. Thereby, a resist pattern is formed.
현상액으로서는, 예를 들어 수산화나트륨, 수산화칼륨, 탄산나트륨, 규산나트륨, 메타규산나트륨, 암모니아수, 에틸아민, n-프로필아민, 디에틸아민, 디-n-프로필아민, 트리에틸아민, 메틸디에틸아민, 디메틸에탄올아민, 트리에탄올아민, 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 피롤, 피페리딘, 1,8-디아자비시클로[5.4.0]-7-운데센, 1,5-디아자비시클로[4.3.0]-5-노난의 수용액을 사용할 수 있다. 또한, 상기 알칼리류의 수용액에 메탄올, 에탄올 등의 수용성 유기 용제나 계면 활성제를 적당량 첨가한 수용액을 현상액으로서 사용할 수도 있다.As a developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5- An aqueous solution of diazabicyclo[4.3.0]-5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution may be used as a developer.
현상 시간은 조성물 중의 각 성분의 종류, 배합 비율, 도막의 두께 등에 따라서 다르지만, 통상 30 내지 600초이다. 현상의 방법은 액고임(液盛)법, 디핑법, 패들법, 스프레이법, 샤워 현상법 등 중 어느 것이어도 된다.The development time varies depending on the kind of each component in the composition, the blending ratio, the thickness of the coating film, and the like, but is usually 30 to 600 seconds. The developing method may be any of a liquid pool method, a dipping method, a paddle method, a spray method, a shower developing method, and the like.
상기와 같이 제작된 레지스트 패턴에 대하여, 용도에 따라서 또한, 추가의 노광(이하 「후노광」이라고 함)이나 가열을 행함으로써 레지스트 패턴을 더욱 경화시킬 수 있다.The resist pattern produced as described above can be further cured by performing additional exposure (hereinafter referred to as "post-exposure") or heating depending on the application.
후노광은 상기 노광과 마찬가지의 방법으로 행할 수 있다. 노광량은 특별히 한정되지 않지만, 고압 수은등 사용의 경우, 100 내지 10,000mJ/cm2가 바람직하다. 가열에 대하여는, 핫 플레이트, 오븐 등의 가열 장치를 사용하여, 소정의 온도, 예를 들어 60 내지 200℃에서 소정의 시간, 예를 들어 핫 플레이트 상이면 5 내지 30분간, 오븐 내에서는 5 내지 60분간 가열 처리를 하면 된다. 이 후처리에 의해, 더욱 양호한 특성을 갖는 패턴의 경화막을 얻을 수 있다.Post-exposure can be performed by a method similar to the above-described exposure. The exposure amount is not particularly limited, but in the case of using a high-pressure mercury lamp, 100 to 10,000 mJ/cm 2 is preferable. For heating, using a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 60 to 200°C, for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 5 to 60 minutes in an oven. Just heat treatment. By this post-treatment, a patterned cured film having more favorable characteristics can be obtained.
레지스트 패턴은 유수 등에 의해 세정해도 된다. 그 후, 에어건 등을 사용하여 풍건하거나, 핫 플레이트나 오븐 등의 가열 하에서 건조시켜도 된다.The resist pattern may be cleaned with running water or the like. After that, it may be air-dried using an air gun or the like, or may be dried under heating such as a hot plate or an oven.
[도금 조형물의 제조 방법][Manufacturing method of plated sculpture]
본 발명의 도금 조형물의 제조 방법은, 전술한 레지스트 패턴의 형성 방법에 의해 형성한 레지스트 패턴을 마스크로 하여, 상기 기판에 대하여 도금 처리를 행하는 공정을 갖는 것을 특징으로 한다.A method of manufacturing a plated article of the present invention is characterized by including a step of performing a plating treatment on the substrate using a resist pattern formed by the above-described method of forming a resist pattern as a mask.
상기 도금 조형물로서는, 범프, 배선 등을 들 수 있다.Examples of the plated sculpture include bumps and wiring.
레지스트 패턴의 형성은 전술한 레지스트 패턴의 형성 방법을 따라서 행한다.The resist pattern is formed according to the method of forming the resist pattern described above.
도금 처리로서는, 전해 도금 처리, 무전해 도금 처리 및 용융 도금 처리 등의 습식 도금 처리, 화학 기층 증착 및 스퍼터 등의 건식 도금 처리를 들 수 있다. 웨이퍼 레벨에서의 가공에 있어서의 배선이나 접속 단자를 형성하는 경우, 도금 처리는 통상, 전해 도금 처리에 의해 행해진다.Examples of the plating treatment include wet plating treatment such as electrolytic plating treatment, electroless plating treatment, and hot dip plating treatment, and dry plating treatment such as chemical substrate deposition and sputtering. In the case of forming wirings or connection terminals in processing at the wafer level, the plating treatment is usually performed by electrolytic plating treatment.
