KR101708343B1 - Photosensitive Resin Composition for Dry Film Photoresist - Google Patents
Photosensitive Resin Composition for Dry Film Photoresist Download PDFInfo
- Publication number
- KR101708343B1 KR101708343B1 KR1020140188491A KR20140188491A KR101708343B1 KR 101708343 B1 KR101708343 B1 KR 101708343B1 KR 1020140188491 A KR1020140188491 A KR 1020140188491A KR 20140188491 A KR20140188491 A KR 20140188491A KR 101708343 B1 KR101708343 B1 KR 101708343B1
- Authority
- KR
- South Korea
- Prior art keywords
- resin composition
- photosensitive resin
- compound
- dry film
- weight
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 48
- -1 urethane compound Chemical class 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-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
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 2
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 2
- LYCNQAIOLGIAFA-UHFFFAOYSA-N 4-[bis[4-(dimethylamino)-2-methylphenyl]methyl]-n,n,3-trimethylaniline Chemical compound CC1=CC(N(C)C)=CC=C1C(C=1C(=CC(=CC=1)N(C)C)C)C1=CC=C(N(C)C)C=C1C LYCNQAIOLGIAFA-UHFFFAOYSA-N 0.000 description 2
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KFJJYOKMAAQFHC-UHFFFAOYSA-N (4-methoxy-5,5-dimethylcyclohexa-1,3-dien-1-yl)-phenylmethanone Chemical compound C1C(C)(C)C(OC)=CC=C1C(=O)C1=CC=CC=C1 KFJJYOKMAAQFHC-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- LIUXTOHGZBUDEX-UHFFFAOYSA-N 1-(2-butoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCCCOC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LIUXTOHGZBUDEX-UHFFFAOYSA-N 0.000 description 1
- DLUPHJKQEIIYAM-UHFFFAOYSA-N 1-(2-ethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCOC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 DLUPHJKQEIIYAM-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- VMCRQYHCDSXNLW-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2-dichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)Cl)C=C1 VMCRQYHCDSXNLW-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- ASUQXIDYMVXFKU-UHFFFAOYSA-N 2,6-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC=C(Br)C=C3C2=C1 ASUQXIDYMVXFKU-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- DXYGJDUJLDXFOD-UHFFFAOYSA-N 2-[2-[2-(2-acetyloxyethoxy)ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCOC(C)=O DXYGJDUJLDXFOD-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- QDPMVUZZMXVFJO-UHFFFAOYSA-N 2-hydroxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound COC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 QDPMVUZZMXVFJO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RTFWHSONHLXREP-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-yloxyphenyl)ethanone Chemical compound CC(C)OC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 RTFWHSONHLXREP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
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- 206010012735 Diarrhoea Diseases 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/0285—Silver salts, e.g. a latent silver salt image
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명은 드라이 필름 포토 레지스트용 감광성 수지 조성물에 관한 것으로, 보다 상세하게는 현상액에 대한 텐트 신뢰성을 향상시키는 동시에 소량의 노광 에너지량으로도 노광시킬 수 있는 레이저 다이렉트 노광기에도 적합하여 노광 공정의 속도가 전체 생산 속도를 좌우하는 업체나, PCB, 리드 프레임, PDP 및 기타 디스플레이 소자 등에 이미지를 생성하는데 있어서 생산성을 극대화시킬 수 있는 드라이 필름 포토 레지스트용 감광성 수지 조성물을 제공한다.The present invention relates to a photosensitive resin composition for a dry film photoresist, and more particularly, to a photosensitive resin composition for a dry film photoresist, which is suitable for a laser direct exposure machine capable of improving tent reliability with respect to a developer and exposing even a small amount of exposure energy, Provided is a photosensitive resin composition for a dry film photoresist capable of maximizing productivity in manufacturing an image, such as a company that affects the entire production speed, or a PCB, a lead frame, a PDP, and other display devices.
Description
본 발명은 드라이 필름 포토 레지스트용 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition for a dry film photoresist.
감광성 수지 조성물은 인쇄회로기판(Printed Circuit Board; PCB)이나 리드 프레임(Lead Frame)에 사용되고 있는 드라이 필름 포토 레지스트(Dry Film Photoresist, DFR), 액상 포토 레지스트(Liquid Photoresist Ink) 등의 형태로 사용되고 있다. The photosensitive resin composition is used in the form of a dry film photoresist (DFR), a liquid photoresist ink, or the like which is used for a printed circuit board (PCB) or a lead frame .
현재는 인쇄회로기판(PCB)나 리드 프레임 제조뿐만 아니라, 플라즈마 디스플레이 패널(PDP)의 립 베리어(Rib barrier)나 기타 디스플레이의 ITO 전극, 버스 어드레스(Bus Address) 전극, 블랙 매트릭스(Black Matrix) 제조 등에도 드라이 필름 포토 레지스트가 널리 사용되고 있다. At present, the present invention can be applied not only to the manufacture of printed circuit boards (PCBs) and lead frames, but also to the production of Rib barriers of plasma display panels (PDPs) and other displays such as ITO electrodes, bus address electrodes, Black Matrix Dry film photoresists are widely used.
PCB, 리드 프레임 등을 제조하는 데 있어서, 가장 중요한 공정 중 하나는 원판인 구리 적층판(Copper Clad Lamination Sheet, 이하 CCLS라 칭함), 동박(Copper Foil)에 회로를 형성하는 공정이다. 이 공정에 사용되는 이미지 전사 방식을 포토 리소그라피(Photo Lithography)라 하며, 이 포토 리소그라피를 하기 위해서 쓰이는 원본 이미지판을 Artwork(PCB, Lead Frame 제조부분에서 통상적으로 사용되는 용어), Photomask(반도체 제조부분에서 통상적으로 사용되는 용어)라 부르고 있다.In manufacturing a PCB, a lead frame, etc., one of the most important processes is a process of forming a circuit on a copper clad lamination sheet (hereinafter referred to as CCLS) and a copper foil. The image transfer method used in this process is called photolithography. The original image plate used for this photolithography is called Artwork (a term commonly used in PCB and lead frame manufacturing parts), Photomask Quot;). ≪ / RTI >
그리고 이 Artwork의 이미지에 빛이 통과하는 부분과 그렇지 못한 부분으로 되어 있으며, 이를 이용하여 이미지를 전사한다. 이 이미지 전사 공정을 노광 공정이라 한다. And the image of this artwork is composed of the part where the light passes and the part that does not, and the image is transferred using this part. This image transfer process is called an exposure process.
Artwork의 이미지는 빛의 투과와 비투과에 의해서 CCLS 또는 Copper Foil로 전사되는데, 이때 이 빛을 받아서 이미지를 형성해 주는 물질이 포토레지스트(Photoresist, 이하 PR이라 칭함)이다. 따라서 PR은 Artwork의 이미지를 전사하기 전에 CCLS, 동박 등에 라미네이션 또는 코팅되어 있어야 한다.The image of the artwork is transferred to the CCLS or the Copper Foil by light transmission and non-transmission, and the material that forms the image by receiving the light is a photoresist (hereinafter referred to as PR). Therefore, PR must be laminated or coated on CCLS, copper foil, etc. before transferring the image of the artwork.
