KR101675822B1 - Photosensitive Resin Composition for Dry Film Photoresist - Google Patents
Photosensitive Resin Composition for Dry Film Photoresist Download PDFInfo
- Publication number
- KR101675822B1 KR101675822B1 KR1020130093584A KR20130093584A KR101675822B1 KR 101675822 B1 KR101675822 B1 KR 101675822B1 KR 1020130093584 A KR1020130093584 A KR 1020130093584A KR 20130093584 A KR20130093584 A KR 20130093584A KR 101675822 B1 KR101675822 B1 KR 101675822B1
- Authority
- KR
- South Korea
- Prior art keywords
- photosensitive resin
- resin composition
- dry film
- film photoresist
- weight
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000007747 plating Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 (2-methylphenyl) Diethylamino Chemical group 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 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
- 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
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 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
- 238000002845 discoloration Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 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 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
- 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 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
- 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 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 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
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 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
- KFZANTDNOBVWKZ-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropoxy)phenyl]-2-phenylethanone Chemical compound CC(C)COC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 KFZANTDNOBVWKZ-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
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- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
본 발명은 드라이 필름 포토레지스트에 포함되는 감광성 수지 조성물에 관한 것으로, 보다 구체적으로는, 우수한 세선 밀착성과 해상도를 유지하면서도 박리속도가 빠르고, 박리속도가 빠르고, 도금액에 대한 내성이 뛰어나 PCB 제조에 있어 품질과 생산성을 향상시킬 수 있다.The present invention relates to a photosensitive resin composition contained in a dry film photoresist, and more particularly, to a photosensitive resin composition contained in a dry film photoresist, which is excellent in fine line adhesion and resolution while exhibiting a rapid peeling speed, Quality and productivity can be improved.
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.
이러한, 일반적으로 드라이 필름 포토레지스트는 동장적층판(Copper Clad Laminates) 상에 적층되는 용도로 많이 사용된다. 이와 관련하여 인쇄회로기판(Printed Circuit Board, PCB)의 제조과정의 일 예로는, PCB의 원판소재인 동장적층판을 라미네이션하기 위해 먼저 전처리 공정을 거친다. 전처리공정은 외층공정에서는 드릴링, 디버링(deburing), 정면 등의 순이며, 내층공정에서는 정면 또는 산세를 거친다. 정면공정에서는 bristle brush 및 jet pumice 공정이 주로 사용되며, 산세는 soft etching 및 5wt% 황산 산세를 거칠 수 있다.Such a dry film photoresist is generally used for the purpose of being laminated on a copper clad laminate. In this regard, as an example of a manufacturing process of a printed circuit board (PCB), a preprocessing process is first performed to laminate a copper-clad laminate, which is the original material of the PCB. The pretreatment process is in the order of drilling, deburring, and frontal in the outer layer process, and is faced or pickled in the inner layer process. Bristle brush and jet pumice process are mainly used in the frontal process, and pickling can be done by soft etching and 5 wt% sulfuric acid pickling.
전처리 공정을 거친 동장적층판에 회로를 형성시키기 위해서는 일반적으로 동장적층판의 구리층 위에 드라이 필름 포토레지스트(이하, DFR이라 함)을 라미네이션한다. 이 공정에서는 라미네이터를 이용하여 DFR의 보호 필름을 벗겨내면서 DFR의 포토레지스트층을 구리 표면 위에 라미네이션시킨다. 일반적으로 라미네이션 속도 0.5∼3.5m/min, 온도 100∼130℃, 로울러 압력 가열롤압력 10∼90psi에서 진행한다.In order to form a circuit on the copper-clad laminate through the pretreatment process, a dry film photoresist (hereinafter referred to as DFR) is laminated on the copper layer of the copper clad laminate. In this process, the photoresist layer of the DFR is laminated on the copper surface while removing the protective film of the DFR using a laminator. Generally, the lamination speed is 0.5 to 3.5 m / min, the temperature is 100 to 130 캜, and the roller pressure is 10 to 90 psi.