전해 도금 처리를 행하기 전에, 레지스트 패턴의 내벽 표면과 도금액의 친화성을 높이기 위해서, 레지스트 패턴의 내벽 표면에 애싱 처리, 플럭스 처리 및 디스미어 처리 등의 전처리를 행할 수 있다.Before performing the electroplating treatment, in order to increase the affinity between the surface of the inner wall of the resist pattern and the plating solution, pretreatment such as an ashing treatment, a flux treatment, and a desmear treatment may be performed on the surface of the inner wall of the resist pattern.
전해 도금 처리의 경우, 스퍼터 또는 무전해 도금 처리에 의해 레지스트 패턴 내벽에 형성한 층을 시드층으로서 사용할 수 있고, 또한 표면에 금속막을 갖는 기판을 기판에 사용하는 경우에는, 상기 금속막을 시드층으로서 사용할 수도 있다.In the case of electrolytic plating treatment, a layer formed on the inner wall of the resist pattern by sputtering or electroless plating treatment can be used as a seed layer, and when a substrate having a metal film on its surface is used for the substrate, the metal film is used as a seed layer. You can also use it.
시드층을 형성하기 전에 배리어층을 형성해도 되고, 시드층을 배리어층으로서 사용할 수도 있다.Before forming the seed layer, a barrier layer may be formed, or the seed layer may be used as a barrier layer.
전해 도금 처리에 사용되는 도금액으로서는, 예를 들어 황산구리 또는 피로인산구리 등을 포함하는 구리 도금액; 시안화금칼륨을 포함하는 금 도금액 처리; 그리고 황산니켈 또는 탄산니켈을 포함하는 니켈 도금액을 들 수 있다.Examples of the plating liquid used in the electrolytic plating treatment include copper plating liquid containing copper sulfate or copper pyrophosphate; Gold plating solution treatment containing gold potassium cyanide; And a nickel plating solution containing nickel sulfate or nickel carbonate can be mentioned.
전해 도금 처리의 조건은 도금액의 종류 등에 의해 적절히 선택할 수 있고, 예를 들어 황산구리를 포함하는 전해 도금 처리의 경우, 통상, 온도 10 내지 90℃, 전류 밀도 0.1 내지 100A/dm2이다.Conditions for the electrolytic plating treatment can be appropriately selected depending on the type of the plating solution, for example, in the case of the electrolytic plating treatment containing copper sulfate, the temperature is usually 10 to 90°C and the current density is 0.1 to 100 A/dm 2 .
도금 처리는 다른 도금 처리를 순차로 행할 수 있다. 예를 들어, 처음에 구리 도금 처리를 행하고, 다음에 니켈 도금 처리를 행하고, 다음에 용융 땜납 도금 처리를 행함으로써, 땜납 구리 필러 범프를 형성할 수 있다.As for the plating treatment, other plating treatments can be sequentially performed. For example, a solder copper filler bump can be formed by performing a copper plating treatment first, then a nickel plating treatment, and then a hot-dip solder plating treatment.
도금 조형물의 두께는 그 용도에 따라서 다르지만, 예를 들어 범프 전극의 경우, 통상 1 내지 300㎛이며, 배선의 경우, 통상 0.1 내지 50㎛이다.Although the thickness of the plated sculpture varies depending on its application, for example, the bump electrode is usually 1 to 300 µm, and the wiring is usually 0.1 to 50 µm.
상기 레지스트 패턴의 형성 방법은, 전술한 감광성 수지 조성물을 사용하여 레지스트 패턴을 형성하는 점에서, 미세한 레지스트 패턴이어도, 목적을 따른 레지스트 패턴을 용이하게 형성할 수 있다. 이 때문에, 상술한 레지스트 패턴 형성 방법에 의해 형성한 레지스트 패턴을 사용하는 본 발명의 도금 조형물의 제조 방법에 있어서는, 미세한 도금 조형물을 고정밀도로 간편하게 제조할 수 있다.In the method of forming the resist pattern, since the resist pattern is formed using the photosensitive resin composition described above, even if it is a fine resist pattern, a resist pattern according to the purpose can be easily formed. For this reason, in the method of manufacturing a plated article of the present invention using a resist pattern formed by the above-described resist pattern forming method, a fine plated article can be easily manufactured with high precision.