노광 공정 시 통상적으로 PCB, 리드 프레임 업체에서는 PR을 초고압 수은 램프가 발하는 i선 (365nm)을 포함하는 자외선(Ultra Violet, 이하 UV라 칭함)으로 노광함으로써 노광 부분을 중합 경화시킨다. 최근에는 레이저에 의한 직접 묘화, 즉, Artwork를 필요로 하지 않는 마스크리스 노광이 급격한 확산을 보이고 있다. 마스크리스 노광의 광원으로는 파장 350 내지 410nm의 광, 특히 i선(365nm) 또는 h선(405nm)이 사용되는 경우가 많다. 그러나 통상적으로 실시되는 초고압 수은등 노광에 비해 마스크리스 노광은 노광하는 시간이 길어서 노광 시간을 짧게 하는 고감도의 PR이 요구되고 있다. In the exposure process, typically, PCB and lead frame makers are exposed to ultraviolet (UV) rays including i-line (365 nm) emitted by a high-pressure mercury lamp to polymerize and cure the exposed portions. In recent years, direct drawing by laser, that is, maskless exposure which does not require artwork, has been rapidly diffused. As a light source for maskless exposure, light of a wavelength of 350 to 410 nm, particularly i-line (365 nm) or h-line (405 nm) is often used. However, compared with the conventional ultra high-pressure mercury lamp exposure, the maskless exposure requires a high-sensitivity PR that shortens the exposure time because of a long exposure time.
최근에는 감광성 수지 조성물에 있어서 초고압 수은등이나 레이져 다이렉트 노광에 대한 감도가 높고, 현상공정에서 현상액에 대한 텐트 신뢰성이 뛰어난 감광성 수지 조성물을 필요로 하고 있다.In recent years, there is a need for a photosensitive resin composition which has a high sensitivity to ultra-high pressure mercury lamps or laser direct exposure in a photosensitive resin composition and has excellent tent reliability with respect to a developer in a developing process.
본 발명의 주된 목적은 현상액에 대한 텐트 신뢰성을 향상시키고, 레이저 다이렉트(Laser Direct) 노광기에서 소량의 노광 에너지량으로도 노광시킬 수 있는 드라이 필름 포토레지스트용 감광성 수지 조성물을 제공하는데 있다.The main object of the present invention is to provide a photosensitive resin composition for a dry film photoresist which improves tent reliability for a developer and can be exposed to a small amount of exposure energy in a Laser Direct exposure machine.
상기의 목적을 달성하기 위하여, 본 발명의 일 구현예는 [A] 광중합 개시제; [B] 알카리 현상성 바인더 폴리머; 및 [C] 광중합성 화합물을 포함하고, 상기 [A] 광중합 개시제는 n-페닐글리신을 포함하며, 상기 [C] 광중합성 화합물은 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물을 포함하는 것을 특징으로 하는 드라이 필름 포토레지스트용 감광성 수지 조성물을 제공한다.In order to achieve the above object, one embodiment of the present invention is directed to a photoresist composition comprising: [A] a photopolymerization initiator; [B] alkali developable binder polymer; And [C] a photopolymerizable compound, wherein the [A] photopolymerization initiator comprises n-phenylglycine, and the [C] photopolymerizable compound has an ethylenic unsaturated group and a urethane bond in its molecule and has a weight average molecular weight of 30,000 To 50,000 g / mol of the photosensitive resin composition for dry film photoresists.
본 발명의 바람직한 일 구현예에서, 상기 감광성 수지 조성물은 [A] 광중합 개시제 0.5 내지 20 중량%, [B] 알카리 현상성 바인더 폴리머 30 내지 70중량% 및 [C] 광중합성 화합물 10 내지 65 중량%를 포함하는 것을 특징으로 할 수 있다.In one preferred embodiment of the present invention, the photosensitive resin composition comprises 0.5 to 20% by weight of the [A] photopolymerization initiator, 30 to 70% by weight of the alkali developable binder polymer, and 10 to 65% by weight of the [C] And a control unit.
본 발명의 바람직한 일 구현예에서, 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물은 감광성 수지 조성물 총 중량에 대하여, 1 내지 20 중량%로 포함하는 것을 특징으로 할 수 있다.In one preferred embodiment of the present invention, the compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol is contained in an amount of 1 to 20% by weight based on the total weight of the photosensitive resin composition . ≪ / RTI >
본 발명의 바람직한 일 구현예에서, 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물은 폴리에테르 화합물의 말단 하이드록시기와 디이소시아네이트 화합물의 이소시아네이트기와의 반응에 유래하는 우레탄 화합물과, 하이드록시기 및 에틸렌성 불포화기를 갖는 화합물을 반응시켜 얻어지는 생성물인 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol is reacted with a terminal hydroxy group of the polyether compound and an isocyanate group of the diisocyanate compound , And a compound having a hydroxyl group and an ethylenic unsaturated group.
본 발명의 바람직한 일 구현예에서, 상기 n-페닐글리신은 감광성 수지 조성물 총 중량에 대하여, 0.05 내지 2 중량%로 포함하는 것을 특징으로 할 수 있다.In one preferred embodiment of the present invention, the n-phenylglycine may be contained in an amount of 0.05 to 2% by weight based on the total weight of the photosensitive resin composition.
본 발명의 바람직한 일 구현예에서, 상기 감광성 수지 조성물은 레이저 다이렉트 전용 노광기로 노광하여 노광부가 광경화되고, 현상공정에 의해서 레지스트 패턴을 형성하는 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the photosensitive resin composition is exposed by a laser direct exposure machine to cure the exposed portion, and a resist pattern is formed by a developing process.
본 발명의 바람직한 일 구현예에서, 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물은 에테르기를 더 가지는 것을 특징으로 할 수 있다.In a preferred embodiment of the present invention, the compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol may further have an ether group.
본 발명에 따른 드라이 필름 포토 레지스트용 감광성 수지 조성물은 현상액에 대한 텐트 신뢰성을 향상시키는 동시에 소량의 노광 에너지량으로도 노광시킬 수 있는 레이저 다이렉트 노광기에도 적합하여 노광 공정의 속도가 전체 생산 속도를 좌우하는 업체나, PCB, 리드 프레임, PDP 및 기타 디스플레이 소자 등에 이미지를 생성하는데 있어서 생산성을 극대화시킬 수 있는 효과가 있다.The photosensitive resin composition for a dry film photoresist according to the present invention is suitable for a laser direct exposure machine capable of improving tent reliability for a developer and capable of exposing even a small amount of exposure energy so that the speed of the exposure process determines the overall production speed It is possible to maximize productivity in generating images in a company, a PCB, a lead frame, a PDP, and other display devices.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법 은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다. Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.
본 발명은 [A] 광중합 개시제; [B] 알카리 현상성 바인더 폴리머; 및 [C] 광중합성 화합물을 포함하고, 상기 [A] 광중합 개시제는 n-페닐글리신을 포함하며, 상기 [C] 광중합성 화합물은 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물을 포함하는 것을 특징으로 하는 드라이 필름 포토레지스트용 감광성 수지 조성물에 관한 것이다.The present invention relates to [A] a photopolymerization initiator; [B] alkali developable binder polymer; And [C] a photopolymerizable compound, wherein the [A] photopolymerization initiator comprises n-phenylglycine, and the [C] photopolymerizable compound has an ethylenic unsaturated group and a urethane bond in its molecule and has a weight average molecular weight of 30,000 To 50,000 g / mol, based on the total weight of the photoresist composition.
본 발명은 현상액에 대한 텐트 신뢰성을 높이고, 레이저 다이렉트 노광기에서 소량의 노광 에너지량으로도 노광시킬 수 있는 드라이 필름 포토레지스트용 감광성 수지 조성물을 제공한다.The present invention provides a photosensitive resin composition for a dry film photoresist capable of enhancing tent reliability for a developer and capable of exposing even a small amount of exposure energy in a laser direct exposure machine.
또한, 본 발명에 따른 드라이 필름 포토레지스트용 감광성 수지 조성물은 [A] 광중합 개시제로 n-페닐글리신을 포함함으로써, 감광성 수지 조성물의 레이저 다이렉트 노광에 대한 감도를 높일 수 있고, 현상공정에서 현상액에 대한 내성을 향상시킬 수 있다.In addition, the photosensitive resin composition for a dry film photoresist according to the present invention can increase the sensitivity of the photosensitive resin composition to laser direct exposure by containing [A] n-phenylglycine as a photopolymerization initiator, The resistance can be improved.
