KR100553245B1 - Photopolymerizable composition - Google Patents
Photopolymerizable composition Download PDFInfo
- Publication number
- KR100553245B1 KR100553245B1 KR1020010043145A KR20010043145A KR100553245B1 KR 100553245 B1 KR100553245 B1 KR 100553245B1 KR 1020010043145 A KR1020010043145 A KR 1020010043145A KR 20010043145 A KR20010043145 A KR 20010043145A KR 100553245 B1 KR100553245 B1 KR 100553245B1
- Authority
- KR
- South Korea
- Prior art keywords
- derivative
- resin composition
- photosensitive resin
- formula
- photopolymerizable monomer
- Prior art date
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- 239000000203 mixture Substances 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 44
- -1 β-unsaturated carbonyl derivative compound Chemical class 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000011342 resin composition Substances 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 18
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004698 Polyethylene Substances 0.000 claims abstract description 3
- 239000004743 Polypropylene Substances 0.000 claims abstract description 3
- 150000002334 glycols Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000573 polyethylene Polymers 0.000 claims abstract description 3
- 229920001155 polypropylene Polymers 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- GDOBGDUGIFUCJV-UHFFFAOYSA-N 2,2-dimethylbutane;2-methylprop-2-enoic acid Chemical class CCC(C)(C)C.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O GDOBGDUGIFUCJV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 abstract description 10
- 230000007423 decrease Effects 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 11
- 239000012965 benzophenone Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 5
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920005596 polymer binder Polymers 0.000 description 5
- 239000002491 polymer binding agent Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 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
- 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
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 2
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N CCCOc1ccccc1 Chemical compound CCCOc1ccccc1 DSNYFFJTZPIKFZ-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 0 C*Oc1ccccc1 Chemical compound C*Oc1ccccc1 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
본 발명은 바인더 폴리머, 다관능성 α,β-불포화 카르보닐 유도체 화합물을 포함하는 광중합성 모노머 및 광개시제를 포함하는 감광성 수지조성물에 있어서, 다관능성 α,β-불포화 카르보닐 유도체 화합물로서 다음 화학식 1 또는 2로 표시되는, 페녹시 알킬류 또는 페녹시 폴리에테르류를 포함하며 말단에 메타크릴레이트기를 갖는 디아크릴레이트 또는 트리아크릴레이트, 또는 폴리우레탄 아크릴레이트를 포함하도록 조성된 것으로서, 이는 일반적인 감광성 수지조성물에서 나타나는 세선밀착력 증대시 해상도가 급격하게 나빠지는 현상을 개선하여 해상도의 저하가 없거나 최소화하면서 세선밀착력을 증대시키는 효과를 나타낸다.The present invention relates to a photopolymerizable resin composition comprising a binder polymer, a photopolymerizable monomer comprising a polyfunctional α, β-unsaturated carbonyl derivative compound and a photoinitiator, wherein the polyfunctional α, β-unsaturated carbonyl derivative compound is represented by the following Chemical Formula 1 or It is composed of diacrylates or triacrylates containing phenoxy alkyls or phenoxy polyethers represented by 2 and having a methacrylate group at the terminal, or polyurethane acrylate, which is a general photosensitive resin composition. In this case, the resolution decreases sharply when the fine line adhesion increases, which increases the fine line adhesion while minimizing or minimizing the resolution loss.
화학식 1Formula 1
상기 식에서, R1, R2는 서로 같거나 다른 것으로서 수소원자 또는 메틸기이고, Y는 페녹시알킬 또는 페녹시폴리에틸렌글리콜이 치환된 폴리에틸렌 글리콜 유도체, 폴리프로필렌 유도체, 폴리에틸렌과 프로필렌의 공중합 유도체, 알킬, 그리고 폴리우레탄 유도체를 나타낸다.Wherein R 1 and R 2 are the same or different and are hydrogen or methyl and Y is a polyethylene glycol derivative substituted with phenoxyalkyl or phenoxypolyethylene glycol, a polypropylene derivative, a copolymer derivative of polyethylene and propylene, alkyl, And polyurethane derivatives.
화학식 2Formula 2
상기 식에서, R3는 수소원자 또는 메틸기이고, Y는 상기 화학식 1에서 정의된 바와 같다. In the above formula, R 3 is a hydrogen atom or a methyl group, Y is as defined in the formula (1).
Description
도 1은 일반적인 인쇄회로기판에 회로를 형성하는 단계를 나타낸 도면이다. 1 is a view illustrating a step of forming a circuit on a general printed circuit board.
본 발명은 감광성 수지조성물에 관한 것으로서, 더욱 상세하게는 일반적인 감광성 수지조성물에서 나타나는 세선밀착력 증대시 해상도가 급격하게 나빠지는 현상을 개선하여 해상도의 저하가 없거나 최소화하면서 세선밀착력을 증대시킬 수 있는 감광성 수지조성물에 관한 것이다. The present invention relates to a photosensitive resin composition, and more particularly, a photosensitive resin capable of increasing fine line adhesion while reducing or minimizing resolution by improving a phenomenon in which resolution rapidly deteriorates when the fine line adhesion strength of a general photosensitive resin composition is increased. It relates to a composition.