라미네이션 공정을 거친 인쇄회로기판은 기판의 안정화를 위하여 15분 이상 방치한 후 원하는 회로패턴이 형성된 포토마스크를 이용하여 DFR의 포토레지스트에 대해 노광을 진행한다. 이 과정에서 포토마스크에 자외선을 조사하면 자외선이 조사된 포토레지스트는 조사된 부위에서 함유된 광개지제에 의해 중합이 개시된다. 먼저 초기에는 포토레지스트내의 산소가 소모되고, 다음 활성화된 모노머가 중합되어 가교반응이 일어나고 그 후 많은 양의 모노머가 소모되면서 중합반응이 진행된다. 한편 미노광부위는 가교 반응이 진행되지 않은 상태로 존재하게 된다.The laminated printed circuit board is exposed to the photoresist of the DFR using a photomask having a desired circuit pattern after being left for 15 minutes or more for stabilizing the substrate. When the ultraviolet rays are irradiated to the photomask in this process, the photoresist irradiated with ultraviolet rays starts to be polymerized by the photo-initiator contained in the irradiated site. Initially, the oxygen in the photoresist is consumed, and the next activated monomer is polymerized to initiate a crosslinking reaction, and then a large amount of monomer is consumed and polymerization proceeds. On the other hand, the unexposed portion exists in a state in which the crosslinking reaction does not proceed.
다음 포토레지스트의 미노광 부분을 제거하는 현상공정을 진행하는데, 알카리 현상성 DFR인 경우 현상액으로 0.8∼1.2wt%의 포타슘카보네이트 및 소듐카보네이트 수용액이 사용된다. 이 공정에서 미노광 부분의 포토레지스트는 현상액내에서 결합제 고분자의 카르복시산과 현상액의 비누화 반응에 의해서 씻겨나가고, 경화된 포토레지스트는 구리표면 위에 잔류하게 된다.Next, a developing process for removing the unexposed portion of the photoresist is carried out. In the case of the alkali developable DFR, 0.8 to 1.2 wt% of potassium carbonate and sodium carbonate aqueous solution are used as the developer. In this process, the photoresist of the unexposed portion is washed away by the saponification reaction between the carboxylic acid of the binder polymer and the developer in the developer, and the cured photoresist remains on the copper surface.
다음 내층 및 외층 공정에 따라 다른 공정을 거쳐 회로가 형성된다. 내층공정에서는 부식과 박리공정을 통하여 기판상에 회로가 형성되며 외층공정에서는 도금 및 텐팅공정을 거친 후 에칭과 솔더 박리를 진행하고 소정의 회로를 형성시킨다.The circuit is then formed through other processes depending on the inner and outer layer processes. In the inner layer process, a circuit is formed on the substrate through the etching and peeling process. In the outer layer process, the plating and the tentering process are performed, and etching and solder peeling are performed to form a predetermined circuit.
일반적으로 도금 공정에서 노광된 드라이 필름 포토레지스트는 강산 혹은 강알카리 액 환경에 놓이게 된다. 이러한 이유로 인해 내화학성이 부족할 경우, 드라이 필름 포토레지스트가 동장 적층판으로부터 이탈하는 현상이 발생한다.In general, the dry film photoresist exposed in the plating process is placed in a strong acid or strong alkaline solution environment. For this reason, when the chemical resistance is insufficient, the dry film photoresist is separated from the copper clad laminate.
특히, 드라이 필름 포토레지스트의 감광성 수지 조성물이 도금액을 오염시키면 도금 처리를 가한 기판 외관에 변색이 생기거나 도금 효율이 저하되어 단선의 원인이 될 수 있다. Particularly, if the photosensitive resin composition of the dry film photoresist contaminates the plating solution, discoloration may occur on the outer surface of the substrate subjected to the plating treatment or the plating efficiency may be lowered, which may cause breakage.
또한, 감광성 수지 조성물은 경화 후의 박리 특성이 요구된다. 박리 특성이 부족한 경우, 도금 처리 후의 레지스트 박리 공정에 있어서 미세한 배선 간의 레지스트를 박리하는 것이 곤란해져 박리시간이 늘어나 생산효율이 저하된다.
Further, the photosensitive resin composition is required to have a peeling property after curing. In the case where the delamination characteristics are insufficient, it is difficult to peel off the resist between fine wirings in the resist stripping process after the plating process, so that the stripping time is increased and the production efficiency is lowered.
본 발명의 주된 목적은 우수한 세선 밀착성과 해상도를 유지하면서도 박리속도가 빠르고, 도금액에 대한 내성이 뛰어난 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 is excellent in fastness to peel adhesion and resolution while exhibiting a rapid peeling speed and excellent resistance to a plating solution.
