KR20060124841A - Photopolymerizable resin composition for sandblast resist and dry film photo resist formed thereof - Google Patents
Photopolymerizable resin composition for sandblast resist and dry film photo resist formed thereof Download PDFInfo
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- KR20060124841A KR20060124841A KR1020050044393A KR20050044393A KR20060124841A KR 20060124841 A KR20060124841 A KR 20060124841A KR 1020050044393 A KR1020050044393 A KR 1020050044393A KR 20050044393 A KR20050044393 A KR 20050044393A KR 20060124841 A KR20060124841 A KR 20060124841A
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- Prior art keywords
- compound
- resin composition
- photosensitive resin
- meth
- sandblast
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- -1 urethane acrylate compound Chemical class 0.000 claims abstract description 41
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 239000001913 cellulose Substances 0.000 claims abstract description 19
- 229920002678 cellulose Polymers 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 12
- 239000003999 initiator Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005192 partition Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 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 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 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 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/027—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
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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
- G03F7/027—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
- 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
Description
본 발명은 샌드블라스트 레지스트용 감광성 수지 조성물 및 이로부터 제조된 드라이 필름 포토레지스트에 관한 것으로서, 더욱 상세하게는 알칼리 가용성 고분자 화합물, 광중합성 단량체, 광중합 개시제 및 기타첨가제를 포함하는 감광성 수지 조성물에서 알칼리 가용성 고분자 화합물로 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체 및 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용한 감광성 수지 조성물을 이용하여 샌드블라스트 레지스트의 탄성과 유연성이 우수하고, 현상액에 대한 내알칼리 약품성과 세선밀착력이 우수한 드라이 필름 포토레지스트에 관한 것이다. The present invention relates to a photosensitive resin composition for sandblast resist and a dry film photoresist prepared therefrom, and more particularly, to an alkali-soluble photosensitive resin composition comprising an alkali-soluble polymer compound, a photopolymerizable monomer, a photopolymerization initiator, and other additives. Excellent elasticity and flexibility of sandblast resist using photosensitive resin composition using a copolymer prepared from urethane acrylate compound, (meth) acrylic acid, and a polymer containing at least one polar group and a carboxyl group-containing cellulose compound as a polymer compound The present invention relates to a dry film photoresist excellent in alkali chemical resistance and thin wire adhesion to a developer.
드라이 필름 레지스트(Dry Film Resist, DFR)는 인쇄회로기판 제조에 있어서 회로 패터닝을 위한 기본 소재로 널리 사용되어지고 있으며 최근에 들어서는 그 활용 범위가 점점 더 확대되고 있다. Dry Film Resist (DFR) is widely used as a basic material for circuit patterning in printed circuit board manufacturing, and in recent years, its application range is expanding.
종래 액상 레지스트에서 행해지던 많은 영역들을 드라이 필름 레지스트로 전환하고자 하는 노력들이 많이 진행중에 있으며, IC 패키징, 리드 프레임(Lead Frame), 또는 BGA(Ball Grid Alley) 공정에서는 드라이 필름 레지스트가 많이 사용되어지고 있다. 최근에 들어서는 플라즈마 디스플레이 패널(Plasma Display Panel, PDP) 제조에 있어서 투명전극인 인듐 틴 옥사이드(Indium Tin Oxide, ITO)의 패터닝 공정과 격벽형성 공정에 드라이 필름 포토레지스트가 많이 사용되어지고 있다. Efforts have been made to convert many areas of the conventional liquid resist into dry film resist, and dry film resist is widely used in IC packaging, lead frame, or ball grid alley (BGA) processes. have. Recently, in the manufacture of plasma display panels (PDPs), dry film photoresists have been used in patterning processes and barrier rib forming processes of indium tin oxide (ITO), which are transparent electrodes.
구체적으로, 드라이 필름 레지스트를 이용하여 PDP 하판의 격벽을 형성하는 공정을 살펴보면, 격벽재가 인쇄된 PDP 소재에 가열 롤러(roller)를 이용하여 드라이 필름 레지스트를 라미네이션 시킴으로써 형성된다. 이 공정에서는 라미네이터를 이용하여 DFR의 보호 필름을 벗겨내면서 DFR의 포토레지스트층을 격벽재 위에 라미네이션시킨다. 이때 라미네이션 조건은 라미네이션 속도 0.5∼3.5m/min, 온도 100∼130℃, 롤러 압력 가열롤 압력 10∼90psi 이다. Specifically, looking at the process of forming the partition wall of the PDP lower plate using the dry film resist, the partition wall material is formed by laminating the dry film resist using a heating roller (roller) on the printed PDP material. In this process, the photoresist layer of the DFR is laminated on the barrier ribs while the protective film of the DFR is peeled off using a laminator. At this time, lamination conditions are lamination speed 0.5-3.5m / min, temperature 100-130 degreeC, roller pressure heating roll pressure 10-90psi.