인쇄회로기판(PCB: Printed Circuit Board)에 회로를 형성하는 데에는 통상 드라이필름 레지스트(Dry Film Resist)가 널리 사용되고 있다.Dry film resists are widely used to form circuits on printed circuit boards (PCBs).
드라이필름 레지스트는 감광성 수지조성물, 보호필름, 그리고 베이스 필름의 3층 구조로 구성되어 있으며, 유기용매 현상형 드라이필름 레지스트와 약알칼리 현상형 드라이필름 레지스트 2종이 개발되어 있다. 이중 유기용매 현상형 드라이필름 레지스트는 현상용액으로 유기용매(Chloro-organic solvent)를 사용하고 있으며, 약알칼리 현상형 드라이필름 레지스트는 약알칼리 수용액인 포타슘카보네이트 수용액이나 소듐카보네이트 수용액을 현상용액으로 사용하고 있다.The dry film resist is composed of a three-layer structure of a photosensitive resin composition, a protective film, and a base film. Two types of organic solvent developing dry film resists and weak alkali developing dry film resists have been developed. The organic solvent developing dry film resist uses a chloro-organic solvent as a developing solution, and the weak alkali developing dry film resist uses an aqueous potassium carbonate solution or an aqueous sodium carbonate solution as a developing solution. have.
따라서, 비용적으로나 환경적인 측면에서 알칼리 현상형 드라이필름 레지스트가 널리 사용되고 있으며, 이를 사용하여 인쇄회로기판에 회로를 형성하는 방법을 개략적으로 살펴보면 도 1과 같다.Therefore, an alkali developing dry film resist is widely used in terms of cost and environment, and a method of forming a circuit on a printed circuit board using the same is shown in FIG. 1.
도 1을 참조하여 설명하면, 우선 PCB의 원판소재인 구리적층판을 라미네이션하기 위해 먼저 전처리 공정(S10)을 거친다. 전처리 공정은 외층 공정에서는 드릴링, 디버링(deburing), 정면 등의 순이며, 내층공정에서는 정면 또는 산세를 거친다. 정면공정에서는 Bristle Brush 및 jet pumice 공정이 주로 사용되며, 산세는 soft etching 및 5중량% 황산 산세를 거친다. Referring to FIG. 1, first, a pretreatment step (S10) is first performed in order to laminate a copper laminated plate, which is a disc material of a PCB. The pretreatment process is in the order of drilling, deburring, front, etc. in the outer layer process, the front or pickling in the inner layer process. Bristle brush and jet pumice processes are mainly used in the frontal process, and pickling is performed through soft etching and 5% by weight sulfuric acid.
전처리 공정을 거친 구리적층판에 회로를 형성시키기 위해서는 일반적으로 구리적층판의 구리층 위에 드라이필름 레지스트를 라미네이션한다(S20). 이 공정에서는 라미네이터를 이용하여 드라이필름 레지스트의 보호필름을 벗겨내면서 드라이필름 레지스트의 포토레지스트층을 구리표면 위에 라미네이션시킨다. 일반적으로 라미네이션 속도 0.5∼3.5m/min, 온도 100∼130℃, 로울러 압력 가열롤 압력 10∼90psi에서 진행한다. In order to form a circuit on the copper laminated plate that has been subjected to the pretreatment process, a dry film resist is generally laminated on the copper layer of the copper laminated plate (S20). In this process, the photoresist layer of the dry film resist is laminated on the copper surface while peeling off the protective film of the dry film resist using a laminator. In general, the lamination speed is 0.5 to 3.5 m / min, temperature 100 to 130 ℃, roller pressure heating roll pressure 10 to 90 psi.
라미네이션 공정을 거친 인쇄회로기판은 기판의 안정화를 위하여 15분 이상 방치(S30)한 후 원하는 회로패턴이 형성된 포토마스크를 이용하여 드라이필름 레지스트이 포토레지스트에 대해 노광을 진행한다(S40). 이 과정에서 포토마스크에 자외선을 조사하면 자외선이 조사된 포토레지스트는 조사된 부위에 함유된 광개시제 에 의해 중합이 개시된다. 먼저 초기에는 포토레지스트 내의 산소가 소모되고, 다음 활성화된 모노머가 중합되어 가교반응이 일어나고 그 후 많은 양의 모노머가 소모되면서 중합반응이 진행된다. 한편, 미노광 부위는 가교반응이 진행되지 않은 상태로 존재하게 된다.After the lamination process, the printed circuit board is left to stand for at least 15 minutes (S30) to stabilize the substrate, and then the dry film resist is exposed to the photoresist using a photomask on which a desired circuit pattern is formed (S40). In this process, when ultraviolet rays are irradiated to the photomask, the photoresist irradiated with ultraviolet rays is initiated by the photoinitiator contained in the irradiated portion. Initially, oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause crosslinking reaction, and then a large amount of monomer is consumed to proceed with the polymerization reaction. On the other hand, the unexposed site is present in a state where the crosslinking reaction does not proceed.