상기의 목적을 달성하기 위하여, 본 발명의 일 구현예는 [A] 광중합 개시제; [B] 알카리 현상성 바인더 폴리머; 및 [C] 광중합성 화합물을 포함하고, 상기 [C] 광중합성 화합물은 하기 화학식 1로 표시되는 화합물을 포함하는 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 [C] photopolymerizable compound comprises a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, l+n은 2 또는 3의 정수이고, m은 12 내지 18의 정수이다.In the general formula (1), l + n is an integer of 2 or 3, and m is an integer of 12 to 18.
본 발명의 바람직한 일 구현예에서, 상기 감광성 수지 조성물은 고형분 기준으로, [A] 광중합 개시제 2 내지 10 중량%, [B] 알카리 현상성 바인더 폴리머 20 내지 80중량% 및 [C] 광중합성 화합물 10 내지 70 중량%를 포함할 수 있다.In a preferred embodiment of the present invention, the photosensitive resin composition comprises, on a solid basis, 2 to 10% by weight of a photopolymerization initiator [A], 20 to 80% by weight of an alkali developable binder polymer, and [C] By weight to 70% by weight.
본 발명의 바람직한 일 구현예에서, 상기 화학식 1로 표시되는 화합물은 감광성 수지 조성물 고형분 총중량에 대하여, 10 내지 60 중량%로 포함할 수 있다.
In one preferred embodiment of the present invention, the compound represented by Formula 1 may be contained in an amount of 10 to 60% by weight based on the total weight of the solid content of the photosensitive resin composition.
본 발명에 따른 드라이 필름 포토 레지스트용 감광성 수지 조성물은 우수한 세선 밀착성과 해상도를 유지하면서도 박리속도가 빠르고, 도금액에 대한 내성이 뛰어나 PCB 제조에 있어 품질과 생산성을 향상시킬 수 있다.
The photosensitive resin composition for a dry film photoresist according to the present invention can improve the quality and productivity in the manufacture of PCBs because the photosensitive resin composition for a dry film photoresist has high speed of peeling and excellent resistance to a plating solution while maintaining excellent fine line adhesion and resolution.
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 [C] 광중합성 화합물은 하기 화학식 1로 표시되는 화합물을 포함하는 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 [C] photopolymerizable compound comprises a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, l+n은 2 내지 3의 정수이고, m은 12 내지 18의 정수이다.In Formula 1, 1 + n is an integer of 2 to 3, and m is an integer of 12 to 18.
본 발명에 따른 드라이 필름 포토레지스트용 감광성 수지 조성물은 [C] 광중합성 화합물에 상기 화학식 1로 표시되는 화합물을 적어도 1종 이상 포함함으로써, 우수한 드라이 필름 포토레지스트의 세선 밀착성과 해상도를 유지하면서도 박리속도가 빠르고, 도금액에 대한 뛰어난 내성을 가질 수 있다.
The photosensitive resin composition for a dry film photoresist according to the present invention contains at least one compound represented by the above formula (1) in the photopolymerizable compound [C], whereby the excellent dry film photoresist can be obtained, And can have excellent resistance to the plating solution.
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.
상기 광중합 개시제로 사용할 수 있는 화합물로는 2-메틸 안트라퀴논, 2-에틸 안트라퀴논 등의 안트라퀴논 유도체; 벤조인 메틸 에테르, 벤조페논, 페난트렌 퀴논, 4,4'-비스-(디메틸아미노)벤조페논 등의 벤조인 유도체를 들 수 있다.Examples of the compound that can be used as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; Benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrenequinone, and 4,4'-bis- (dimethylamino) benzophenone.
이외에도 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)-2하이드록시-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 중에서 선택된 화합물을 광중합 개시제로 사용할 수 있으나, 이에 한정되는 것은 아니다.(2-chlorophenyl) -4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2- 2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3, 1-chloro-4-propoxyoxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan- 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4- Dimethyl aminobenzoate, butyl 4-dimethylaminoben 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzylketone dimethyl acetal, benzyl ketone? -Methoxydiethyl acetal, 1 Benzoyl benzoate, bis [4-dimethylaminophenyl) ketone, 4,4'-bis (2-methylphenyl) Diethylamino) benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone , Dibenzosuberone,?,? -Dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as photopolymerization initiators, In it not limited.