라미네이션 공정을 거친 유리 기판은 기판의 안정화를 위하여 15분 이상 방치시킨 후, 원하는 회로패턴이 형성된 포토마스크를 이용하여 드라이 필름 레지스트의 포토레지스트에 대해 노광을 진행한다. 이 과정에서 포토마스크에 자외선을 조사하면 자외선이 조사된 포토레지스트는 조사된 노광 부위에서 함유된 광개시제에 의해 중합이 개시된다. 먼저 초기에는 포토레지스트 내의 산소가 소모되고, 다음 활성화된 단량체가 중합되어 가교반응이 일어나고, 그 후 많은 양의 단량체가 소모되면서 중합반응이 진행된다. 한편 미노광 부위는 가교 반응이 진행되지 않은 상태로 존재하게 된다. The glass substrate subjected to the lamination process is left to stand for at least 15 minutes to stabilize the substrate, and then exposed to the photoresist of the dry film resist using a photomask on which a desired circuit pattern is formed. 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 exposure site. Initially, oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of monomer is consumed to proceed with the polymerization. On the other hand, the unexposed portion is present in a state where the crosslinking reaction does not proceed.
다음 포토레지스트의 미노광 부분을 제거하는 현상 공정을 진행하는데, 알칼리 현상성 드라이 필름 레지스트인 경우 현상액으로 0.2∼1.2wt%의 포타슘카보네이트 및 소듐카보네이트 수용액이 사용된다. 이 공정에서 미노광 부분의 포토레지스트는 현상액 내에서 알칼리 가용성 고분자 화합물의 카르복시산과 현상액의 비누화 반응에 의해서 씻켜 나가고, 경화된 포토레지스트는 격벽재 표면위에 잔류하게 된다. Next, a developing process of removing the unexposed portions of the photoresist is performed. In the case of an alkaline developable dry film resist, 0.2 to 1.2 wt% of potassium carbonate and sodium carbonate aqueous solution is used as a developer. In this process, the photoresist of the unexposed portion is washed out by the saponification reaction between the carboxylic acid of the alkali-soluble polymer compound and the developer in the developer, and the cured photoresist remains on the partition wall surface.
위와 같이 드라이 필름이 패터닝된 유리기판은 샌드블라스팅 공정에 의하여 격벽 패턴을 형성하게 된다. 상기 샌드블라스팅 공정에서 격벽재 위에 형성된 드라이 필름 패턴은 밑에 있는 격벽재료가 깍이는 것을 방지하는 보호막 역할을 한다. As described above, the glass substrate patterned with the dry film forms a partition pattern by a sandblasting process. The dry film pattern formed on the partition wall material in the sandblasting process serves as a protective film to prevent the underlying partition material from being chipped.
그 후, 상기 드라이 필름 레지스트의 패턴을 제거하는 박리공정, 그리고 격벽재를 경화시키는 소성공정을 함으로서 격벽형성이 완성된다. Thereafter, partition formation is completed by performing a peeling step of removing the pattern of the dry film resist and a baking step of curing the partition material.
종래 샌드블라스트 레지스트용 감광성 수지 조성물에 대한 기술로는 한국 특허 1999-0198725호(US 6,200,733 B1 ; US 5,924,912 ; US 6,322,947 B1)에서는, 광중합 개시제; 알칼리 가용성 고분자 화합물; 그리고 사슬 말단에 히드록시기를 포함한 폴리에테르 또는 폴리에스테르 화합물; 디이소시아네이트 화합물과 히드록시기를 포함한 (메타)아크릴레이트화합물로부터 얻어진 사슬 말단에 (메타)아트릴레이트기를 포함한 우레탄 화합물을 광중합성 올리고머로 포함한다. As a technique for the conventional photosensitive resin composition for sandblast resist, Korean Patent No. 1999-0198725 (US 6,200,733 B1; US 5,924,912; US 6,322,947 B1), a photopolymerization initiator; Alkali-soluble polymer compounds; And polyether or polyester compound containing a hydroxyl group at the chain terminal; The urethane compound containing a (meth) atryl group in the chain terminal obtained from the diisocyanate compound and the (meth) acrylate compound containing a hydroxyl group is included as a photopolymerizable oligomer.
그러나, 상기와 같이 사슬 말단에 (메타)아트릴레이트기를 포함한 우레탄 화합물을 반응성 올리고머로 사용한 경우, 반응성이 떨어져 내알칼리 현상성이 저하되어 드라이 필름의 밀착력이 떨어지는 동시에 현상 후 드라이 필름 패턴의 팽윤성 (swelling)이 증가되어 해상도에도 악영향을 끼친다. However, when a urethane compound containing a (meth) atrylate group is used as a reactive oligomer at the chain end as described above, however, the reactivity is poor and alkali developability is lowered, resulting in poor adhesion of the dry film and at the same time swelling property of the dry film pattern after development ( Swelling is increased, adversely affecting resolution.