다음, 포토레지스트의 미노광 부분을 제거하는 현상공정(S50)을 진행하는데, 알카리 현상성 드라이필름 레지스트인 경우 현상액으로 0.8∼1.2중량%의 포타슘카보네이트 및 소듐카보네이트 수용액을 사용한다. 이 공정에서 미노광 부분의 포토레지스트는 현상액 내에서 바인더 폴리머의 카르복시산과 현상액의 비누화 반응에 의해서 씻겨나가고 경화된 포토레지스트는 구리표면 위에 잔류하게 된다.Next, a developing step (S50) of removing the unexposed portion of the photoresist is performed. In the case of an alkaline developable dry film resist, 0.8 to 1.2 wt% of potassium carbonate and sodium carbonate aqueous solution are used as a 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 외층공정(S60)에 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. 따라서, 드라이필름 레지스트는 도금, 에칭 및 다른 화학적 공정에서 여러 가지 화학물질에 대한 화학내성을 가져야 한다. Next, a circuit is formed through different processes according to the inner layer and outer layer processes (S60). In the inner layer process, a circuit is formed on the substrate through a corrosion and peeling process, and in the outer layer process, after the plating and tenting process, etching and solder peeling are performed to form a predetermined circuit. Thus, dry film resists must have chemical resistance to various chemicals in plating, etching and other chemical processes.
한편, 드라이필름 레지스트를 이용하여 PCB에 회로를 패터닝하는 경우, 통상 0.1mm 정도까지의 회로선폭을 얻을 수 있다. On the other hand, when patterning a circuit on a PCB using a dry film resist, a circuit line width of up to about 0.1 mm can usually be obtained.
그러나, 최근 전자기기의 소형화, 경량화, 고성능화, 고신뢰성화에 따라 여기에 사용되는 인쇄회로기판에 대해서는 고밀도화, 고성능화, 고정밀화가 강력히 요구되고 있어 회로선폭을 보다 줄일 수 있는 방안이 요구되고 있는 실정이며, 이에 따라 드라이필름 레지스트의 해상도 향상 및 세선밀착력 증대 또한 요구되어지 고 있다.However, due to the recent miniaturization, light weight, high performance, and high reliability of electronic devices, high density, high performance, and high precision have been strongly required for printed circuit boards. Accordingly, it is also required to improve the resolution and fine wire adhesion of dry film resists.
해상도 및 세선밀착력을 증대시키는 방안으로 감광성 수지조성물을 구성하는 바인더 폴리머, 광중합성 모노머 및 광개시제 등 드라이필름 레지스트 자체에 관한 연구 및 공정개발 연구와 관련된 수많은 기술들이 진행되었다.In order to increase the resolution and fine line adhesion, numerous technologies related to the research and process development research on the dry film resist itself such as the binder polymer, the photopolymerizable monomer and the photoinitiator constituting the photosensitive resin composition have been conducted.
바인더 폴리머에 관한 연구에 있어서는 바인더 폴리머의 기본조성물 변경을 통하여 드라이필름 레지스트의 물성을 조절하는 연구가 진행되었으며, 광중합성 모노머의 경우에는 비스페놀 A를 포함하는 다관능성 α,β-불포화 카르보닐 화합물에 대한 연구를 비롯한 관련기술들이 보고되어 있다.In the research on the binder polymer, studies on controlling the physical properties of the dry film resist by changing the basic composition of the binder polymer have been conducted. In the case of the photopolymerizable monomer, a polyfunctional α, β-unsaturated carbonyl compound containing bisphenol A was applied. Related studies, including research, have been reported.
그런데, 세선밀착력과 고해상은 반비례 관계에 있는 바, 종래의 감광성 수지 조성물의 경우 고세선밀착력, 고해상을 구현하기 위해 세선밀착력을 증대시킬 경우 해상도가 급격히 나빠지며, 해상도를 증대시킬 경우 세선밀착력이 나빠지는 특성을 나타내는 문제가 있었다.However, the thin line adhesion and high resolution are inversely related. In the case of conventional photosensitive resin compositions, the fine line adhesion and the high resolution in order to realize high resolution sharply deteriorate the resolution, and the fine line adhesion worsens when the resolution is increased. There was a problem indicating the characteristics.
이에, 본 발명자들은 세선밀착력 증대시 해상도가 급격히 나빠지는 종래 감광성 수지조성물의 문제점을 해결하기 위해 연구노력하던 중, 페녹시 알킬 또는 페녹시 폴리에테르류를 포함하는 α,β-불포화 카르보닐 유도체 화합물을 기능성 모노머로서 도입한 결과, 레지스트의 밀착력을 획기적으로 증대시키면서 해상도 저하를 없애거나 최소화시킬 수 있음을 알게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors, while trying to solve the problem of the conventional photosensitive resin composition that the resolution sharply worsens when the fine line adhesion is increased, α, β-unsaturated carbonyl derivative compound containing phenoxy alkyl or phenoxy polyethers As a result of introducing the as a functional monomer, it was found that the resolution reduction can be eliminated or minimized while significantly increasing the adhesion of the resist, thereby completing the present invention.
따라서, 본 발명의 목적은 일반적인 감광성 수지조성물에서 나타나는 세선밀 착력 증대시 해상도가 급격히 나빠지는 현상을 개선하여 해상도를 유지시키거나 해상도의 저하를 최소화하면서 세선밀착력을 증대시킬 수 있는 감광성 수지조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a photosensitive resin composition that can improve the thin line adhesion while maintaining the resolution or minimizing the degradation of the resolution by improving the phenomenon that the resolution sharply worsens when the fine line adhesion is increased in the general photosensitive resin composition There is.