상기 광중합 개시제의 함량은 고형분 기준으로, 감광성 수지 조성물 총 중량에 대하여 2 내지 10중량%로 포함된다. 상기 광중합 개시제의 함량이 상기 범위 내에 있는 경우 충분한 감도를 얻을 수 있다.
The content of the photopolymerization initiator is 2 to 10% by weight based on the total weight of the photosensitive resin composition based on the solid content. 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 중량평균분자량이 30,000 내지 150,000이며, 유리전이온도는 20 내지 150℃인 고분자 화합물로서, 고형분 기준으로 감광성 수지 조성물 총중량에 대하여, 20 내지 80중량%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 is a polymer having a weight average molecular weight of 30,000 to 150,000 and a glass transition temperature of 20 to 150 ° C in consideration of coating property, followability, and mechanical strength of the resist itself after formation of a circuit, As a compound, 20 to 80% by weight based on the total weight of the photosensitive resin composition based on the solid content. 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.
이상 또는 이하에서 중량평균분자량은 Waters 450 GPC를 이용하여 폴리스타이렌을 스텐다드로 측정하였고, 컬럼은 Shodex 105, 104, 103을 사용하였으며, 유리전이온도는 Perkin Elmer사의 DSC 7을 이용하여 측정하였다.
The weight average molecular weight was measured by using Waters 450 GPC, polystyrene as a standard, Shodex 10 5 , 10 4 , and 10 3 columns, and the glass transition temperature was measured using a Perkin Elmer DSC 7 .
[C] 광중합성 화합물[C] Photopolymerizable compound
본 발명의 광중합성 화합물은 하기 화학식 1로 표시되는 화합물을 단독으로 사용하거나, 또는 말단에 적어도 2 개 이상의 에틸렌기를 포함하는 단량체와 함께 사용할 수 있다.The photopolymerizable compound of the present invention can be used alone or in combination with a monomer having at least two ethylene groups at the terminal.
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, l+n은 2 또는 3의 정수이고, m은 12 내지 18의 정수이다.In the general formula (1), l + n is an integer of 2 or 3, and m is an integer of 12 to 18.
상기 화학식 1로 표시되는 화합물은 감광성 수지 조성물의 소수성을 향상시켜 현상액 및 도금액에 대한 내성을 현격히 증가시키고, 경화막의 박리 시간을 단축시킬 수 있다.The compound represented by the above formula (1) can improve the hydrophobicity of the photosensitive resin composition to remarkably increase the resistance to the developer and the plating solution, and shorten the peeling time of the cured film.
본 발명에서는 상기 화학식 1로 표시되는 화합물을 감광성 수지 조성물 고형분 총 중량에 대하여 10 ~ 60중량%로 포함하는 것이 바람직하며, 더욱 바람직하게는 20 ~ 40중량%일 수 있다. In the present invention, the compound represented by the formula (1) is preferably contained in an amount of 10 to 60% by weight, more preferably 20 to 40% by weight based on the total weight of the solid content of the photosensitive resin composition.
만일 상기 화학식 1로 표시되는 화합물의 함량이 감광성 수지 조성물 고형분 총 중량에 대하여, 10 중량% 미만일 경우, 화학식 1로 표시되는 화합물의 첨가에 따른 효과가 미흡하고, 60중량%를 초과할 경우에는 소수성이 증가하여 노광 후 현상 공정에서의 현상시간이 급격히 증가하는 문제점이 발생될 수 있다.If the content of the compound represented by the formula (1) is less than 10% by weight based on the total weight of the solid content of the photosensitive resin composition, the effect due to the addition of the compound represented by the formula (1) is insufficient. And the development time in the post-exposure development process may be rapidly increased.
본 발명의 광중합성 화합물은 상기 화학식 1로 표시되는 화합물 이외에도 말단에 적어도 2개의 에틸렌기를 포함하는 단량체를 포함할 수 있다.The photopolymerizable compound of the present invention may contain a monomer having at least two ethylene groups at the terminal thereof in addition to the compound represented by the above formula (1).