또한, 본 발명에 따른 드라이 필름 포토레지스트용 감광성 수지 조성물은 [C] 광중합성 화합물로 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물을 포함함으로써, 레이저 다이렉트 노광에 대한 감도를 더욱 높일 수 있고, 현상공정에서 현상액에 대한 텐트 신뢰성을 향상시킬 수 있어 생산성을 극대화시킬 수 있다.Further, the photosensitive resin composition for a dry film photoresist according to the present invention is a photopolymerizable compound [C] containing a compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol, The sensitivity to direct exposure can be further increased and the reliability of the tent for the developing solution can be improved in the developing step, thereby maximizing the productivity.
이하, 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
[A] 광중합 개시제 [A] Photopolymerization initiator
본 발명에 따른 드라이 필름 포토레지스트용 감광성 수지 조성물에 포함되는 광중합 개시제는 UV 및 기타 radiation에 의해서 광중합성 모노머의 연쇄반응을 개시시키는 물질로서, 드라이 필름 포토레지스트의 경화에 중요한 역할을 한다. The photopolymerization initiator contained in the photosensitive resin composition for a dry film photoresist according to the present invention is a substance that initiates a chain reaction of a photopolymerizable monomer by UV and other radiation and plays an important role in the curing of a dry film photoresist.
본 발명에서는 광중합 개시제로 n-페닐글리신을 포함한다. 상기 n-페닐글리신은 350 내지 410nm에 극단적으로 민감하게 반응하여 적은 노광 에너지만으로도 충분한 광반응을 일으켜 레이저 다이렉트 노광에 대한 감도를 높이고, 현상공정에서 현상액에 대한 내성을 향상시켜 양호한 회로 형성을 할 수 있다.In the present invention, n-phenylglycine is included as a photopolymerization initiator. The n-phenylglycine reacts with extreme sensitivity to 350 to 410 nm, thereby achieving sufficient photoreaction even with a small exposure energy, thereby enhancing sensitivity to laser direct exposure and improving resistance to a developing solution in a developing process to form a good circuit have.
이 같은 역할을 하는 n-페닐글리신의 함량은 전체 수지 조성물 중 0.05 ~ 2중량%인 바, 그 함량이 0.05중량% 미만이면 개시제의 반응성이 약해져서 적은 노광 에너지량(약 30mJ/cm2 이하)에서 사용이 불가능하며, 2중량%를 초과하면 노광 후 회로의 단면이 심한 역사다리 형태를 갖게 되어 에칭 공정 후 회로에서 원하는 회로폭을 구현할 수 없으며, 심한 경우 단선(open) 불량을 유발할 수 있다. If the content of the n- phenylglycine to the same role, the total resin composition of about 0.05 to the bar, in amounts of 2% by weight less than 0.05% by weight low exposure energy quantity weak reactivity of the initiator (about 30mJ / cm 2 Or more), and if it is more than 2% by weight, the cross-section of the circuit after exposure has a severe history leg shape, and the desired circuit width can not be realized in the circuit after the etching process. In severe cases, have.
본 발명에 따른 광중합 개시제는 n-페닐글리신 이외에도 통상적으로 사용하는 광중합 개시제를 더 포함할 수 있다. The photopolymerization initiator according to the present invention may further comprise a photopolymerization initiator that is commonly used in addition to n-phenylglycine.
상기 통상적으로 사용하는 광중합 개시제로는 2,2'-비스(2-클로로페닐)-4,4'-5,5'-테트라페닐비스이미다졸, 1-히드록시시클로헥실페닐케톤, 2,2-디메톡시-1,2-디페닐에탄-1-온, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-[4-모르폴리노페닐)부탄-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 1-[4-(2-히드록시메톡시)페닐]-2-히드록시-2-메틸프로판-1-온, 2,4-디에틸티옥산톤, 2-클로로티옥산톤, 2,4-디메틸티옥산톤, 3,3-디메틸-4-메톡시벤조페논, 벤조페논, 1-클로로-4-프로폭시티옥산톤, 1-(4-이소프로필페닐)2-히드록시-2-메틸프로판-1-온, 1-(4-도데실페닐)-2하이두록시-2-메틸프로판-1-온, 4-벤조일-4'-메틸디메틸설파이드, 4-디메틸아미노벤조산, 메틸 4-디메틸아미노벤조에이트, 에틸 4-디메틸아미노벤조에이트, 부틸 4-디메틸아미노벤조에이트, 2-에틸헥실 4-디메틸아미노벤조에이트, 2-이소아밀 4-디메틸아미노벤조에이트, 2,2-디에톡시아세토페논, 벤질케톤 디메틸아세탈, 벤질케톤 β-메톡시 디에틸아세탈, 1-페닐-1,2-프로필디옥심-o,o'-(2-카르보닐)에톡시에테르, 메틸 o-벤조일벤조에이트, 비스[4-디메틸아미노페닐)케톤, 4,4'-비스(디에틸아미노)벤조페논, 4,4'-디클로로벤조페논, 벤질, 벤조인, 메톡시벤조인, 에톡시벤조인, 이소프로폭시벤조인, n-부톡시벤조인, 이소부톡시벤조인, tert-부톡시벤조인, p-디메틸아미노아세토페논, p-tert-부틸트리클로로아세토페논, p-tert-부틸디클로로아세토페논, 티옥산톤, 2-메틸티옥산톤, 2-이소프로필티옥산톤, 디벤조수베론, α-α-디클로로-4-페녹시아세토페논, 펜틸 4-디메틸아미노벤조에이트, 9-페닐아크리딘, n-페닐글리신, 아크리딘 화합물, 티옥산톤계 화합물, 안트라센 화합물, 쿠마린계 화합물, 피라졸린계 화합물, 헥사아릴-이미다졸(hexaaryl-imidazole)의 다이머(dimer) 등을 들 수 있으나, 이에 한정되는 것은 아니다. The commonly used photopolymerization initiators include 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenylketone, 2,2'- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- Amino-1- [4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- -Dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxyoxanthone and 1- (4-isopropylphenyl) 2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4 - dimethylaminobenzoate, ethyl 4-dimethylamino Dimethyl aminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone beta Benzoyl benzoate, bis [4-dimethylaminophenyl) ketone (hereinafter, referred to as " , 4,4'-bis (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzo Butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone , 2-isopropylthioxanthone, dibenzosuberone,? -? - dichloro-4-phenoxyacetophenone, pentyl 4-dimethylaminobenzoate, 9-phenylacridine, But are not limited to, lysine, acridine compounds, thioxanthone compounds, anthracene compounds, coumarin compounds, pyrazoline compounds, hexaaryl-imidazole dimers, and the like .
상기 광중합 개시제의 함량은 감광성 수지 조성물 중에 0.5 내지 20중량%로 포함된다. 상기 광중합 개시제의 함량이 상기 범위 내에 있는 경우 충분한 감도를 얻을 수 있다.
The content of the photopolymerization initiator is in the range of 0.5 to 20% by weight in the photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained.