또한 알칼리 가용성 고분자 화합물로는 (메타)아크릴산; (메타)아크릴산과 (메타)아크릴산 에스테르와의 공중합체 및 카르복시기 함유 셀룰로오즈 화합물 등이 사용되는 바, (메타)아크릴산과 (메타)아크릴산 에스테르와의 공중합체는 막의 강도와 유연성이 약한 단점이 있으며, 특히 카르복시기 함유 셀룰로오즈 화합물을 사용한 경우, 알칼리 수용액에 대한 내약품성이 매우 나빠져 현상 공정에서 형성된 패턴의 손상이 심해지므로 고해상, 고밀착성의 패턴 형성이 어렵게 된다.Moreover, as an alkali-soluble high molecular compound, (meth) acrylic acid; Since copolymers of (meth) acrylic acid and (meth) acrylic acid esters and carboxyl group-containing cellulose compounds are used, copolymers of (meth) acrylic acid and (meth) acrylic acid esters have a weak strength and flexibility of the membrane. In particular, when the carboxyl group-containing cellulose compound is used, the chemical resistance to the aqueous alkali solution is very poor, and the damage of the pattern formed in the developing step becomes severe, making it difficult to form a high resolution and high adhesion pattern.
또한 상기 특허에서는 광중합성 단량체(단일작용성 단량체 & 다작용성 단량체)의 함량을 분자말단에 (메타)아크릴레이트기를 가지는 폴리우레탄 화합물 100중량부에 대하여 20중량부 이하로 한정하고 있는 바, 만일 20중량부를 초과하여 포함될 경우에는 자외선 경화공정 후 레지스트가 부서지기 쉬워 내샌드브레이트성이 떨어지기 때문이다. In addition, the patent limits the content of the photopolymerizable monomer (monofunctional monomer & polyfunctional monomer) to 20 parts by weight or less based on 100 parts by weight of the polyurethane compound having a (meth) acrylate group at the molecular end. This is because when included in an amount exceeding parts by weight, the resist is brittle after the ultraviolet curing process and the sandbrate resistance is inferior.
따라서, 상기와 같은 종래 샌드블라스트 레지스트용 감광성 수지조성물의 문제점을 보완하기 위해서는 유연성과 내약품성이 강화된 알칼리 가용성 고분자 화합물과, 밀착력을 강화시키는 광중합성 올리고머를 포함하는 조성물의 개발이 필요하다. Therefore, in order to supplement the problems of the conventional photosensitive resin composition for a sandblast resist as described above, it is necessary to develop a composition comprising an alkali-soluble polymer compound having enhanced flexibility and chemical resistance and a photopolymerizable oligomer for enhancing adhesion.
이에 본 발명자들은 상기와 같은 종래 샌드블라스트 레지스트용 감광성 수지 조성물이 가지고 있던 문제점을 해결하기 위하여 연구 노력 하던 중, 종래 샌드블 라스트 레지스트용 감광성 수지 조성물에서 알칼리 가용성 고분자 화합물로 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 공중합체; 및 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용한 감광성 수지 조성물을 이용하여 드라이 필름 레지스트를 제조한 결과 유연성과 탄성이 우수하고 미세한 패턴의 형성이 가능할 뿐만 아니라, 내알칼리 약품성이 우수하여 현상공정 후 레지스트의 세선밀착력이 우수하다는 것을 알게 되어 본 발명을 완성하게 되었다. Accordingly, the present inventors, while trying to solve the problems of the conventional photosensitive resin composition for sandblast resist as described above, urethane acrylate compound, (meth) as an alkali-soluble polymer compound in the conventional photosensitive resin composition for sandblast resist ) Copolymers from acrylic acid and a compound containing at least one polar group; And a dry film resist using a photosensitive resin composition using a mixture of carboxyl group-containing cellulose compounds, resulting in excellent flexibility and elasticity, formation of a fine pattern, and excellent alkali chemical resistance, resulting in fine line adhesion of the resist after development. It has been found to be excellent to complete the present invention.
따라서, 본 발명의 목적은 유연성과 탄성이 우수하고 미세한 패턴의 형성이 가능할 뿐만 아니라, 내알칼리 약품성이 우수하여 현상공정 후 레지스트의 세선밀착력이 우수한 샌드블라스트 레지스트용 감광성 수지 조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a photosensitive resin composition for sandblast resists excellent in flexibility and elasticity and capable of forming a fine pattern, excellent alkali chemical resistance and excellent fine line adhesion of the resist after the development process.