상기 말단에 적어도 2개의 에틸렌기를 포함하는 단량체로는 에틸렌글리콜디메타크릴레이트(ethylene glycol dimethacrylate), 디에틸렌글리콜디메타크릴레이트(diethylene glycol dimethacrylate), 테트라에틸렌글리콜디메타크릴레이트(tetraethylene glycol dimethacrylate), 프로필렌글리콜디메타크릴레이트(propylene 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), 우레탄기를 함유한 다관능 (메트)아크릴레이트 등을 들 수 있다.Examples of the monomer having at least two ethylene groups at the terminal thereof include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, Hexane glycol dimethacrylate, trimethyolpropane trimethacrylate, trimethyolpropane triacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, (glycerin dimethacrylate), pentaerythritol dimethacrylate But are not limited to, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis (4-methacryloxy diethoxyphenyl) propane (2 2-bis (4-methacryloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, A diethylene glycol diglycidyl ether dimethacrylate, a phthalic acid diglycidyl ester dimethacrylate, a glycerin polyglyceride ether polymethacrylate, lycidyl ether polymethacrylate, and polyfunctional (meth) acrylate containing urethane groups.
상기 광중합성 화합물의 함량은 고형분 기준으로 감광성 수지 조성물 총 중량에 대하여, 10 내지 70중량%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 70% by weight based on the total weight of the photosensitive resin composition based on the solid content. 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] 용제 및 기타 첨가제[D] Solvents and other additives
본 발명의 감광성 수지 조성물의 용제로는 일반적으로 메틸에틸케톤(MEK), 메탄올, THF, 톨루엔, 아세톤 중에서 선택된 것을 사용하며 상기 용제로 특별히 한정되어지는 것은 아니며, 함량 역시, 광중합 개시제, 알카리 현상성 바인더 폴리머 및 광중합성 화합물의 함량에 따라 조절하여 함유될 수 있다.As the solvent for the photosensitive resin composition of the present invention, a solvent selected from among methyl ethyl ketone (MEK), methanol, THF, toluene and acetone is generally used, and the content is not limited to the photopolymerization initiator, The binder polymer and the photopolymerizable compound.
또한, 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. In addition, the photosensitive resin composition of the present invention may further contain other additives as required. 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 루이코 염료나 착색 물질을 넣을 수도 있다. 상기 루이코 염료로는, 트리스(4-디메틸아미노-2-메틸페닐)메탄, 트리스(4-디메틸아미노-2메틸페닐)메탄, 플루오란 염료 등을 들 수 있다. 그중에서도, 루이코 크리스탈 바이올렛을 사용한 경우, 콘트라스트가 양호하여 바람직하다. 루이코 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.In the present invention, a ricoco dye or a coloring material may be added to improve the handleability of the photosensitive resin composition. Examples of the Ruicho dyes include tris (4-dimethylamino-2-methylphenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane and fluororan dyes. Among them, when using Ruicho crystal violet, it is preferable because contrast is good. The content of the Luikos dye in the photosensitive resin composition is preferably 0.1 to 10% by weight. 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 5 내지 200㎛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.
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 to a thickness of 5 to 200 mu m 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.
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.
[[ 제조예Manufacturing example 1] One]
4구 둥근바닥 플라스크에 기계식 교반기(mechanical stirrer)와 환류장치를 장착한 다음, 질소로 플라스크 내부를 퍼지하였다. 상기 질소로 퍼지된 플라스크에 MEK(Methyl Ethyl Ketone) 90g 및 PGMEA(Propylene Glycol Monomehtyl Ether Acetate) 10g를 투입한 다음, 아조비스이소부티로니트릴(azobisisobutyronitrile, AIBN) 0.8g을 투입하여 완전히 용해시켰다. 여기에 메틸메타크릴산 20g, 메틸메타크릴레이트 70g 및 스티렌모노머 10g 단량체 혼합물을 투입하고, 80℃까지 승온한 다음 6시간 동안 중합하여 알칼리 현상성 바인더 폴리머를 제조하였다.
A four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then purged with nitrogen into the flask. 90 g of Methyl (Methyl Ethyl Ketone) and 10 g of PGMEA (PGMEA) were added to the flask purged with nitrogen, and then 0.8 g of azobisisobutyronitrile (AIBN) was added thereto to completely dissolve. 20 g of methyl methacrylate, 70 g of methyl methacrylate and 10 g of a monomer mixture of styrene monomer were charged, the temperature was raised to 80 DEG C and polymerization was carried out for 6 hours to prepare an alkali developable binder polymer.