[B] 알카리 현상성 바인더 폴리머[B] Alkali developing binder polymer
본 발명의 알카리 현상성 바인더 폴리머는 (메타)아크릴산과 (메타)아크릴산에스테르의 공중합체이다. 구체적으로는, 메틸 아크릴레이트, 메틸 메타크릴레이트, 에틸아크릴레이트, 메틸 메타크릴레이트, 부틸 아크릴레이트, 부틸 메타크릴레이트, 아크릴산, 메타크릴산, 2-히드록시 에틸 아크릴레이트, 2-히드록시 에틸 메타크릴레이트, 2-히드록시 프로필 아크릴레이트, 2-히드록시 프로필 메타크릴레이트, 아크릴아마이드, 메타크릴아마이드, 스타이렌, α-메틸 스타이렌으로 합성된 선형 아크릴산 고분자 중에서 선택된 둘 이상의 모노머들의 공중합을 통해 얻어진 공중합 아크릴산 고분자이다. The alkali developable binder polymer of the present invention is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester. Specific examples of the monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2- The copolymerization of two or more monomers selected from linear acrylic acid polymers synthesized from methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, styrene, ≪ / RTI >
본 발명의 알카리 현상성 바인더 폴리머는 드라이 필름 포토레지스트의 코팅성, 추종성, 그리고 회로형성 후 레지스트 자체의 기계적 강도를 고려해서 수평균분자량이 30,000 내지 150,000g/mol이며, 유리전이온도는 20 내지 150℃인 고분자 화합물로서, 감광성 수지 조성물 중에 30 내지 70중량%로 포함된다. 상기 알카리 현상성 바인더 폴리머의 함량이 상기 범위 내에 있는 경우 회로형성 후, 세선 밀착력을 강화시키는 효과를 얻을 수 있다. The alkali developable binder polymer of the present invention has a number average molecular weight of 30,000 to 150,000 g / mol and a glass transition temperature of 20 to 150 g / mol in consideration of the coating property, followability and mechanical strength of the resist itself after the formation of the circuit, Deg.] C, and is contained in the photosensitive resin composition in an amount of 30 to 70% by weight. When the content of the alkali developable binder polymer is within the above range, an effect of enhancing the fine line adhesion force after the circuit formation can be obtained.
이때, 이상 및 이하의 분자량은 겔 투과 크로마토그래피(GPC)(Waters: Waters707)에 의해 측정된 폴리스티렌 환산 중량평균분자량(Mw) 및 수평균분자량(Mn)으로, 측정 대상물을 4000ppm의 농도가 되도록 테트라히드로푸란에 용해시켜 GPC에 100㎕를 주입하여 측정하였다. 이때, GPC의 이동상은 테트라히드로푸란을 사용하고, 1.0mL/분의 유속으로 유입하였으며, 분석은 35℃에서 수행하였다. 컬럼은 Waters HR-05,1,2,4E 4개를 직렬로 연결하였다. 검출기로는 RI and PAD Detecter를 이용하여 35℃에서 측정하였다.
Herein, the molecular weights above and below are the polystyrene reduced weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Waters: Waters 707) Dissolved in hydrofuran, and 100 μl was injected into GPC. At this time, the moving phase of GPC was tetrahydrofuran, and the flow rate was 1.0 mL / min. The analysis was carried out at 35 ° C. The column was connected in series with four Waters HR-05, 1, 2, and 4E. Detector was measured at 35 ℃ using RI and PAD Detector.
[C] 광중합성 화합물[C] Photopolymerizable compound
본 발명의 광중합성 화합물은 현상액에 대한 텐트 신뢰성을 높이기 위해서 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물을 포함한다.The photopolymerizable compound of the present invention includes a compound having an ethylenic unsaturated group and a urethane bond in the molecule in order to improve the tent reliability of the developer.
상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물은 양 말단에 하이드록실기를 가지는 폴리에테르 화합물과 디이소시아네이트 화합물을 반응시켜 우레탄 화합물을 수득하고, 상기 수득된 우레탄 화합물과 하이드록실기 및 에틸렌성 불포화기를 가지는 화합물을 축합반응시켜 얻을 수 있다.The compound having an ethylenic unsaturated group and a urethane bond in the molecule is obtained by reacting a polyether compound having a hydroxyl group at both terminals with a diisocyanate compound to obtain a urethane compound and reacting the obtained urethane compound with a hydroxyl group and an ethylenic Can be obtained by a condensation reaction of a compound having an unsaturated group.
이렇게 얻은 화합물은 분자 내에 에틸렌성 불포화기, 우레탄 결합 및 에테르기를 가지는 화합물일 수 있다. The compound thus obtained may be a compound having an ethylenic unsaturated group, a urethane bond and an ether group in the molecule.
상기 하이드록실기를 가지는 폴리에테르 화합물은 폴리에테르글리콜로서 폴리옥시에틸렌, 폴리옥시프로필렌, 폴리옥시테트라히드로푸란 등의 글리콜이 사용된다.As the polyether compound having a hydroxyl group, a polyether glycol such as polyoxyethylene, polyoxypropylene, or polyoxytetrahydrofuran is used.
상기 디이소시아네이트 화합물로서는, 예를 들면, 알킬렌기 등의 2가 지방족기를 가지는 지방족 디이소시아네이트 화합물, 시클로알킬렌 등의 2가의 지환기 기를 가지는 지환식 디이소시아네이트 화합물, 방향족 디이소이사네이트 화합물 및 이들의 이소시아누레이트화 변성물, 카르보디이미드화 변성물, 뷰렛화 변성물 등을 들 수 있다. Examples of the diisocyanate compound include aliphatic diisocyanate compounds having a bivalent aliphatic group such as an alkylene group, alicyclic diisocyanate compounds having a divalent tricyclic group such as cycloalkylene, aromatic diisocyanate compounds, An isocyanurate modified product, a carbodiimide modified product, and a buret tail modified product.
이때, 상기 지방족 디이소시아네이트 화합물로서는 헥사메틸렌이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트 등을 들 수 있다. 지환식 디이소시아네이트 화합물로서는 이소포론디이소시아네이트, 메틸렌비스(시클로헥실)디이소시아네이트, 1,3- 혹은 1,4-비스(이소시아네이트메틸)시클로헥산 등을 들 수 있다. 방향족 디이소시아네이트 화합물로서는 2,4-톨로엔디이소시아네이트, 2,6-톨로엔디이소시아네이트, 2,4-톨로엔디이소시아네이트 또는 2,6-톨로엔디이소시아네이트의 2량화 중합체, (o, p 또는 m)-크실렌디이소시아네이트, 디페닐메탄디이소시아네이트, 1,5-나프탈렌디이소시아네이트 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종류 이상을 조합시켜 사용된다. 또한, 트리페닐메탄트리이소시아네이트, 트리스(이소시아네이트페닐)티오포스페이트 등의 2 이상의 이소시아네이트기를 가지는 이소시아네이트 화합물이 포함되어 있어도 좋다. 이들 중에서도 광경화물의 유연성과 강인성 높여 텐트 신뢰성을 향상시키는 관점에서 지환식 디이소시아네이트 화합물이 바람직하다.Examples of the aliphatic diisocyanate compound include hexamethylene isocyanate, trimethylhexamethylene diisocyanate, and the like. Examples of the alicyclic diisocyanate compound include isophorone diisocyanate, methylene bis (cyclohexyl) diisocyanate, and 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane. Examples of the aromatic diisocyanate compound include dimerized polymers of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, (o, p or m) Diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate. These may be used alone or in combination of two or more. Further, an isocyanate compound having two or more isocyanate groups such as triphenylmethane triisocyanate and tris (isocyanate phenyl) thiophosphate may be contained. Among them, an alicyclic diisocyanate compound is preferable from the viewpoints of enhancing flexibility and toughness of a light-cured product to improve tent reliability.