또한, 본 발명의 다른 목적은 상기와 같은 샌드블라스트 레지스트용 감광성 수지 조성물로부터 제조된 드라이 필름 포토레지스트를 제공하는 데도 있다.In addition, another object of the present invention is to provide a dry film photoresist prepared from the photosensitive resin composition for sandblast resist as described above.
이러한 본 발명에 따른 샌드블라스트 레지스트용 감광성 수지 조성물은 알칼리 가용성 고분자 화합물, 광중합성 단량체, 광중합 개시제 및 기타첨가제를 포함하는 감광성 수지 조성물에 있어서, 상기 알칼리 가용성 고분자 화합물은 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체; 및 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용한 것을 그 특징으로 한다.The photosensitive resin composition for a sandblast resist according to the present invention is a photosensitive resin composition comprising an alkali-soluble polymer compound, a photopolymerizable monomer, a photopolymerization initiator and other additives, wherein the alkali-soluble polymer compound is a urethane acrylate compound, (meth) Copolymers prepared from acrylic acid, and compounds containing at least one polar group; And a carboxyl group-containing cellulose compound.
또한, 본 발명은 상기와 같은 감광성 수지 조성물로부터 얻어진 드라이 필름 포토레지스트에도 그 특징이 있다. Moreover, this invention has the characteristics also in the dry film photoresist obtained from the above photosensitive resin composition.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 종래 알칼리 가용성 고분자 화합물, 광중합성 단량체, 광중합 개시제 및 기타첨가제를 포함하는 샌드블라스트 레지스트용 감광성 수지 조성물에서, 알칼리 가용성 고분자 화합물로서 유연성과 내약품성이 강화된 알칼리 가용성 고분자는 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체; 및 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용한 샌드블라스팅 레지스트용 감광성 수지 조성물 및 이로부터 제조된 드라이 필름 포토레지스트에 관한 것이다. The present invention relates to a photosensitive resin composition for a sandblast resist comprising a conventional alkali-soluble polymer compound, a photopolymerizable monomer, a photopolymerization initiator, and other additives, wherein the alkali-soluble polymer having enhanced flexibility and chemical resistance as an alkali-soluble polymer compound is a urethane acrylate compound. Copolymers prepared from (meth) acrylic acid, and compounds containing at least one polar group; And a photosensitive resin composition for sandblasting resists using a carboxyl group-containing cellulose compound in a mixed state, and a dry film photoresist prepared therefrom.
일반적으로 감광성 수지 조성물은 특히 샌드블라스팅 공정 동안 지지체에 대한 밀착성이 우수하여야 하며, 샌드블라스팅의 기계적인 내 충격성을 가지기 위하여 우수한 탄성과 유연성이 요구된다. In general, the photosensitive resin composition should have excellent adhesion to the support, particularly during the sandblasting process, and excellent elasticity and flexibility are required to have mechanical impact resistance of the sandblasting.
본 발명의 알칼리 가용성 고분자에 포함되는 공중합체 제조시 사용되는 상기 우레탄 아크릴레이트 화합물은 분자 사슬 말단에 히드록시기를 함유한 폴리에테르 또는 폴리에스테르 화합물을 과량의 디이소시아네이트 화합물과 반응시켜 분자 사슬 말단에 이소시아네이트기를 함유한 폴리에테르 또는 폴리에스테르 화합물을 얻은 다음, 이소시아네이트기와 동일 몰량의 분자 말단에 히드록시기를 함유한 (메타)아크릴레이트 화합물을 반응시켜 얻어진 분자 말단에 (메타)아크릴레이트기를 함유한 것으로, 본 발명에서는 Ebecryl 4815, Photomer 6294, Setacure AP 565, Craynor CN 961와 같은 상용화된 우레탄 아크릴레이트 화합물을 사용한다. 상기 우 레탄 아크릴레이트 화합물은 중량 평균 분자량이 5,000 내지 100,000의 것이 바람직하다. The urethane acrylate compound used in the preparation of the copolymer included in the alkali-soluble polymer of the present invention is a polyether or polyester compound containing a hydroxyl group at the molecular chain terminal and reacted with an excess diisocyanate compound to give an isocyanate group at the molecular chain terminal. In the present invention, a (meth) acrylate group is contained at a molecular terminal obtained by obtaining a polyether or polyester compound containing the same, and then reacting a (meth) acrylate compound containing a hydroxy group at the same molar amount of the terminal of the isocyanate group. Commercially available urethane acrylate compounds such as Ebecryl 4815, Photomer 6294, Setacure AP 565, Craynor CN 961 are used. The urethane acrylate compound preferably has a weight average molecular weight of 5,000 to 100,000.