이와같은 목적을 달성하기 위한 본 발명의 감광성 수지조성물은 바인더 폴리머, 다관능성 α,β-불포화 카르보닐 유도체 화합물을 포함하는 광중합성 모노머 및 광개시제를 포함하는 것으로서, 상기 다관능성 α,β-불포화 카르보닐 유도체 화합물은 다음 화학식 1 또는 2로 표시되는, 페녹시 알킬류 또는 페녹시 폴리에테르류를 포함하며 말단에 메타크릴레이트기를 갖는 디아크릴레이트 또는 트리아크릴레이트, 또는 폴리우레탄 아크릴레이트인 것임을 그 특징으로 한다.The photosensitive resin composition of the present invention for achieving the above object includes a photopolymerizable monomer and a photoinitiator comprising a binder polymer, a polyfunctional α, β-unsaturated carbonyl derivative compound, and the polyfunctional α, β-unsaturated car The carbonyl derivative compound may be a diacrylate or a triacrylate, or a polyurethane acrylate, containing phenoxy alkyls or phenoxy polyethers represented by the following Chemical Formulas 1 or 2 and having a methacrylate group at the terminal thereof. It is done.
상기 식에서, R1, R2는 서로 같거나 다른 것으로서 수소원자 또는 메틸기이고, Y는 페녹시알킬 또는 페녹시폴리에틸렌글리콜이 치환된 폴리에틸렌 글리콜 유도체, 폴리프로필렌 유도체, 폴리에틸렌과 프로필렌의 공중합 유도체, 알킬, 그리고 폴리우레탄 유도체를 나타낸다.Wherein R 1 and R 2 are the same or different and are hydrogen or methyl and Y is a polyethylene glycol derivative substituted with phenoxyalkyl or phenoxypolyethylene glycol, a polypropylene derivative, a copolymer derivative of polyethylene and propylene, alkyl, And polyurethane derivatives.
상기 식에서, R3는 수소원자 또는 메틸기이고, Y는 상기 화학식 1에서 정의 된 바와 같다.
In the above formula, R 3 is a hydrogen atom or a methyl group, Y is as defined in the formula (1).
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 바인더 폴리머, 광중합성 모노머 및 광개시제를 포함하는 감광성 수지 조성물에 관한 것으로서, 각 조성성분을 구체적으로 살펴보면 다음과 같다.The present invention relates to a photosensitive resin composition comprising a binder polymer, a photopolymerizable monomer and a photoinitiator, and the respective composition components will be described in detail as follows.
(1)바인더 폴리머(1) binder polymer
본 발명에서 바인더 폴리머는 선형 아크릴산 고분자로서, 이는 둘 이상의 모노머들의 공중합을 통해 얻어진 공중합 아크릴산 고분자이다. 여기서 모노머로는 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 부틸메타크릴레이트, 부틸메타크릴레이트, 아크릴산, 메타크릴산, 2-히드록시에틸 아크릴레이트, 2-히드록시에틸 메타크릴레이트, 2-히드록시프로필 아크릴레이트, 2-히드록시프로필 메타크릴레이트, 아크릴아마이드, 메타크릴아마이드, 스티렌, α-메틸 스티렌 등을 들 수 있다.In the present invention, the binder polymer is a linear acrylic acid polymer, which is a copolymerized acrylic acid polymer obtained through copolymerization of two or more monomers. The monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, styrene, α-methyl styrene, and the like.
이와같은 모노머들로부터 합성된 선형 아크릴산 고분자는 드라이필름 레지스트의 코팅성, 추종성, 그리고 회로형성 후 레지스트 자체의 기계적 강도를 고려해서 평균분자량은 40,000∼150,000이며, 유리전이온도가 20∼120℃이고, 산가는 50∼250mgKOH/g인 고분자를 사용할 수 있다.The linear acrylic acid polymer synthesized from such monomers has an average molecular weight of 40,000 to 150,000, a glass transition temperature of 20 to 120 ° C, in consideration of the coating property, the followability of the dry film resist, and the mechanical strength of the resist itself after circuit formation. The acid value can use the polymer of 50-250 mgKOH / g.
(2)광중합성 모노머(2) photopolymerizable monomer
본 발명의 광중합성 모노머는 통상 감광성 수지 조성 중에 포함되는 모노머와 더불어 다관능성 α,β-불포화 카르보닐 유도체 화합물을 포함하는 바, 이는 광개시제에 의해서 개시반응이 일어나는 물질이다. 이와 같은 광중합성 모노머는 전체 감광성 수지조성물 중에서 10∼35중량%를 차지한다. The photopolymerizable monomer of the present invention usually contains a polyfunctional α, β-unsaturated carbonyl derivative compound together with the monomer contained in the photosensitive resin composition, which is a substance in which an initiation reaction occurs by a photoinitiator. Such photopolymerizable monomer accounts for 10 to 35% by weight in the total photosensitive resin composition.