본 발명의 우레탄 화합물은 하이드록실기를 가지는 폴리에테르 화합물과 디이소시아네이트 화합물을 반응시킴으로써 얻어진다. 상기 반응에 있어서 하이드록실기를 가지는 폴리에테르 화합물의 1몰에 대해서 디이소시아네이트 화합물을 1.01 ~ 2.0 몰비로 하는 것이 바람직하고, 1.1 ~ 2.0 몰비로 하는 것이 보다 바람직하다. 만일 디이소시아네이트 화합물의 함량이 1.01 몰 미만 또는 2.0 몰을 넘으면, 양 말단에 이소시아네이트기를 가지는 우레탄 화합물을 안정적으로 얻을 수 없는 경향이 있다. The urethane compound of the present invention is obtained by reacting a polyether compound having a hydroxyl group with a diisocyanate compound. In the above reaction, the diisocyanate compound is preferably used in an amount of 1.01 to 2.0 mol, more preferably 1.1 to 2.0 mol, per mol of the polyether compound having a hydroxyl group. If the content of the diisocyanate compound is less than 1.01 mol or more than 2.0 mol, the urethane compound having isocyanate groups at both terminals tends not to be stably obtained.
또한, 우레탄 화합물을 합성하는 반응에서는 촉매로서 디부틸주석디라우레이트를 투입하는 것이 바람직하다. 반응 온도는 60 ~ 120℃로 하는 것이 바람직하다. 60℃ 미만이면 반응이 충분히 진행되지 않는 경향이 있고, 120℃를 넘으면 급격한 발열에 의해, 반응 조작이 위험할 수 있다.In the reaction for synthesizing the urethane compound, it is preferable to add dibutyltin dilaurate as a catalyst. The reaction temperature is preferably 60 to 120 占 폚. If the temperature is lower than 60 deg. C, the reaction tends not to proceed sufficiently, and if it exceeds 120 deg. C, the reaction operation may be dangerous due to rapid heat generation.
이와 같이 제조된 우레탄 화합물과 반응하여 분자내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물을 제조할 수 있는, 하이드록실기 및 에틸렌성 불포화 기를 가지는 화합물로는 분자 중에 하이드록실기 및 (메타)아크릴로일기를 가지는 화합물을 들 수 있다. 이러한 화합물로서는, 하이드록시(메타)아크릴레이트, 이것의 카프로락톤 부가물 또는 산화 알킬렌 부가물, 글리세린 등의 다가의 알코올과 (메타)아크릴산과의 에스테르 화합물, 및 글리시딜(메타)아릴레이트아크릴산 부가물을 들 수 있다.Examples of the compound having a hydroxyl group and an ethylenic unsaturated group capable of reacting with the urethane compound thus prepared to produce a compound having an ethylenic unsaturated group and a urethane bond in the molecule include hydroxyl group and (meth) acryloyl A compound having a diarrhea. Examples of such compounds include hydroxy (meth) acrylates, caprolactone adducts thereof or alkylene oxide adducts thereof, ester compounds of polyhydric alcohols such as glycerin with (meth) acrylic acid, and glycidyl (meth) Acrylic acid adduct.
상기 하이드록시(메타)아크릴레이트로서는 2-하이드록시에틸(메타)아크릴레이트, 하이드록시프로필(메타)아크릴레이트, 하이드록시부틸(메타)아크릴레이트를 들 수 있다. 이들의 카프로락톤 부가물로서는 하이드록시에틸(메타)아크릴레이트카프로락톤 부가물, 하이드록시프로필(메타)아크릴레이트카프로락톤 부가물, 하이드록시부틸(메타)아크릴레이트카프로락톤 부가물을 들 수 있고, 산화알킬렌 부가물로서는, 하이드록시에틸(메타)아크릴레이트산화알킬렌 부가물, 하이드록시프로필(메타)아크릴레이트산화프로필렌 부가물, 하이드록시부틸(메타)아크릴레이트산화부틸렌 부가물을 들 수 있다. 에스테르 화합물로서는, 예를 들면, 글리세린 모노(메타)아크릴레이트, 글리세린디(메타)아크릴레이트, 펜에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 트리메티롤프로판모노(메타)아크릴레이트, 디트리메티롤프로판트리(메타)아크릴레이트, 트리메티롤프로판의 산화에틸렌 부가물의 디(메타)아크릴레이트, 트리메티롤프로판의 산화프로필렌 부가물의 디(메타)아크릴레이트를 들 수 있다. 이들은 1종을 단독으로 또는 2종류 이상을 조합시켜 사용된다.Examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. Examples of the caprolactone adducts of these compounds include hydroxyethyl (meth) acrylate caprolactone adduct, hydroxypropyl (meth) acrylate caprolactone adduct, and hydroxybutyl (meth) acrylate caprolactone adduct. Examples of the alkylene oxide adducts include alkylene oxide adducts of hydroxyethyl (meth) acrylate, propylene oxide adducts of hydroxypropyl (meth) acrylate, and adducts of hydroxybutyl (meth) acrylate oxide have. Examples of the ester compound include glycerin mono (meth) acrylate, glycerin di (meth) acrylate, phenerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylol propane mono (Meth) acrylates of ethylene oxide adducts of trimethylolpropane, di (meth) acrylates of propylene oxide adducts of trimethylolpropane, and di (meth) acrylates of ditrimethylolpropane tri have. These may be used alone or in combination of two or more.
상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물은 우레탄 화합물에 하이드록실기 및 에틸렌 불포화기를 가지는 화합물을 부가 반응에 유래하는 화합물로, 우레탄 화합물 1몰에 대해서 하이드록실기 및 에틸렌 불포화기를 가지는 화합물의 투입량을 2.0 ~ 2.4 몰비로 60 내지 90℃에서 부가 반응시킴으로써 얻을 수 있다.The compound having an ethylenic unsaturated group and a urethane bond in the molecule is a compound derived from an addition reaction of a compound having a hydroxyl group and an ethylenic unsaturated group in a urethane compound and a compound having a hydroxyl group and an ethylenic unsaturated group per mole of the urethane compound In an amount of 2.0 to 2.4 molar ratio at 60 to 90 캜.
또한, 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물은 통상의 방법에 의해 합성해도 좋고, 시판되고 있는 것을 입수해도 좋다, The compound having an ethylenic unsaturated group and a urethane bond in the molecule may be synthesized by a common method or commercially available one,
상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물은 중량평균분자량이 30,000g/mol 미만일 경우, 유연성과 강인성을 충분히 높이기 어려워져 텐트 신뢰성을 향상시킬 수 없고, 중량평균분자량이 50,000g/mol를 초과하는 경우에는 현상성이 나빠져서 현상 시간이 느려지는 문제점이 발생될 수 있어, 본 발명에 따른 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물은 중량평균분자량이 30,000 ~ 50,000g/mol인 것이 바람직하다.When the weight average molecular weight of the compound having an ethylenic unsaturated group and a urethane bond in the molecule is less than 30,000 g / mol, it is difficult to sufficiently increase the flexibility and toughness and the tent reliability can not be improved. When the weight average molecular weight is 50,000 g / mol The compound having an ethylenic unsaturated group and a urethane bond in the molecule according to the present invention preferably has a weight average molecular weight of 30,000 to 50,000 g / mol, more preferably 30,000 to 50,000 g / mol, Do.
본 발명에서는 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물을 감광성 수지 조성물 중에 1 내지 20중량%로, 바람직하게는 1.5 내지 15중량%로 포함한다. 상기 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 중량평균분자량이 30,000 내지 50,000g/mol인 화합물의 함량이 1중량% 미만일 경우, 그 효과가 미흡하고, 20중량%를 초과하는 경우에는 노광 후 현상 공정에서의 현상시간이 급격히 증가하는 단점이 발생될 수 있다. In the present invention, a compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol is contained in the photosensitive resin composition in an amount of 1 to 20% by weight, preferably 1.5 to 15% by weight . When the content of the compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol is less than 1% by weight, the effect is insufficient. When the content is more than 20% by weight, There is a drawback that the development time in the process is rapidly increased.