본 발명에서는 상기 상용화된 우레탄 아크릴레이트 화합물에 (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물을 공중합시켜 얻어진 공중합체를 사용한다. In the present invention, a copolymer obtained by copolymerizing (meth) acrylic acid and a compound containing at least one polar group in the commercially available urethane acrylate compound is used.
상기 (메타)아크릴산은 메타크릴산 또는 아크릴산으로서, 현상박리 특성을 향상시키기 위하여 첨가된다. The (meth) acrylic acid is methacrylic acid or acrylic acid, and is added to improve development and peeling characteristics.
또한, 1종 이상의 극성기를 함유한 화합물의 예를 들면, 메틸메타크릴레이트, 히드록시 에틸메타크릴레이트, 글리시딜메타크릴레이트, 아크릴로니트릴, 히드록시 프로필 아크릴레이트 또는 스타이렌 중에서 선택된 것으로, 이들은 밀착력을 위해서 첨가된다. Further, examples of the compound containing one or more polar groups include those selected from methyl methacrylate, hydroxy ethyl methacrylate, glycidyl methacrylate, acrylonitrile, hydroxy propyl acrylate or styrene, These are added for adhesion.
즉, 본 발명의 공중합체는 1종 이상의 극성기를 함유한 화합물 10 내지 30중량%; (메타)아크릴산 10 내지 30 중량%; 및 상용화된 우레탄 아크릴레이트 40 내지 80중량%를 포함되는 조성으로부터 제조된다. 그 제조방법은 상기 혼합물을 혼합한 후, 개시제(AIBN)와 용매 메틸렌크로라이드을 투입한 후, 적정한 온도와 시간에서 반응시킨다. 반응 종료 후, 진공하에서 용매를 제거하여 본 발명의 공중합체를 제조한다. That is, the copolymer of the present invention is 10 to 30% by weight of a compound containing at least one polar group; 10-30% by weight of (meth) acrylic acid; And 40 to 80% by weight of commercialized urethane acrylate. In the preparation method, after the mixture is mixed, an initiator (AIBN) and a solvent methylene chloride are added thereto, and then reacted at an appropriate temperature and time. After completion of the reaction, the solvent was removed under vacuum to prepare a copolymer of the present invention.
상기와 같은 방법으로 제조된 본 발명의 공중합체의 중량 평균 분자량은 30,000 내지 1,000,000, 바람직하기로는 40,000 내지 200,000이며, 산가는 50 내지 250mgKOH/g이다. 상기 분자량이 30,000 미만에서는 충분한 유연성을 주지 못하며, 막 형성능, 현상성, 장기보관시의 에지 퓨젼(edge fusion) 등의 문제를 유발하고, 또한 1,000,000을 초과할 경우에는 현상 속도가 급격히 늦어지게 된다.The weight average molecular weight of the copolymer of the present invention prepared by the above method is 30,000 to 1,000,000, preferably 40,000 to 200,000, the acid value is 50 to 250mgKOH / g. If the molecular weight is less than 30,000, it does not give sufficient flexibility, and causes problems such as film formation ability, developability, edge fusion during long-term storage, and, if it exceeds 1,000,000, the development speed is drastically slowed.
본 발명의 알칼리 가용성 고분자 화합물은 상기 제조된 공중합체와 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용하는 것이 바람직한 바, 상기 공중합체의 함량은 전체 알칼리 가용성 고분자 화합물의 고형분 함량 중 10 내지 80 중량%가 바람직하며, 더욱 바람직하기로는 20 내지 60중량%이다. 상기 함량이 80 중량%를 초과하면 현상 시간이 길어지고, 지지체(substrate)에 대한 밀착성이 약해지고, 10 중량% 미만일 경우 유연성과 탄성이 약해진다. The alkali-soluble polymer compound of the present invention is preferably a mixture of the copolymer prepared above and the carboxyl group-containing cellulose compound, the content of the copolymer is preferably 10 to 80% by weight of the solid content of the total alkali-soluble polymer compound, More preferably, it is 20 to 60 weight%. When the content exceeds 80% by weight, the development time is long, the adhesion to the substrate is weak, and when the content is less than 10% by weight, the flexibility and elasticity are weakened.