[[ 실시예Example 1 내지 3과 1 to 3 and 비교예Comparative Example 1 및 2] 1 and 2]
드라이 필름 포토레지스트용 감광성 수지 조성물은 하기 표 1과 같은 조성에 따라 조합 및 코팅하여 평가하였다. 우선 광중합 개시제류들을 용제인 메틸에틸케톤(MEK)에 녹인 후, 광중합성 화합물과 제조예 1의 알칼리 현상성 바인더 폴리머를 첨가하여 기계적 교반기를 이용하여 약 1시간 정도 혼합하여 감광성 수지 조성물을 수득하였다. 상기 수득된 감광성 수지 조성물을 40㎛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 40㎛이였다. 건조가 완료된 필름은 감광성 수지층 위에 보호필름(폴리에틸렌)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) as a solvent. Then, a photopolymerizable compound and an alkali developable binder polymer of Preparation Example 1 were added and mixed for about 1 hour using a mechanical stirrer to obtain a photosensitive resin composition . The photosensitive resin composition thus obtained was coated on a 40 탆 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 40 μm. The dried film was laminated on the photosensitive resin layer using a protective film (polyethylene).
Component (% by weight)
Photopolymerization initiator
Photopolymerizable compound
additive
(1) EAB: 4,4’-(비스디에틸아미노)벤조페논(Aldrich Chemical)
(2) BCIM: 2,2’-비스-(2-클로로페틸-4,5,4’,5’-테트라페닐비스이미다졸(Aldrich Chemical)
(3) M-2183: 본 발명 화학식 1에서, l+n는 3이며, m는 18임
(4) M-2053: 본 발명 화학식 1에서, l+n는 6이며, m는 12임
(5) BPE-500: 2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane(신나카무라)
(6) 루이코 크리스탈 바이올렛: 일본 Hodogaya Co.
(7) 다이아몬드 그린 GH: 일본 Hodogaya Co.(week)
(1) EAB: 4,4 '- (bisdiethylamino) benzophenone (Aldrich Chemical)
(2) BCIM: 2,2'-bis- (2-chlorophenyl-4,5,4 ', 5'-tetraphenylbisimidazole (Aldrich Chemical)
(3) M-2183: In the present invention, l + n is 3 and m is 18
(4) M-2053: In the present invention, l + n is 6 and m is 12
(5) BPE-500: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (Shin Nakamura)
(6) Rui Ko Crystal Violet: Japan Hodogaya Co.
(7) Diamond Green GH: Japan Hodogaya Co.
상기 조성에 의해 제조된 감광성 수지 조성물을 사용하여 제조된 드라이 필름 포토레지스트는 다음과 같은 공정으로 수행하였다.
The dry film photoresist prepared using the photosensitive resin composition prepared above was subjected to the following steps.
<라미네이션><Lamination>
드라이 필름 포토레지스트를 브러시(brush) 연마 처리된 1.6mm 두께의 동장적층판에 기판 예열롤 온도 120℃, 라미네이터 롤 온도 115℃, 롤 압력 4.0kgf/㎠, 롤 속도 2.5min/m의 조건으로 HAKUTO MACH 610i를 이용하여 라미네이션을 수행하였다.
A dry film photoresist was applied to a 1.6 mm thick copper-clad laminated plate with a dry film photoresist under the conditions of a substrate preheating roll temperature of 120 캜, a laminator roll temperature of 115 캜, a roll pressure of 4.0 kgf / cm 2, and a roll speed of 2.5 min / 610i. ≪ / RTI >
<현상 및 해상도><Phenomenon and resolution>
동장적층판에 라미네이션한 드라이 필름 포토레지스트를 회로평가용 포토마스크를 사용하여 Perkin-ElmerTM OB7120(평행광 노광기)을 이용하여 40mJ의 노광량으로 자외선을 조사한 후 20분 방치하였다. 그 후 Na2CO3 1.0wt% 수용액으로 Spray 분사 방식의 현상조건으로 현상을 실시하였다. 동장 적층판 상의 미노광 부위의 드라이 필름 포토레지스트가 현상액에 완전히 씻겨지기까지 소요된 시간을 초시계를 이용하여 측정하였으며(최소현상시간) 제품 평가시는 브레이크 포인트 50%로 고정하였다(최소현상시간의 2배).