본 발명의 광중합성 화합물은 분자 내에 에틸렌성 불포화기 및 우레탄 결합을 가지는 화합물 이외에도 말단에 적어도 2개의 에틸렌기를 갖는 화합물을 더 포함할 수 있다. The photopolymerizable compound of the present invention may further contain, in addition to the compound having an ethylenic unsaturated group and a urethane bond in the molecule, a compound having at least two ethylene groups at the terminals.
상기 말단에 적어도 2개의 에틸렌기를 갖는 화합물로는 에틸렌글리콜디메타크릴레이트(ethylene glycol dimethacrylate), 디에틸렌글리콜디메타크릴레이트(diethylene glycol dimethacrylate), 테트라에틸렌글리콜디메타크릴레이트(tetraethylene glycol dimethacrylate), 프로필렌글리콜디메타크릴레이트(propylene glycol dimethacrylate), 폴리에틸렌글리콜디메타크릴레이트(polyethylene glycol dimethacrylate), 폴리프로필렌글리콜디메타크릴레이트(polypropylene glycol dimethacrylate), 부틸렌글리콜디메타크릴레이트(butylene glycol dimethacrylate), 네오펜틸글리콜디메타크릴레이트(neopentyl glycol dimethacrylate), 1,6-헥산글리콜디메타크릴레이트(1,6-hexane glycol dimethacrylate), 트리메틸올프로판 트리메타크릴레이트(trimethyolpropane trimethacrylate), 트리메틸올프로판 트리아크릴레이트(trimethyolpropane triacrylate), 글리세린 디메타크릴레이트(glycerin dimethacrylate), 펜타에리트리톨 디메타크릴레이트(pentaerythritol dimethacrylate), 펜타에리트리톨 트리메타크릴레이트(pentaerythritol trimethacrylate), 디펜타에리트리톨 펜타메타크릴레이트(dipentaerythritol pentamethacrylate), 2,2-비스(4-메타크릴옥시디에톡시페닐)프로판(2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2,2-비스(4-메타크릴옥시폴리에톡시페닐)프로판(2,2-bis(4-methacryloxypolyethoxyphenyl)propane), 2-히드록시-3-메타크릴로일옥시프로필 메타크릴레이트(2-hydroxy-3-methacryloyloxypropyl methacrylate), 에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(ethylene glycol diglycidyl ether dimethacrylate), 디에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(diethylene glycol diglycidyl ether dimethacrylate), 프탈산 디글리시딜에스테르 디메타크릴레이트(phthalic acid diglycidyl ester dimethacrylate), 글리세린 폴리글리시딜에테르 폴리메타크릴레이트(glycerin polyglycidyl ether polymethacrylate) 및 우레탄기를 함유한 다관능 (메트)아크릴레이트 등을 들 수 있다.Examples of the compound having at least two ethylene groups at the terminal thereof include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, But are not limited to, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, But are not limited to, neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethyolpropane trimethacrylate, trimethylolpropane triacrylate, Trimethyolpropane triacrylate, glycerine di But are not limited to, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis Bis (4-methacryloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, methacryloxypolyethoxyphenyl) propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate (ethylene glycol diglycidyl ether dimethacrylate ), Diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, and the like. Glycerin polyglycidyl ether polymethacrylate and polyfunctional (meth) acrylate containing a urethane group, and the like.
상기 광중합성 화합물의 함량은 감광성 수지 조성물 중에 10 내지 65 중량%로 포함되는 것이 바람직하다. 상기 광중합성 화합물의 함량이 상기 범위 내에 있는 경우 광감도와 해상도, 밀착성 등을 강화시키는 효과를 얻을 수 있다.
The content of the photopolymerizable compound is preferably 10 to 65% by weight in the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the effect of enhancing photosensitivity, resolution, adhesion and the like can be obtained.
[D] 기타 첨가제[D] Other additives
본 발명의 감광성 수지 조성물은 필요에 따라 기타 첨가제를 더 포함할 수 있는데, 기타 첨가제로는 가소제로서 프탈산 에스테르 형태의 디부틸 프탈레이트, 디헵틸 프탈레이트, 디옥틸 프탈레이트, 디알릴 프탈레이트; 글리콜 에스테르 형태인 트리에틸렌 글리콜 디아세테이트, 테트라에틸렌 글리콜 디아세테이트; 산 아미드 형태인 p-톨루엔 설폰아미드, 벤젠설폰아미드, n-부틸벤젠설폰아미드; 트리페닐 포스페이트 등을 사용할 수 있다. The photosensitive resin composition of the present invention may further contain other additives as necessary. Examples of other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, Triethylene glycol diacetate in the glycol ester form, tetraethylene glycol diacetate; P-toluenesulfonamide in the acid amide form, benzenesulfonamide, n-butylbenzenesulfonamide; Triphenyl phosphate and the like can be used.
본 발명에 있어서 감광성 수지 조성물의 취급성을 향상시키기 위해서 류코 염료나 착색 물질을 넣을 수도 있다.In the present invention, a leuco dye or a coloring material may be added to improve the handleability of the photosensitive resin composition.
상기 루코 염료로는, 트리스(4-디메틸아미노-2-메틸페닐)메탄, 트리스(4-디메틸아미노-2메틸페닐)메탄, 플루오란 염료 등을 들 수 있다. 그중에서도, 루코 크리스탈 바이올렛을 사용한 경우, 콘트라스트가 양호하여 바람직하다. 류코 염료를 함유하는 경우의 함유량은 감광성 수지 조성물 중에 0.1 내지 10 중량%가 바람직하다. 콘트라스트의 발현이라는 관점에서, 0.1중량% 이상이 바람직하고, 보존 안정성을 유지한다는 관점에서는 10 중량% 이하가 바람직하다.Examples of the Luco dyes include tris (4-dimethylamino-2-methylphenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane and fluororan dyes. Among them, when Luco Crystal Violet is used, the contrast is favorable. The content of the leuco dye is preferably 0.1 to 10% by weight in the photosensitive resin composition. From the viewpoint of the appearance of contrast, the content is preferably 0.1% by weight or more, and 10% by weight or less from the viewpoint of maintaining storage stability.
착색 물질로는, 예를 들어 톨루엔술폰산1수화물, 푸크신, 프탈로시아닌 그린, 오라민 염기, 파라마젠타, 크리스탈 바이올렛, 메틸 오렌지, 나일 블루 2B, 빅토리아 블루, 말라카이트 그린, 다이아몬드 그린, 베이직 블루 20 등을 들 수 있다. 상기 착색 물질을 함유하는 경우의 첨가량은 감광성 수지 조성물 중에 0.001 내지 1중량%가 바람직하다. 0.001중량% 이상의 함량에서는 취급성 향상이라는 효과가 있고, 1중량% 이하의 함량에서는 보존 안정성을 유지한다는 효과가 있다.Examples of the coloring materials include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, aramine base, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, diamond green, . When the coloring material is contained, the amount added is preferably 0.001 to 1% by weight in the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving handling properties. When the content is 1% by weight or less, storage stability is maintained.
그 외에 기타 첨가제로는 열중합 방지제, 염료, 변색제(discoloring agent), 밀착력 촉진제 등을 더 포함할 수 있다. Other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.
본 발명에서는 상기와 같은 조성으로 된 감광성 수지 조성물은 드라이 필름 포토레지스트용 감광성 수지 조성물로 제조할 수 있으며, 폴리에틸렌테레프탈레이트와 같은 통상의 기재 필름 위에 통상의 코팅 방법을 이용하여 두께 10 내지 400㎛로 감광성 수지층을 코팅시킨 다음, 건조시키고, 상기 건조된 감광성 수지층은 상면에 폴리에틸렌과 같은 통상의 보호 필름을 이용하여 라미네이션시켜 드라이 필름을 제조할 수 있다. 이와 같이 제조된 드라이 필름은 노광, 현상시켜 각각의 물성을 평가하는 방법으로 수행한다. 상기 노광은 UV, 가시광선 레이저 등을 포함하는 Laser Direct 노광기를 이용하는 것이 바람직하다.