본 발명과 같이 상기 공중합체와 카르복시기 함유 셀룰로오즈 화합물을 혼합 사용하여 알칼리 가용성 고분자 화합물로 첨가할 경우, 종래 카르복시기 함유 셀룰로오즈 화합물만을 단독으로 사용시의 알칼리 수용액에 대한 내약품성이 매우 나빠져 현상 공정에서 형성된 패턴의 손상이 심해지므로 고해상, 고밀착성의 패턴 형성이 어렵게 되는 문제를 해결할 수 있다. 특히, 카르복시기 함유 셀롤로오즈 화합물을 단독 사용시, 자외선 경화된 부위에 대한 현상 후 감광성 수지조성물의 표면의 손상이 현저히 개선됨에 따라서 고해상도 및 고해상의 PDP 제조가 가능해 진다. When the copolymer and the carboxyl group-containing cellulose compound are mixed and added as an alkali-soluble polymer compound as in the present invention, the chemical resistance to the aqueous alkali solution when the conventional carboxyl group-containing cellulose compound is used alone is very poor. Since the damage is severe, it is possible to solve the problem of forming a pattern with high resolution and high adhesion. In particular, when the carboxyl group-containing cellulose compound alone is used, the damage of the surface of the photosensitive resin composition after development on the UV-cured site is remarkably improved, thereby enabling the production of high resolution and high resolution PDP.
이러한 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체와 카르복실기를 포함하는 셀룰로오즈 화합물을 혼합한 본 발명의 알칼리 가용성 고분자 화합물은 전체 감광성 수지 조성 중 10 내지 60 중량%로 포함되는 것이 바람직한 바, 그 범위를 벗어날 경우에는 현상 시간이 길어지고, 지지체(substrate)에 대한 밀착성이 약해진다. Alkali-soluble polymer compounds of the present invention in which a copolymer prepared from such a urethane acrylate compound, (meth) acrylic acid, and a compound containing at least one polar group and a cellulose compound including a carboxyl group are mixed in the range of 10 to 10 in the total photosensitive resin composition It is preferable to include 60 wt%. If it is out of the range, the developing time becomes long, and the adhesion to the substrate is weakened.
또한, 본 발명의 광중합성 단량체는 1)분자 말단이 알킬그룹인 폴리알킬렌글리콜 모노(메타)아크릴레이트 화합물; 2)폴리알킬렌글리콜 디(메타)아크릴레이트 화합물; 및 3)분자 사슬 말단에 히드록시기를 함유한 폴리에테르 또는 폴리에스테르 화합물, 디이소시아네이트화합물과 히드록시기를 함유한 (메타)아크릴레이트 화합물로부터 얻어진 분자말단에 (메타)아크릴레이트기를 함유한 우레탄 화합물로 구성된 그룹으로부터 선택된 1종 이상의 것이다. In addition, the photopolymerizable monomer of the present invention is 1) a polyalkylene glycol mono (meth) acrylate compound whose molecular terminal is an alkyl group; 2) polyalkylene glycol di (meth) acrylate compound; And 3) a group consisting of a polyether or polyester compound containing a hydroxy group at the molecular chain terminal, a urethane compound containing a (meth) acrylate group at the molecular end obtained from a (meth) acrylate compound containing a diisocyanate compound and a hydroxy group At least one selected from.
상기와 같은 구조의 본 발명의 광중합성 단량체는 분자 내에 적어도 하나 이상의 (메타)아크릴레이트기를 가지는 폴리우레탄 화합물 외에, 에틸렌옥사이드 또는 프로필렌옥사이드 공중합체를 포함하는 광중합성 화합물로 이루어져 있으므로 드라이 필름 포토레지스트의 노광 공정에서 반응성을 높이고, 노광공정 후에는 탄성, 유연성 및 내현상액 약품성을 증가시켜 고밀착성 및 고해상도를 구현할 수 있다. Since the photopolymerizable monomer of the present invention having the structure described above is composed of a photopolymerizable compound including an ethylene oxide or a propylene oxide copolymer, in addition to a polyurethane compound having at least one (meth) acrylate group in its molecule, In the exposure process, the reactivity may be increased, and after the exposure process, elasticity, flexibility, and chemical resistance may be increased to achieve high adhesion and high resolution.
본 발명의 광중합성 단량체는 상기 1)성분과 2)성분이 전체 광중합성 단량체 100중량부에 대하여 80중량부 이하의 함량으로 사용하는 것이 바람직한 바, 이는 지지체에 대한 밀착성을 향상시키기 위함이다. In the photopolymerizable monomer of the present invention, the components 1) and 2) are preferably used in an amount of 80 parts by weight or less based on 100 parts by weight of the total photopolymerizable monomer, which is intended to improve adhesion to a support.
상기 광중합성 단량체는 전체 감광성 수지 조성 중 15 내지 50 중량%로 포함되는 것이 바람직한 바, 그 범위를 벗어날 경우에는 지지체(substrate)에 대한 밀착성이 약해진다. The photopolymerizable monomer is preferably included in 15 to 50% by weight of the total photosensitive resin composition, if it is out of the range, the adhesion to the substrate (substrate) is weakened.