실시예Example
이하, 본 발명을 실시예에 기초하여 더욱 구체적으로 설명하지만, 본 발명은 이들 실시예에 한정되지 않는다. 이하의 실시예 등의 기재에 있어서, 「부」는 「질량부」의 의미로 사용한다.Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, "part" is used in the sense of "mass part".
알칼리 가용성 수지의 중량 평균 분자량(Mw)은, 하기 조건에서 겔 투과 크로마토그래피법에 있어서의 폴리스티렌 환산에 의해 산출한 값이다.The weight average molecular weight (Mw) of an alkali-soluble resin is a value calculated by polystyrene conversion in a gel permeation chromatography method under the following conditions.
·칼럼: 도소 가부시키가이샤제 칼럼의 TSK-M 및 TSK2500을 직렬로 접속.Column: TSK-M and TSK2500 of the Tosoh Corporation column are connected in series.
·용매: 테트라히드로푸란Solvent: tetrahydrofuran
·칼럼 온도: 40℃·Column temperature: 40℃
·검출 방법: 굴절률법·Detection method: refractive index method
·표준 물질: 폴리스티렌·Standard material: Polystyrene
·GPC 장치: 도소 가부시키가이샤제, 장치명 「HLC-8220-GPC」GPC device: manufactured by Tosoh Corporation, device name "HLC-8220-GPC"
<감광성 수지 조성물의 제조><Production of photosensitive resin composition>
[실시예 1A 내지 8A 및 비교예 1A 내지 7A][Examples 1A to 8A and Comparative Examples 1A to 7A]
용제로서 프로필렌글리콜모노메틸에테르아세테이트를 사용하여, 하기 표 1에 나타내는 양의 각 성분을 상기 용제에, 고형분 농도가 55질량％가 되도록 첨가하여 혼합하고, 캡슐 필터(구멍 직경 3㎛)로 여과하여, 실시예 1A 내지 8A 및 비교예 1A 내지 7A의 감광성 수지 조성물을 제조하였다. 또한, 표 1 중에 나타내는 각 성분의 상세한 것은 이하와 같다.Using propylene glycol monomethyl ether acetate as a solvent, each component in the amount shown in Table 1 below was added to the solvent so as to have a solid content concentration of 55% by mass, mixed, and filtered through a capsule filter (pore diameter 3 μm). , Examples 1A to 8A and Comparative Examples 1A to 7A photosensitive resin compositions were prepared. In addition, the details of each component shown in Table 1 are as follows.
중합성 화합물 (A1): 폴리에스테르아크릴레이트(제품명 「아로닉스 M-8060」, 도아 고세(주)제)Polymerizable compound (A1): Polyester acrylate (product name "Aronix M-8060", manufactured by Toa Kose Co., Ltd.)
광중합 개시제 (B1): 하기 식 (B1)에 나타내는 화합물Photopolymerization initiator (B1): a compound represented by the following formula (B1)
광중합 개시제 (B2): 2,4,6-트리메틸벤조일디페닐포스핀옥시드Photoinitiator (B2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide
티올 화합물 (C1): 펜타에리트리톨테트라키스(3-머캅토부티레이트)(제품명 「카렌즈 MT PE1」, 쇼와 덴코(주)제)Thiol compound (C1): pentaerythritol tetrakis (3-mercaptobutyrate) (product name "Carenz MT PE1", manufactured by Showa Denko Co., Ltd.)
티올 화합물 (C2): 스테아릴-3-머캅토프로피오네이트(제품명 「STMP」, 사까이 가가꾸 고교(주)제)Thiol compound (C2): Stearyl-3-mercaptopropionate (product name "STMP", manufactured by Sakai Chemical Industry Co., Ltd.)
티올 화합물 (C3): 1,4-비스(3-머캅토부티릴옥시)부탄(제품명 「카렌즈 MT-BD-1」, 쇼와 덴코(주)제)Thiol compound (C3): 1,4-bis(3-mercaptobutyryloxy)butane (product name "Carenz MT-BD-1", manufactured by Showa Denko Co., Ltd.)