본 발명의 감광성 수지에 있어서 광중합성 모노머로서 포함되는 다관능성 α,β-불포화 카르보닐 유도체 화합물은 특히 상기 화학식 1 또는 2로 표시되는 바와 같다.In the photosensitive resin of the present invention, the polyfunctional α, β-unsaturated carbonyl derivative compound included as the photopolymerizable monomer is particularly represented by the above formula (1) or (2).
상기 화학식 1 또는 2로 표시되는 바와 같이 다관능성 α,β-불포화 카르보닐 유도체 화합물은 분자 내의 보조사슬(side chain)에 페녹시 알킬류, 페녹시 폴리에테르류, 또는 페녹시 폴리에스테르류를 포함하며 말단에 메타크릴레이트기를 가지는 디아크릴레이트, 트리아크릴레이트 또는 폴리우레탄 아크릴레이트이다.As represented by Formula 1 or 2, the multifunctional α, β-unsaturated carbonyl derivative compound includes phenoxy alkyls, phenoxy polyethers, or phenoxy polyesters in the side chain in the molecule. And diacrylate, triacrylate or polyurethane acrylate having a methacrylate group at the terminal.
상기 화학식 1 또는 2에 있어서, 보조사슬에 포함되는 페녹시 알킬류, 페녹시 폴리에테르류, 또는 페녹시 폴리에스테르류, 즉 Y를 구체적으로 살펴보면 다음과 같다.In Formula 1 or 2, the phenoxy alkyls, phenoxy polyethers, or phenoxy polyesters, that is, Y contained in the auxiliary chain will be described in detail.
Y;, Y; ,
, ,
, ,
, ,
(여기서, R4는 또는 (x는 1∼12이다)이고, R5는 디이소시아네이트 유도체이고, R6는 폴리에테르 또는 폴리에스테르의 유도체이다.) Where R 4 is or (x is 1 to 12), R 5 is a diisocyanate derivative, and R 6 is a derivative of polyether or polyester.)
여기서, '디아크릴레이트 또는 트리아크릴레이트 화합물, 또는 폴리우레탄 아크릴레이트 화합물'이라 함은 주사슬의 구성성분이 알킬, 폴리에테르, 그리로 폴리우레탄 화합물인 유도체로서, 알킬사슬의 경우 탄소수 4∼32인 화합물이며, 폴리에테르 사슬인 경우 반복단위가 4∼30인 화합물이며, 폴리우레탄의 경우 폴리우레탄의 반복단위가 7이하인 주사슬 구조를 갖는 화합물을 의미한다. Here, the term "diacrylate or triacrylate compound or polyurethane acrylate compound" is a derivative whose main component is an alkyl, polyether, and polyurethane compound. It is a phosphorus compound, and, in the case of a polyether chain, it is a compound having a repeating unit of 4 to 30, and in the case of polyurethane, a compound having a main chain structure having a repeating unit of polyurethane of 7 or less.
그리고, '페녹시'는 페닐기에 있어서 C-O 결합을 갖는 1번 위치를 제외한 2~6번 위치의 수소원자 중의 적어도 하나가 C,N,O 또는 S 원소를 포함하는 작용기로 치환된 것으로, 여기서의 작용기라 함은 C,N,O 또는 S 원소를 포함하는 알킬, 알콕시 또는 이민 등을 포함할 수 있다. In addition, "phenoxy" is a phenyl group substituted with a functional group containing a C, N, O or S element at least one of the hydrogen atoms in positions 2-6 except for the position 1 having a CO bond, wherein The functional group may include alkyl, alkoxy or imine including C, N, O or S elements.
'페녹시 알킬'이라 함은 보조사슬(side chain)에 알킬체인, -O-알킬, 그리고 -CO2-알킬- 결합을 가지는 화합물로서, 알킬사슬의 탄소수가 2∼13인 디아크릴레이트 또는 트리아크릴레이트 화합물을 의미한다."Phenoxy alkyl" is a compound having an alkyl chain, -O-alkyl, and -CO 2 -alkyl- bond in the side chain, and dialkyl or tri-alkyl having 2 to 13 carbon atoms in the alkyl chain It means an acrylate compound.
그리고, '페녹시 폴리에테르'라 함은 보조사슬에 -폴리에테르-, 그리고 -CO-폴리에테르- 결합을 가지는 화합물로서, '에테르'란 에틸렌, 프로필렌, 부틸렌, 그 리고 펜틸렌글리콜의 유도체를 의미하며 반복단위가 1∼12인 디아크릴레이트 또는 트리아크릴레이트 화합물을 의미한다.In addition, "phenoxy polyether" is a compound having a -polyether- and -CO-polyether- bond in the auxiliary chain, 'ether' is a derivative of ethylene, propylene, butylene, and pentylene glycol It means a diacrylate or triacrylate compound having a repeating unit of 1 to 12.
상기 화학식 1 또는 2로 표시되는 모노머들은 감광성 수지조성물에서 동(Cu)과의 밀착력이 우수한 것으로 알려진 페녹시 그룹과의 상호작용으로 인하여 용이하게 세선밀착력을 증대시키는 역할을 한다.The monomers represented by Formula 1 or 2 serve to easily increase fine wire adhesion due to interaction with phenoxy groups which are known to have excellent adhesion with copper (Cu) in the photosensitive resin composition.