In the present invention, the photosensitive resin composition having the above composition may be prepared from a photosensitive resin composition for a dry film photoresist. The photosensitive resin composition may be coated on a conventional base film such as polyethylene terephthalate by a conventional coating method to a thickness of 10 to 400 占 퐉 The photosensitive resin layer is coated and dried, and the dried photosensitive resin layer is laminated on the upper surface using a conventional protective film such as polyethylene to produce a dry film. The thus prepared dry film is subjected to a method of evaluating physical properties by exposure and development. The exposure is preferably performed using a Laser Direct exposure apparatus including UV, visible light laser, and the like.
이하 본 발명의 바람직한 실시예 및 비교예를 설명한다. 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일 뿐, 본 발명이 하기한 실시예에 한정되는 것은 아니다.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.
[실시예 3과 비교예 1 내지 7][Example 3 and Comparative Examples 1 to 7]
드라이 필름 포토레지스트용 감광성 수지 조성물은 하기 표 1과 같은 조성에 따라 조합 및 코팅하여 평가하였다. 우선 광중합 개시제류들을 용매인 메틸에틸케톤(MEK)과 메탄올(MeOH)에 녹인 후, 광중합성 모노머와 알칼리 현상성 바인더 폴리머를 첨가하여 기계적 교반기를 이용하여 약 1시간 정도 혼합하여 감광성 수지 조성물을 수득하였다. 상기 수득된 감광성 수지 조성물을 30㎛의 PET 필름 위에 코팅 바(bar)를 이용하여 코팅시켰다. 코팅된 감광성 수지 조성물층은 열풍오븐을 이용하여 건조시키는데, 이때 건조 온도는 80℃이고, 건조 시간은 5분이며, 건조후 감광성 수지 조성물층 두께는 30㎛이였다. 건조가 완료된 필름은 감광성 수지층 위에 보호필름(PE)를 이용하여 라미네이션하였다.The photosensitive resin composition for a dry film photoresist was evaluated by combining and coating according to the composition shown in Table 1 below. First, photopolymerization initiators were dissolved in methyl ethyl ketone (MEK) and methanol (MeOH) as solvents. Then, a photopolymerizable monomer and an alkali developable binder polymer were added and mixed for about 1 hour using a mechanical stirrer to obtain a photosensitive resin composition Respectively. The photosensitive resin composition thus obtained was coated on a 30 mu m PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven at a drying temperature of 80 ° C. and a drying time of 5 minutes. The thickness of the photosensitive resin composition layer after drying was 30 μm. The dried film was laminated on the photosensitive resin layer using a protective film (PE).
드라이 필름의 반응성은 드라이 필름을 CCL위에 라미네이션 장비(Hakuto Mach610i)를 이용하여 110℃, 라미네이션 롤 압력 4kgf/cm2, 속도 2.0m/min로 라미네이션시키고, 드라이 필름의 표면 위에 Stuffer Step Tablet을 위치시킨 다음, INPREX IP-3600H를 이용하여 노광시켰다. 이와 같이 노광된 드라이 필름을 Na2CO3 1중량% 수용액, 30℃, 스프레이 압력 1.5kgf/cm2의 조건에서 현상시켰다. The reactivity of the dry film was evaluated by laminating the dry film on a CCL using a lamination equipment (Hakuto Mach610i) at 110 ° C, a lamination roll pressure of 4 kgf / cm 2 and a speed of 2.0 m / min, placing the Stuffer Step Tablet on the surface of the dry film Then, exposure was performed using INPREX IP-3600H. The exposed dry film was developed in a 1 wt% aqueous solution of Na 2 CO 3 at 30 ° C and a spray pressure of 1.5 kgf / cm 2 .
드라이 필름의 회로물성은 주어진 감도에서 KOLON Test Artwork을 이용하여 평가하였으며, 그 결과를 하기 표 2에 나타내었다.The circuit properties of the dry film were evaluated using a KOLON Test Artwork at a given sensitivity, and the results are shown in Table 2 below.
(Nippon Kayaku)(5) UX-4001-M35
(Nippon Kayaku) (5)
(Nippon Kayaku)(6) UX-4101
(Nippon Kayaku) (6)
(QENTOP)(7) QU-2750
(QENTOP) (7)
(고형분 50%)KOLON BP-1 (8)
(Solid content 50%)
(주) (1) BCIM : 2,2'-비스(2-클로로페닐)-4,4'-5,5'-테트라페닐비스이미다졸(1) BCIM: 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenylbisimidazole
(2) BPE-500 :2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane(2) BPE-500: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
(3) M281 : polyethylene glycol dimethacrylate(3) M281: polyethylene glycol dimethacrylate
(4) UX-0937 : 폴리에테르계 우레탄 올리고머(중량평균분자량: 4,000g/mol, 관능기수 :올리고머 양 쪽 말단에 아크릴레이트기가 결합된 것으로서 2개의 아크릴레이트기를 가짐)(4) UX-0937: polyether-based urethane oligomer (weight average molecular weight: 4,000 g / mol, number of functional groups: oligomer having two acrylate groups with acrylate groups bonded to both ends)
(5) UX-4001-M35: 폴리에테르계 우레탄 올리고머(중량평균분자량: 35,000g/mol, 관능기수 :올리고머 양 쪽 말단에 아크릴레이트기가 결합된 것으로서 2개의 아크릴레이트기를 가짐)(5) UX-4001-M35: polyether-based urethane oligomer (weight average molecular weight: 35,000 g / mol, number of functional groups: oligomer having two acrylate groups,
(6) UX-4101 : 폴리에스테르계 우레탄 올리고머(중량평균분자량: 6,500g/mol, 관능기수 :올리고머 양 쪽 말단에 아크릴레이트기가 결합된 것으로서 2개의 아크릴레이트기를 가짐)(6) UX-4101: Polyester-based urethane oligomer (weight average molecular weight: 6,500 g / mol, number of functional groups: oligomer having two acrylate groups,
(7) QU-2750 : 폴리카보네이트계 우레탄 올리고머(중량평균분자량: 25,000g/mol, 관능기수 :올리고머 양 쪽 말단에 아크릴레이트기가 결합된 것으로서 2개의 아크릴레이트기를 가짐)(7) QU-2750: Polycarbonate-based urethane oligomer (weight average molecular weight: 25,000 g / mol, number of functional groups: oligomer having two acrylate groups with acrylate groups bonded to both ends)
(8) KOLON BP-1 : Methacryliacid : Acrylc acid : Methylmethacrylate = 10:10:80 비율의 선형고분자
(8) KOLON BP-1: Methacryliacid: Acrylic acid: Methylmethacrylate = 10: 10: 80 ratio of linear polymer
상기 실시예 및 비교예에서 제조된 드라이 필름 포토 레지스트를 이용하여 다음과 같이 동판에 대한 노광량, 광감도, 세선 밀착력, 해상도, 텐트 신뢰성 등을 측정하였으며, 그 결과를 하기 표 2에 나타내었다.
Using the dry film photoresist prepared in the above Examples and Comparative Examples, the exposure amount, photosensitivity, fine line adhesion, resolution, and tent reliability of the copper plate were measured as follows. The results are shown in Table 2 below.
(1) 노광량 측정(1) Measurement of exposure dose
노광장치 INPREX IP-3600H를 사용하여 노광하였다.
And exposed using an exposure apparatus INPREX IP-3600H.
(2) 광감도 측정(2) Photosensitivity measurement
반응성의 측도로 사용되는 감도는 Stouffer Graphic Arts Equipment Co.의 21단 스텝 tablet을 사용하여 레지스트를 기준으로 하여 측정하였다.