The dry film photoresist laminated on the copper-clad laminate was irradiated with ultraviolet rays at an exposure dose of 40 mJ using a Perkin-Elmer (TM) OB7120 (parallel light exposing machine) using a circuit evaluation photomask, and left for 20 minutes. Thereafter, the development was carried out under the development conditions of spraying method with a 1.0 wt% aqueous solution of Na 2 CO 3 . The time taken until the dry film photoresist on the uncoated portion of the copper clad laminate was completely washed in the developing solution was measured using a stopwatch (minimum developing time), and the product was fixed at a breaking point of 50% ship).
상기 실시예 및 비교예에서 제조한 감광성 수지 조성물을 사용하여 제조된 드라이 필름 포토레지스트의 물성을 아래 방법으로 측정하여 그 결과를 하기 표 2에 나타내었다.The properties of the dry film photoresist prepared using the photosensitive resin compositions prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.
<세선 밀착력(단위: ㎛)>≪ Fine wire adhesion (unit: 占 퐉)
현상 후 독립된 레지스트가 살아남아 있는 최소선폭으로 ZEISS AXIOPHOT Microscope으로 측정하였다.The ZEISS AXIOPHOT Microscope was used to measure the minimum line width at which independent resist remained after development.
<해상도(단위: ㎛)><Resolution (unit: 탆)>
회로라인과 회로라인 사이의 공간을 1:1로 하여 측정한 값으로, ZEISS AXIOPHOT Microscope으로 측정하였다.The space between the circuit line and the circuit line was measured at 1: 1 and measured with a ZEISS AXIOPHOT Microscope.
<도금에 대한 오염 방지성 평가><Evaluation of Pollution Prevention for Plating>
상기 감광성 수지 조성물로 제조된 드라이 필름 포토레지스트를 40cm×50cm 크기로 자르고, 보호필름을 제거하여 스텝 타블렛이 20단이 되는 노광량으로 노광을 실시한 다음, PET 필름을 박리하여 경화막을 얻었다. 이 경화막을 황산구리/황산 수용액의 도금액 1L에 3일간 침지하였다. 할셀 시험 욕조(정도시험기연구소 제품)를 이용하여 동판에 전류 2A로 15분간 전해 동도금을 실시하였다. The dry film photoresist made of the photosensitive resin composition was cut into a size of 40 cm x 50 cm, and the protective film was removed. The step tablet was exposed at an exposure amount of 20 steps, and then the PET film was peeled off to obtain a cured film. This cured film was immersed in 1 L of a plating solution of copper sulfate / sulfuric acid aqueous solution for 3 days. The copper plate was electrolytically plated for 15 minutes at a current of 2 A using a Halsel test bath (manufactured by Precision Testers Lab.).
경화막을 침지하지 않은 도금액을 레퍼런스로 하여 경화막을 침지한 도금액으로 도금했을 때 도금의 외관을 눈으로 관찰하여 도금 외관에 이상이 있거나 변색이 발생한 경우 X, 레퍼런스와 동일하여 전혀 이상이 없는 경우 ○로 판단하였다.When the plating solution immersed in the cured film is used as a reference and the plating solution immersed in the cured film is observed, the appearance of the plating is visually observed to see if there is any abnormality in the plating appearance or discoloration. X: Respectively.
< 박리속도(단위: 초)><Peeling speed (unit: second)>
박리속도는 제조된 감광성 드라이 필름 레지스트의 PE 필름을 제거하고 난 후, 가열압착롤러를 이용하여 동판에 라미네이션시키고, 감광성 수지 조성물을 노광하고 현상하여, 50mm×50mm의 크기의 광경화막을 제작하였다. 그리고 3% 수산화나트륨 수용액(온도 50℃)을 사용하여 박리를 하였다. 박리속도의 평가는 광경화막이 동판에서 떨어지는 시간을 측정하였다.The peeling speed was obtained by removing the PE film of the prepared photosensitive dry film resist and then laminating it on a copper plate using a heat press roller, exposing the photosensitive resin composition to light, and developing it to produce a photocured film having a size of 50 mm x 50 mm. And peeling was performed using a 3% aqueous solution of sodium hydroxide (at a temperature of 50 ° C). The evaluation of the peeling speed was performed by measuring the time at which the photocured film fell off the copper plate.