한편, 본 발명에서는 상기 알칼리 가용성 고분자 화합물과 상기 광중합성 단량체는 75:25 내지 30:70의 중량비로 포함되는 것이 바람직한 바, 상기 중량비의 범위를 벗어날 경우 내샌드성이 떨어지고, 현상시간이 길어지며, 필름 형성에 불리한 문제가 있을 수 있다. On the other hand, in the present invention, the alkali-soluble polymer compound and the photopolymerizable monomer are preferably included in the weight ratio of 75:25 to 30:70 bar, when out of the range of the weight ratio is less sand resistance, the development time is longer There may be disadvantageous problems in film formation.
또한, 본 발명의 광중합 개시제로는 종래 감광성 수지 조성물에 포함되던 것이면 어떤 것이든 가능한 바, 예를 들면, 벤조페논, 4,4'-(비스디에틸아미노)벤조페논 등이 있다. In addition, as a photoinitiator of this invention, as long as it was contained in the conventional photosensitive resin composition, whatever is possible is, for example, benzophenone, 4,4'- (bisdiethylamino) benzophenone, etc. are mentioned.
이러한 광중합 개시제는 전체 감광성 수지 조성물 중 0.1 내지 20중량%로 포함되는 것이 바람직하다. Such a photopolymerization initiator is preferably included in 0.1 to 20% by weight of the total photosensitive resin composition.
또한, 상기 조성 이외에 열중합 금지제, 염료, 변색제(discoloring agent), 밀착력 촉진제 및 가소제와 같은 기타첨가제를 포함할 수 있다. In addition to the above composition, other additives such as thermal polymerization inhibitors, dyes, discoloring agents, adhesion promoters and plasticizers may be included.
한편, 본 발명에서는 상기와 같은 감광성 수지 조성물을 이용하여 기재 필름 위에 감광성 수지층을 도포시켜, 통상의 감광성 수지 필름 제조과정을 거쳐 감광성 수지층을 형성한 후, 필요에 따라, 보호필름을 상기 감광성 수지층에 도포시킨 드라이 필름 포토레지스트를 제조한다. 드라이 필름 포토레지스트의 제조 과정은 통상의 드라이 필름 포토레지스트를 제조하는 과정에 준하여 실시한다. On the other hand, in the present invention, by using a photosensitive resin composition as described above to apply a photosensitive resin layer on the base film, through the usual photosensitive resin film manufacturing process to form a photosensitive resin layer, if necessary, the protective film is the photosensitive The dry film photoresist apply | coated to the resin layer is manufactured. The manufacturing process of a dry film photoresist is performed according to the process of manufacturing a normal dry film photoresist.
실시예Example
이하, 본 발명을 실시예에 의거하여 보다 상세하게 설명하면 다음과 같은 바, 본 실시예는 이해를 돕기 위한 것이며 본 발명이 여기에 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following Examples, which are intended to help the understanding and the present invention is not limited thereto.
제조예 : 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 공중합체의 제조Preparation Example: Preparation of copolymer from urethane acrylate compound, (meth) acrylic acid, and compound containing at least one polar group
스타이렌 20.0g을 15.0g의 아크릴산(Acrylic Acid)과 65.0g의 상용화 우레탄 아크릴레이트(Ebecryl 4815)에 첨가, 혼합하였다. 이후 5.0g의 개시제(AIBN), 500g의 용매 메틸렌크로라이드를 투입한 후 45℃를 유지하면서 4시간 동안 반응시켰다. 반응 종료 후 진공 하에서 용제를 제거하여 알칼리 가용성 우레탄 공중합체를 제조하였다. 최종 제조된 공중합체의 중량평균분자량은 100,000이었다.20.0 g of styrene was added and mixed with 15.0 g of acrylic acid and 65.0 g of commercially available urethane acrylate (Ebecryl 4815). Thereafter, 5.0 g of initiator (AIBN) and 500 g of solvent methylene chloride were added thereto, followed by reaction for 4 hours while maintaining 45 ° C. After completion of the reaction, the solvent was removed under vacuum to prepare an alkali-soluble urethane copolymer. The weight average molecular weight of the final copolymer produced was 100,000.
실시예 1 내지 6Examples 1-6
상기 제조예에서 제조된 알칼리 가용성 고분자 화합물 및 다음 표 1과 같은 조성으로 감광성 수지조성물을 제조하였다. 다만, 각 실시예 1 내지 6에서는 카르복시기 함유 셀룰로오즈 화합물은 그대로 사용하고, 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물의 함량과 종류를 달리하면서 공중합체를 제조하고, 이렇게 제조된 공중합체를 이용하여 감광성 수지 조성물을 제조하였으며, 그 구체적인 화합물 및 함량을 다음 표 2에 나타내었다. The photosensitive resin composition was prepared by using the alkali-soluble polymer compound prepared in Preparation Example and the composition shown in Table 1 below. In Examples 1 to 6, however, the carboxyl group-containing cellulose compound was used as it was, and a copolymer was prepared while varying the content and type of the urethane acrylate compound, (meth) acrylic acid, and a compound containing at least one polar group, The photosensitive resin composition was prepared using the copolymer thus prepared, and specific compounds and contents thereof are shown in Table 2 below.