티올 화합물 (C4): 1,3,5-트리스(2-(3-술파닐부타노일옥시)에틸)-1,3,5-트리아지난-2,4,6-트리온(제품명 「카렌즈 MT-NR-1」, 쇼와 덴코(주)제)Thiol compound (C4): 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinan-2,4,6-trione (product name ``Carens MT-NR-1'', Showa Denko Corporation)
중합 금지제 (D1): 힌더드 페놀계 중합 금지제(제품명 「Irganox1010」, BASF사제)Polymerization inhibitor (D1): Hindered phenolic polymerization inhibitor (product name "Irganox1010", manufactured by BASF)
중합 금지제 (D2): 페놀계 중합 금지제(제품명 「키노 파워 QS20」, 가와사키 가세이 고교(주)제)Polymerization inhibitor (D2): Phenolic polymerization inhibitor (product name "Kino Power QS20", manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
중합 금지제 (D3): p-벤조퀴논Polymerization inhibitor (D3): p-benzoquinone
중합 금지제 (D4): 페노티아진Polymerization Inhibitor (D4): Phenothiazine
알칼리 가용성 수지 (E1): 하기 식 (E1)에 나타내는, 기호 a 내지 c를 첨부한 구조 단위를 갖는 아크릴계 수지(Mw: 8000, 구조 단위 a 내지 c의 함유 비율: a/b/c=50/30/20(질량％))Alkali-soluble resin (E1): an acrylic resin having a structural unit to which symbols a to c are attached, represented by the following formula (E1) (Mw: 8000, content ratio of structural units a to c: a/b/c=50/ 30/20 (mass%))
계면 활성제 (F1): 디글리세린에틸렌옥시드(평균 부가 몰수: 18) 부가물Surfactant (F1): diglycerine ethylene oxide (average added mole number: 18) adduct
퍼루플루오로노네닐에테르(제품명 「프타젠트 FTX-218」, 네오스(주)제)Perfluorononenyl ether (product name "Ptagent FTX-218", manufactured by Neos Co., Ltd.)
<레지스트 패턴의 형성><Formation of resist pattern>
[실시예 1B][Example 1B]
6인치 실리콘 웨이퍼 상에 구리 스퍼터막을 구비하는 기판에, 실시예 1A의 감광성 수지 조성물을 스핀 코팅법으로 도포하고, 핫 플레이트에서 110℃에서 180초간 가열하여, 12㎛의 막 두께를 갖는 수지 도막을 형성하였다.The photosensitive resin composition of Example 1A was applied to a substrate having a copper sputtered film on a 6-inch silicon wafer by spin coating, and heated at 110° C. for 180 seconds on a hot plate to obtain a resin coating film having a film thickness of 12 μm. Formed.
상기 수지 도막을, i선 노광용 스테퍼(장치명 「NSR-i12D」, (주)니콘제)를 사용하여, 2㎛의 1L/1S 레지스트 패턴 형성에 대응하는 영역(이하, 「BF 대응 영역」이라고 함) 및 2㎛의 1L/3S 레지스트 패턴 형성에 대응하는 영역(이하, 「DF 대응 영역」이라고 함)을 갖는 포토마스크를 통해 노광하였다. 노광은 20mJ/cm2로부터 10mJ/cm2씩 증가시킨 샷을 260mJ/cm2까지 25샷 행하였다.The resin coating film is an area corresponding to the formation of a 2 μm 1L/1S resist pattern (hereinafter referred to as a “BF-adaptive area” using a stepper for i-line exposure (device name “NSR-i12D”, manufactured by Nikon)). ) And a region corresponding to the formation of a 2 μm 1L/3S resist pattern (hereinafter referred to as “DF correspondence region”). Exposure was carried out 25 shots 20mJ / shot was increased by 10mJ / cm 2 from 2 cm up to 260mJ / cm 2.
노광 후의 수지 도막을, 현상액으로서 2.38질량％ 테트라메틸암모늄히드록시드수를 사용하여 액고임법으로 현상하고, 유수 세정, 건조시켜 레지스트 패턴을 형성하였다.The resin coating film after exposure was developed by a liquid retention method using 2.38 mass% tetramethylammonium hydroxide water as a developer, washed with running water, and dried to form a resist pattern.
BF 대응 영역에 있어서 2㎛의 1L/1S 레지스트 패턴을 최적으로 형성하는 노광량인 최적 노광량(EOP), BF에 있어서, 고정밀도의 미세한 레지스트 패턴을 형성할 수 있었던 노광량 범위, 및 DF에 있어서, 고정밀도의 미세한 레지스트 패턴을 형성할 수 있었던 노광량 범위, 그리고 상기 BF에 있어서의 노광량 범위와 상기 DF에 있어서의 노광량 범위가 중복되는 노광량 범위(중복 노광량 범위)를, 상기 레지스트 패턴을 전자 현미경 관찰함으로써 구하였다.Optimum exposure amount (EOP), which is the exposure amount that optimally forms a 2 μm 1L/1S resist pattern in the BF-adaptive region, the exposure amount range in which a high-precision, fine resist pattern could be formed in BF, and high-precision in DF. The exposure range in which a fine resist pattern in Fig. was formed, and the exposure range in which the exposure range in the BF and the exposure range in the DF overlap (overlap exposure range) was determined by observing the resist pattern with an electron microscope. I did.