*2 해상도는 회로라인과 회로라인 사이의 공간을 1:1로 하여 측정한 값이다. * 1 Cessen adhesion is the minimum line width at which independent line width survives after development.
* 2 Resolution is measured by setting the space between the circuit line and the circuit line to 1: 1.
상기 표 2에 나타난 바와 같이, 실시예 1 내지 3은 비교예 1 및 2에 비해 유사 수준의 세선 밀착력 및 해상도를 유지하면서도 박리속도가 빠르고, 도금액에 대한 내성이 현저히 우수함을 알 수 있었다.
As shown in Table 2, it can be seen that Examples 1 to 3 have a higher peel rate and a better resistance to the plating solution while maintaining a similar level of fine line adhesion and resolution, as compared with Comparative Examples 1 and 2.
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 (3)
[화학식 1]
상기 화학식 1에서, l+n은 2 또는 3의 정수이고, m은 12 내지 18의 정수임.
[A] a photopolymerization initiator; [B] alkali developable binder polymer; And [C] a photopolymerizable compound, wherein the [C] photopolymerizable compound comprises a compound represented by the following formula (1):
[Chemical Formula 1]
In Formula 1, 1 + n is an integer of 2 or 3, and m is an integer of 12 to 18.
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises, on a solid basis, from 2 to 10% by weight of [A] a photopolymerization initiator, from 20 to 80% by weight of an alkali developable binder polymer, and from 10 to 70% by weight of a [C] % Of the photosensitive resin composition for a dry film photoresist.
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| PCT/KR2014/007306 WO2015020445A1 (en) | 2013-08-07 | 2014-08-07 | Photoresist resin composition for dry film photoresist |
| CN201480044108.9A CN105705998B (en) | 2013-08-07 | 2014-08-07 | For the photosensitive resin composition of dry film photoresist |
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| DE3223104A1 (en) * | 1982-06-21 | 1983-12-22 | Hoechst Ag, 6230 Frankfurt | PHOTOPOLYMERIZABLE MIXTURE AND PHOTOPOLYMERIZABLE COPY MATERIAL MADE THEREOF |
| JPH0718042A (en) * | 1993-06-30 | 1995-01-20 | Nippon Oil & Fats Co Ltd | Diluent for photopolymerizable resin and photopolymerizable resin composition |
| EP0797791A4 (en) * | 1994-12-13 | 1999-06-23 | Hercules Inc | Photosensitive compositions and clean running photopolymer printing plates therefrom |
| JP3876540B2 (en) * | 1998-07-27 | 2007-01-31 | 東レ株式会社 | Waterless planographic printing plate precursor |
| JP3859934B2 (en) * | 1999-05-27 | 2006-12-20 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board |
| JP3775142B2 (en) * | 1999-11-30 | 2006-05-17 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method |
| KR100718919B1 (en) * | 2001-11-15 | 2007-05-16 | 주식회사 코오롱 | Photosensitive resin composition |
| KR100521999B1 (en) * | 2002-09-03 | 2005-10-18 | 주식회사 코오롱 | Photopolymerizable Resin Composition For Sandblast Resist |
| JP2007003740A (en) * | 2005-06-23 | 2007-01-11 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition and photoresist film using same |
| CN101379434A (en) * | 2006-02-08 | 2009-03-04 | 日合·莫顿株式会社 | Photosensitive resin composition and photoresist film using the same |
| WO2008059670A1 (en) * | 2006-11-15 | 2008-05-22 | Taiyo Ink Mfg. Co., Ltd. | Photocurable/thermosetting resin composition, cured object, and printed wiring board |
| JP5393198B2 (en) * | 2009-02-27 | 2014-01-22 | 東京応化工業株式会社 | Photosensitive resin composition |
| KR102019580B1 (en) * | 2010-12-24 | 2019-09-06 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Photosensitive resin composition |
| CN102650826B (en) * | 2011-02-28 | 2014-08-13 | 中山市立顺实业有限公司 | Dry film photoresist containing specific adhesive and plasticizer |
| KR20130073509A (en) * | 2011-12-23 | 2013-07-03 | 코오롱인더스트리 주식회사 | Photosensitive resin composition for dry film photoresist |
| CN102608867B (en) * | 2012-03-27 | 2014-04-02 | 惠州联大电子材料有限公司 | Photosensitive water developing corrosion-resistant composition and photosensitive water developing corrosion-resistant dry film |
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