이와같은 다관능성 α,β-불포화 카르보닐 유도체 화합물은 바인더 폴리머 및 광개시제와 더불어 드라이필름 레지스트의 기본물성인 해상도 및 세선밀착력에 중요한 영향을 주는 인자로서 작용한다.Such a multifunctional α, β-unsaturated carbonyl derivative compound, together with a binder polymer and a photoinitiator, acts as an important factor in the resolution and fine line adhesion, which are the basic properties of dry film resists.
다관능성 α,β-불포화 카르보닐 유도체 화합물 이외에 사용할 수 있는 통상의 광중합성 모노머로는 주사슬의 구조가 폴리에테르디메타크릴레이트 유도체, 에톡시레이티드 비스페놀 디메타크릴레이트 유도체, 에톡시레이티드 트리메틸 프로판 트리메타크릴레이트 그리고 알킬디메타크릴레이트 유도체 등을 들 수 있다. Conventional photopolymerizable monomers that can be used in addition to the polyfunctional α, β-unsaturated carbonyl derivative compounds include a polyether dimethacrylate derivative, an ethoxylated bisphenol dimethacrylate derivative, and an ethoxylated main chain. Trimethyl propane trimethacrylate and alkyldimethacrylate derivatives.
여기서, 폴리에테르는 에틸렌글리콜, 프로필렌글리콜, 부틸렌글리콜, 펜틸렌글리콜, 에틸렌글리콜과 프로필렌글리콜의 공중합체로서 분자량이 200∼1,500인 화합물이며, 에톡시레이티드 비스페놀 디메타크릴레이트와 에톡시레이티드 트리메틸 프로판 트리메타크릴레이트는 에톡시의 반복단위가 4∼30인 화합물이고, 알킬 디메타크릴레이트 유도체는 주사슬인 알킬기의 분자량이 70∼500인 화합물이며 보조사슬에 C, N, O, S를 포함하는 작용기를 가지는 화합물을 통칭한다.Here, the polyether is a copolymer of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, ethylene glycol and propylene glycol, a compound having a molecular weight of 200 to 1500, ethoxylated bisphenol dimethacrylate and ethoxylay Tide trimethyl propane trimethacrylate is a compound having 4 to 30 repeating units of ethoxy, and an alkyl dimethacrylate derivative is a compound having a molecular weight of 70 to 500 of an alkyl group as the main chain and C, N, O, The compound which has a functional group containing S is named collectively.
상기 다관능성 α,β-불포화 카르보닐 유도체 화합물과 기타 광중합성 모노머를 포함하는 광중합성 모노머군에 있어서, 상기 화학식 1 또는 2로 표시되는 다관능성 α,β-불포화 카르보닐 유도체 화합물을 전체 광중합성 모노머군 중 2 내지 98중량%로 포함하고 기타 광중합성 모노머를 2~98중량%로 포함할 수 있다. In the photopolymerizable monomer group including the polyfunctional α, β-unsaturated carbonyl derivative compound and other photopolymerizable monomers, the polyfunctional α, β-unsaturated carbonyl derivative compound represented by Formula 1 or 2 may be totally photopolymerizable. It may contain from 2 to 98% by weight of the monomer group and may contain from 2 to 98% by weight of other photopolymerizable monomer.
만일, 상기 화학식 1 또는 2로 표시되는 다관능성 α,β-불포화 카르보닐 유도체 화합물을 광중합성 모노머군 중 2중량% 미만으로 첨가하면 상기 모노머로부터 밀착력 향상 효과를 기대하기 어렵다.If the polyfunctional α, β-unsaturated carbonyl derivative compound represented by Formula 1 or 2 is added in less than 2% by weight of the photopolymerizable monomer group, it is difficult to expect the effect of improving adhesion from the monomer.
그리고, 전체 감광성 수지조성물 중 화학식 1 또는 2로 표시되는 다관능성 α,β-불포화 카르보닐 유도체 화합물을 포함하는 광중합성 모노머를 10∼35중량%로 함유하는 바, 만일 광중합성 모노머의 함량이 전체 감광성 수지조성물 중 10중량% 미만이면 드라이 필름레지스트의 유리전이온도가 높아져 레지스트층이 취약(brittle)해지며 추종성이 급격히 떨어지고, 35중량% 초과면 드라이 필름레지스트의 유리전이온도가 너무 낮아져 제품 보관시 콜드 플로우(cold flow)라 불리는 에지 퓨젼(edge fusion) 문제가 발생한다.In addition, the total photosensitive resin composition contains 10 to 35% by weight of a photopolymerizable monomer including a polyfunctional α, β-unsaturated carbonyl derivative compound represented by the general formula (1) or (2). If less than 10% by weight of the photosensitive resin composition, the glass transition temperature of the dry film resist becomes high, the resist layer becomes brittle and the followability is drastically decreased, and if it exceeds 35% by weight, the glass transition temperature of the dry film resist becomes too low. An edge fusion problem called cold flow arises.
한편, 광중합성 모노머와 바인더 폴리머는 10:90∼60:40중량비 되도록 사용하는 것이 바람직하다.On the other hand, it is preferable to use a photopolymerizable monomer and a binder polymer so that it may be 10: 90-60: 40 weight ratio.