또한, 상기 EOP에 대한 상기 중복 노광량 범위의 비율로부터, BF와 DF의 공통의 EL을 산출하였다.Further, the common EL of BF and DF was calculated from the ratio of the overlapping exposure amount range to the EOP.
평가 결과를 표 2에 나타낸다. 실시예 1B의 전자 현미경의 사진을 도 1에 도시한다.Table 2 shows the evaluation results. A photograph of the electron microscope of Example 1B is shown in FIG. 1.
[실시예 2B 내지 8A, 비교예 1B 내지 7B][Examples 2B to 8A, Comparative Examples 1B to 7B]
실시예 1B에 있어서, 표 2 중에 나타내는 감광성 수지 조성물을 사용한 것 이외에는 실시예 1B와 마찬가지의 조작으로 레지스트 패턴을 형성하고, BF 대응 영역 및 DF 대응 영역에 있어서의 노광량 범위, 및 중복 노광량 범위, 그리고 공통의 EL을 측정하였다. 평가 결과를 표 2에 나타낸다.In Example 1B, except for using the photosensitive resin composition shown in Table 2, a resist pattern was formed by the same operation as in Example 1B, and the exposure amount range in the BF correspondence region and the DF correspondence region, and the overlapping exposure amount range, and Common EL was measured. Table 2 shows the evaluation results.
실시예 2B 및 비교예 3B의 전자 현미경의 사진을 도 1에 도시한다.A photograph of the electron microscope of Example 2B and Comparative Example 3B is shown in FIG. 1.
<도금 조형물의 제조><Manufacture of plated sculptures>
[실시예 1C][Example 1C]
실시예 1B에서 형성한 레지스트 패턴을 갖는 기판을 애싱 처리하였다. 애싱 처리 후의 기판을 구리 도금액(제품명 「MICROFAB Cu300」, EEJA사제) 1리터 중에 25℃에서 15분간 침지하고, 전해 도금 반응을 행하였다. 이어서, 레지스트 패턴을 레지스트 박리액(제품명 「ELPAC THB-S17」, JSR(주)제)을 사용하여 박리하고, 도금 조형물을 제조하였다.The substrate having the resist pattern formed in Example 1B was subjected to ashing treatment. The substrate after the ashing treatment was immersed in 1 liter of a copper plating solution (product name "MICROFAB Cu300", manufactured by EEJA) at 25°C for 15 minutes, and electroplating reaction was performed. Subsequently, the resist pattern was peeled off using a resist stripper (product name "ELPAC THB-S17", manufactured by JSR Corporation) to prepare a plated article.
도 2는, EOP에 있어서의 2㎛의 1L/1S 레지스트 패턴을 마스크로 한 도금 조형물의 전자 현미경의 사진이다.Fig. 2 is a photograph of an electron microscope of a plated sculpture in which a 2 µm 1L/1S resist pattern is used as a mask in EOP.
Claims (8)
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| PCT/JP2019/035753 WO2020066633A1 (en) | 2018-09-26 | 2019-09-11 | Photosensitive resin composition, method for forming resist pattern, and method for manufacturing plated shaped body |
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| JP4090307B2 (en) | 2002-08-22 | 2008-05-28 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP2006267745A (en) | 2005-03-24 | 2006-10-05 | Fuji Photo Film Co Ltd | Image forming material |
| WO2011021620A1 (en) * | 2009-08-17 | 2011-02-24 | Izumo Yumin | Aquatic float unit body using waste tires and aquatic float structure obtained by connecting aquatic float unit bodies |
| JP5537864B2 (en) | 2009-08-19 | 2014-07-02 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP5439256B2 (en) * | 2010-03-31 | 2014-03-12 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition |
| KR102208741B1 (en) * | 2016-05-27 | 2021-01-28 | 후지필름 가부시키가이샤 | Curable composition, cured film, color filter, light-shielding film, solid-state imaging device, image display device, and method for producing cured film |
| KR102197805B1 (en) | 2016-08-25 | 2021-01-05 | 후지필름 가부시키가이샤 | Membrane manufacturing method, laminate manufacturing method, and electronic device manufacturing method |
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| JPWO2020066633A1 (en) | 2021-09-16 |
| JP7331855B2 (en) | 2023-08-23 |
| TW202012453A (en) | 2020-04-01 |
| WO2020066633A1 (en) | 2020-04-02 |
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