The sensitivity used as a measure of reactivity was measured on a resist basis using a 21-step tablet from Stouffer Graphic Arts Equipment Co.
(3) 세선 밀착력 측정(3) Measurement of adhesion of fine wire
실시예 및 비교예에서 제조된 감광성 드라이 필름 레지스트의 PE 필름을 제거하고 난 후, 가열압착롤러를 이용하여 동판에 라미네이션시켰다. 여기에 5㎛ 단위로 나누어져 있는 10~150㎛의 배선패턴을 가지는 포토툴을 이용하여 노광하고 현상한 후 레지스트의 밀착력을 측정하였다.The PE film of the photosensitive dry film resist prepared in Examples and Comparative Examples was removed and laminated on a copper plate using a heat press roller. After exposing and developing the resist using a phototool having a wiring pattern of 10 to 150 mu m divided into 5 mu m units, the adhesion of the resist was measured.
밀착력의 배선패턴은 Line/Space=x:400(단위:㎛)이며, 독립 세선 중 사행을 제외한 직선의 최소값을 읽어 표 2에 기재하였다.
The wiring pattern of adhesion is Line / Space = x: 400 (unit: 占 퐉), and the minimum value of the straight line excluding the meandering line among the independent fine lines is read in Table 2.
(4) 해상도 측정(4) Resolution measurement
Line/Space=10:10 ~ 150:150(단위:㎛)의 배선패턴을 가지는 포토툴을 이용하여 노광하고 현상한 후 레지스트의 해상도를 측정하였다. 해상도는 노광 후의 현상에 의해서 형성된 레지스트 패턴에 있어서, 미노광부가 깨끗하게 제거된 패턴의 최소값을 읽어 표 2에 기재하였다.
Line / space = 10: 10-150: 150 (unit: 占 퐉), and the resist resolution was measured. The resolution of the resist pattern formed by the development after exposure is shown in Table 2 by reading the minimum value of the pattern in which the unexposed portions are cleanly removed.
(5) 텐트 신뢰성 측정(5) Tent reliability measurement
직경 6mm 구멍이 100개인 1.6mm 두께의 CCL위에 라미네이션 장비(Hakuto Mach610i)를 이용하여 110℃, 라미네이션 롤 압력 4kgf/cm2, 속도 2.0m/min로 드라이 필름을 라미네이션시킨 후에 드라이 필름의 표면위에 Stuffer Step Tablet을 위치시킨 후, INPREX IP-3600H를 이용하여 21단 스텝 tablet 기준으로 8단이 되는 에너지의 양으로 노광시키고, Na2CO3 1중량% 수용액, 30℃, 스프레이 압력 1.5kgf/cm2의 조건에서 60초간 현상시켰다. 구멍 위에 형성된 광경화막의 파괴 개수를 측정하여 텐트 파괴율을 계산하였다. 그리고 6mm 구멍 위에 형성된 광경화막에 지름이 3mm인 프로브를 이용하여 파단까지의 강도(N)와 신장(mm)을 측정하였다.
A dry film was laminated on a CCL having a diameter of 6 mm and a thickness of 1.6 mm using a lamination equipment (Hakuto Mach610i) at a lamination roll pressure of 4 kgf / cm 2 and a speed of 2.0 m / min at 110 ° C., After the step tablets were placed, they were exposed using an INPREX IP-3600H in an energy amount of 8 stages based on a 21-step tablet, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C and a spray pressure of 1.5 kgf / cm 2 For 60 seconds. The tent destruction rate was calculated by measuring the number of destruction of the photocured film formed on the hole. Then, the intensity (N) and the elongation (mm) to the fracture were measured using a probe having a diameter of 3 mm in the photocuring film formed on the 6 mm hole.
상기 표 2에 나타난 바와 같이, 실시예 3은 비교예 1 내지 4에 비해 광감도, 세선 밀착력 및 해상도가 동등 이상으로 향상됨을 확인할 수 있었고, 텐트 신뢰성에 있어서는 비교예 1 내지 4에 비해 현저히 높아진 것을 확인할 수 있었다. As shown in Table 2, it was confirmed that the photosensitivity, fine wire adhesion and resolution were improved to be equal to or better than those of Comparative Examples 1 to 4, and that the tent reliability was significantly higher than Comparative Examples 1 to 4 I could.
특히, 비교예 3은 폴리에스테르계 우레탄 올리고머를 사용하여 광경화막의 강도가 약하여 텐트 파괴율이 높아지는 문제가 있었고, 비교예 4는 폴리카보네이트게 우레탄 올리고머를 사용하여 광경화막의 신장이 작아서 텐트 파괴율이 높아지는 문제가 있었다. In particular, in Comparative Example 3, there was a problem that the strength of the photocurable film was weak and the tent destruction rate was increased by using a polyester-based urethane oligomer. In Comparative Example 4, the elongation of the photocured film was small using a polycarbonate urethane oligomer, There was an increasing problem.
본 발명에서는 광중합성 화합물에 폴리에테르계 우레탄 올리고머를 사용하여 광경화막의 강도와 신도를 향상시키는 작용에 의하여 텐트 파괴율이 높아지는 문제점을 해결할 수 있었다.In the present invention, the polyether-based urethane oligomer is used in the photopolymerizable compound to solve the problem that the tent destruction rate increases due to the action of improving the strength and elongation of the photocured film.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
상기 [A] 광중합 개시제는 n-페닐글리신을 포함하며,
상기 에틸렌성 불포화기 및 우레탄 결합을 가지며 중량평균분자량이 30,000 내지 50,000g/mol인 화합물은 폴리에테르 화합물의 말단 하이드록시기와 디이소시아네이트 화합물의 이소시아네이트기와의 반응에 유래하는 우레탄 화합물과, 하이드록시기 및 에틸렌성 불포화기를 갖는 화합물을 반응시켜 얻어지는 생성물이며, 에테르기를 가지는 것임을 특징으로 하는 드라이 필름 포토레지스트용 감광성 수지 조성물.
[A] a photopolymerization initiator; [B] alkali developable binder polymer; And [C] a photopolymerizable compound having an ethylenic unsaturated group and a urethane bond in the molecule and having a weight average molecular weight of 30,000 to 50,000 g / mol in an amount of 1 to 20% by weight based on the total weight of the photosensitive resin composition,
The [A] photopolymerization initiator includes n-phenylglycine,
The compound having an ethylenic unsaturated group and a urethane bond and having a weight average molecular weight of 30,000 to 50,000 g / mol is obtained by reacting a urethane compound derived from a reaction between a terminal hydroxy group of a polyether compound and an isocyanate group of a diisocyanate compound, A photosensitive resin composition for a dry film photoresist, which is a product obtained by reacting a compound having an ethylenically unsaturated group and has an ether group.
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises 0.5 to 20% by weight of the photopolymerization initiator [A], 30 to 70% by weight of the alkali developable binder polymer, and 10 to 65% by weight of the [C] Wherein the photosensitive resin composition for dry film photoresists is a photosensitive resin composition for a dry film photoresist.
The photosensitive resin composition for a dry film photoresist according to claim 1, wherein the n-phenylglycine is contained in an amount of 0.05 to 2% by weight based on the total weight of the photosensitive resin composition.
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| KR20100078035A (en) * | 2008-12-30 | 2010-07-08 | 주식회사 코오롱 | Photopolymerizable resin compositions |
| WO2011081150A1 (en) * | 2009-12-28 | 2011-07-07 | 旭硝子株式会社 | Photosensitive composition, partition wall, color filter and organic el element |
| KR20130073509A (en) * | 2011-12-23 | 2013-07-03 | 코오롱인더스트리 주식회사 | Photosensitive resin composition for dry film photoresist |
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| TW201527889A (en) | 2015-07-16 |
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