(3)광개시제(3) photoinitiators
광개시제는 전체 감광성 수지조성물 중 0.1∼20중량%를 차지하며, UV 및 기타 방사(radiation)에 의해서 상기와 같은 기능성 광중합성 모노머들의 연쇄반응을 개시시키는 물질이다. 드라이필름 레지스트의 경화에 중요한 역할을 하는 물질로서, 구체적인 화합물의 예로는 안트라퀴논 유도체, 즉 2-메틸 안트라퀴논과 2-에틸 안트라퀴논, 벤조인 유도체, 즉 벤조인 메틸에테르, 벤조페논, 페난트렌퀴논, 그리고 4,4'-비스-(디메틸아미노)벤조페논 등을 들 수 있다. 이들 광개시제들은 단독 또는 혼합하여 사용할 수 있다.The photoinitiator occupies 0.1 to 20% by weight of the total photosensitive resin composition, and is a substance which initiates a chain reaction of the functional photopolymerizable monomers by UV and other radiation. As a material that plays an important role in curing the dry film resist, examples of specific compounds include anthraquinone derivatives, such as 2-methyl anthraquinone and 2-ethyl anthraquinone, benzoin derivatives, such as benzoin methyl ether, benzophenone, and phenanthrene. Quinones, and 4,4'-bis- (dimethylamino) benzophenone. These photoinitiators may be used alone or in combination.
본 발명에 따라 새로이 도입된 기능성 광중합성 모노머 즉, 페녹시 알킬 또는 페녹시 폴리에테르류를 포함하는 α,β-불포화 카르보닐 유도체 화합물을 광중합성 모노머 중 포함하는 감광성 수지조성물의 경우 드라이필름 레지스트의 밀착력을 획기적으로 증대시킬 수 있으며, 이들의 함량을 적절히 조절할 경우에 세선밀착력 증대시 유발되는 해상도 저해를 없애거나 최소화시킬 수 있다.In the case of the photosensitive resin composition containing the newly introduced functional photopolymerizable monomer, ie, α, β-unsaturated carbonyl derivative compound containing phenoxy alkyl or phenoxy polyether, in the photopolymerizable monomer, dry film resist Adhesion can be significantly increased, and when the content thereof is properly adjusted, resolution degradation caused by fine wire adhesion can be eliminated or minimized.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1∼10 및 비교예 1∼2Examples 1-10 and Comparative Examples 1-2
다음 표 1 내지 5에 나타낸 바와 같은 조성으로 통상의 방법에 따라 드라이필름 레지스트를 제조한 후, 도 1에 나타낸 바와 같은 일반적인 PCB 제조공정에 따라 드라이필름의 물성을 평가하였다.Next, after the dry film resist was manufactured according to a conventional method with the composition as shown in Tables 1 to 5, the physical properties of the dry film were evaluated according to the general PCB manufacturing process as shown in FIG.
상기 실시예 및 비교예에 따라 얻어진 감광성 수지조성물들을 수지층의 두께가 30㎛ 되도록 폴리에틸렌 테레프탈레이트 필름(두께 19㎛)에 균일하게 코팅한 후 건조하였다. 이렇게 제조된 드라이필름 레지스트를 CCL(Copper Clad Laminates)에 라미네이션시킨 후 다음의 노광에너지 즉, 30mJ/㎠, 50mJ/㎠, 그리고 70mJ/㎠ 되도록 조사한 후 현상공정을 거쳐 드라이필름의 감도, 해상도, 그리고 세선밀착력을 평가하였다. 그 결과는 다음 표 6 내지 10에 나타낸 바와 같다.The photosensitive resin compositions obtained according to the above Examples and Comparative Examples were uniformly coated on a polyethylene terephthalate film (thickness 19 μm) so that the thickness of the resin layer was 30 μm and then dried. The dry film resist thus prepared is laminated on CCL (Copper Clad Laminates), and then irradiated with the following exposure energy, that is, 30mJ / cm 2, 50mJ / cm 2, and 70mJ / cm 2, and then subjected to a developing process to give sensitivity, resolution, and Thin wire adhesion was evaluated. The results are as shown in Tables 6 to 10 below.
상기 표 6의 결과는 페녹시 알킬 또는 페녹시 폴리에테르류를 포함하는 α,β-불포화 카르보닐 유도체 화합물이 도입됨에 따라 감광선 수지조성물의 세선밀착력 및 해상도 변화를 나타낸 것으로서, 광중합성 모노머 중 기능성 모노머 PA-1이 도입됨에 따라 5∼10㎛ 정도의 세선밀착력 증대를 보이는 바, 이 경우 해상도의 저해가 거의 없거나 미약한 것으로 볼 수 있다. 이와같은 현상은 비단 상기 실시예에서 사용된 PA-1 유도체 뿐만 아니라 페녹시 알킬 또는 페녹시 폴리에테르류를 포함하는 α,β-불포화 카르보닐 유도체 화합물에서도 비슷한 양상을 나타낸다.The results of Table 6 show the thin line adhesion and resolution change of the photosensitive resin composition as the α, β-unsaturated carbonyl derivative compound including phenoxy alkyl or phenoxy polyethers is introduced. As the introduction of the monomer PA-1 shows an increase in the fine wire adhesion of about 5 to 10㎛, in this case it can be seen that little or no inhibition of resolution. This phenomenon is similar to the PA-1 derivative used in the above examples, as well as the α, β-unsaturated carbonyl derivative compounds containing phenoxy alkyl or phenoxy polyethers.
상기 실시예 3과 4는 화학식 1의 화합물 중 Y가 폴리에테르 단위로 이루어진 페녹시 알킬을 포함하는 α,β-불포화 카르보닐 유도체 화합물의 효과를 나타낸 것으로서, Y가 알킬기인 실시예 1과 2와 비교하여 볼 때 감도 및 해상도는 유사한 물성치를 나타내나 세선밀착력에 있어서는 다소 향상된 결과를 보임을 알 수 있다. Examples 3 and 4 illustrate the effects of α, β-unsaturated carbonyl derivative compounds containing phenoxy alkyl, wherein Y is a polyether unit, and Y is an alkyl group. In comparison, the sensitivity and resolution show similar properties, but the thin line adhesion shows a somewhat improved result.
상기 실시예 5는 화학식 1의 Y가 이소프로필렌 옥사이드 단위일 때의 효과를 확인하고자 한 것이며, 실시예 6은 보조 사슬의 -O-알킬에 의한 효과를 확인하고자 한 것이고, 실시예 7은 폴리에틸렌과 이소프로필렌 옥사이드의 공중합체인 효과를 확인하고자 한 것이다. 실시예 5 내지 7의 경우 페녹시 알킬 디아크릴레이트 화합물을 조성에 첨가했을 경우 세선밀착력의 향상이 일어남을 알 수 있다.Example 5 is to determine the effect of when the Y in the formula 1 isopropylene oxide unit, Example 6 is to confirm the effect of the -O-alkyl of the auxiliary chain, Example 7 It is intended to confirm the effect of the copolymer of isopropylene oxide. In Examples 5 to 7, it can be seen that when the phenoxy alkyl diacrylate compound is added to the composition, the fine wire adhesion is improved.
상기 실시예 8 내지 10은 페녹시기의 페닐기의 치환체 종류에 따른 해상도 및 밀착력 변화를 확인하고자 한 것으로서, 페닐기의 치환체가 Electron withdrawing group이 치환된 경우에 감도는 저하되나 해상도 및 세선 밀착력은 상당히 향상되는 반면 치환체가 Electron donation group인 경우에는 감도는 향상되나 해상도는 다소 감소되는 현상을 나타냄을 알 수 있다.Examples 8 to 10 are intended to confirm the change in resolution and adhesion according to the substituent type of the phenyl group of the phenoxy group, and the sensitivity of the phenyl group when the electron withdrawing group is substituted, but the resolution and fine line adhesion are significantly improved. On the other hand, when the substituent is an electron donation group, the sensitivity is improved but the resolution is slightly decreased.
실시예 11은 화학식 1중 Y가 폴리우레탄 유도체일 때의 효과를 나타낸 결과이다.Example 11 is a result showing the effect when Y in the formula (1) is a polyurethane derivative.
이상에서 상세히 살펴본 바와 같이, 본 발명에 따라 분자 내의 보조사슬에 페녹시 알킬류, 페녹시 폴리에테르류, 그리고 페녹시 폴리에스테르류를 포함하며 말단에 메타크릴레이트기를 가지는 기능성 모노머 또는 폴리우레탄 아크릴레이트를 광중합성 모노머 성분 중 포함하는 감광성 수지조성물은 고세선밀착력, 고해상을 구현하기 위해 세선밀착력을 증대시키는 경우 발생되는 해상도의 저하나, 해상도를 증대시킬 경우 나타나는 세선밀착력의 저하없이 해상도를 동등 이상으로 유지하면서 세선밀착력을 향상시키는 효과를 얻을 수 있다.As described in detail above, a functional monomer or polyurethane acrylate including phenoxy alkyls, phenoxy polyethers, and phenoxy polyesters in the auxiliary chain in the molecule and having a methacrylate group at the terminal according to the present invention. The photosensitive resin composition containing among the photopolymerizable monomer components has a resolution higher than or equal to the resolution without deteriorating the resolution generated when the fine wire adhesion is increased to achieve high fine wire adhesion and high resolution, or the fine wire adhesion that is increased when the resolution is increased. The effect of improving fine wire adhesion can be obtained while maintaining.
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KR19980083460A (en) * | 1997-05-15 | 1998-12-05 | 구광시 | Photocurable composition with improved resolution and tentability |
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KR960002240A (en) * | 1994-06-27 | 1996-01-26 | 오오가 노리오 | Autoreverse type tape player and its operation switching mechanism |
KR0126436B1 (en) * | 1994-06-30 | 1997-12-18 | 하기주 | Photocuring composition |
JPH08339082A (en) * | 1995-04-11 | 1996-12-24 | Dainippon Ink & Chem Inc | Photosensitive composition and photosensitive planographic printing plate |
KR19990077032A (en) * | 1996-01-04 | 1999-10-25 | 페라 스타르크, 요헨 카르크 | Radiation curable coatings |
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