상기와 같은 감광성 수지조성물을 조액하여 폴리에틸렌테레프탈레이트 기재 필름 위에 건조 후 두께가 40㎛가 되도록 코팅하고, 건조시켰다. 건조 후 보호필름으로 폴리에틸렌 필름을 화이트 립(rib)이 인쇄된 유리판에 기판예열 롤 온도 80 ℃, 라미네이터 롤 온도 115 ℃, 롤 압력 4.0 kgf/cm2, 롤 속도 1.0 min/m의 조건으로 HAKUTO MACH 610i를 이용하여 라미네이션하여 드라이 필름 포토레지스트를 제조하였다.The photosensitive resin composition as described above was prepared and dried on a polyethylene terephthalate base film to have a thickness of 40 μm, followed by drying. A polyethylene film as a protective film after drying white rib (rib) of the substrate pre-heating roll temperature of 80 ℃ the printed glass plate, a laminator roll temperature of 115 ℃, roll pressure 4.0 kgf / cm 2, Dry film photoresist was prepared by laminating using HAKUTO MACH 610i under the condition of a roll speed of 1.0 min / m.
비교예 1Comparative Example 1
상기 실시예의 조성 중에서, 본 발명에 따라 제조된 공중합체를 사용하지 않고 카르복시기 함유 셀룰로오즈 화합물을 단독으로 45 중량% 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였으며, 이하 드라이 필름 포토레지스트의 제조 과정도 상기 실시예 1에서와 같은 방법으로 수행하였다. Of the composition of the above Example, except that 45% by weight of the carboxyl group-containing cellulose compound alone was used without using the copolymer prepared according to the present invention, the photosensitive resin composition was prepared in the same manner as in Example 1, The manufacturing process of the film photoresist was also performed in the same manner as in Example 1.
상기 실시예 및 비교예 따른 감광성 수지 조성물로부터 제조된 드라이 필름 포토레지스트의 세선밀착력, 해상도, 및 내샌드성과 같은 물성을 다음과 같이 평가하였으며, 그 결과를 다음 표 3에 나타내었다. Physical properties such as thin wire adhesion, resolution, and sand resistance of the dry film photoresist prepared from the photosensitive resin compositions according to the Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 3 below.
(1) 세선밀착력는 현상후 독립된 선폭이 살아남아 있는 최소선폭이다.(1) Fine line adhesion is the minimum line width in which independent line widths survive after development.
(2) 현상 및 해상도는 화이트 립(rib)이 인쇄된 유리판에 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 스프레이 분사 방식의 현상조건으로 현상을 실시하였다. 유리판 상의 미노광 부위의 드라이 필름 포토레지스트가 현상액에 완전히 씻겨지기까지 소요된 시간을 초시계를 이용하여 측정하였으며(최소현상시간) 제품 평가시는 브레이크 포인트 66%로 고정하였다(최소현상시간의 1.5배). 해상도는 회로라인과 회로라인 사이의 공간을 1:1로 하여 측정한 값이다.(2) The development and resolution were obtained by using a Perkin-Elmer TM OB7120 (parallel exposure machine) with a dry film photoresist laminated on a glass plate on which white ribs were printed, using a photomask for circuit evaluation. It was left for 20 minutes after checking. Thereafter, the development was carried out under the development conditions of spray injection method with Na 2 CO 3 1.0wt% aqueous solution. The time required for the dry film photoresist on the unexposed areas on the glass plate to be completely washed in the developer was measured using a stopwatch (minimum development time). ). The resolution is measured by using a 1: 1 space between the circuit lines.
(3) 내샌드성(3) sand resistance
현상기를 통과하여 제조된 시료를 열풍오븐에서 100도에서 2분간 건조하고 Crystal Mark사의 swam-blaster(샌드블라스트기기)의 콘노즐로 연마제를 분사하여 드라이필름포토레지스트가 뚫리는 시간을 측정하였다. The sample prepared by passing through the developer was dried at 100 ° C. in a hot air oven for 2 minutes and sprayed with an abrasive of a crystal mark swam-blaster (sandblast machine) to measure dry time of the dry film photoresist.
(4) 내알칼리 약품성(4) alkali chemical resistance
드라이필름을 투과율이 21단계(Stouffer 21 Step)로 되어 있는 포토마스크로 노광하고 현상한 후 남아있는 레지스트의 침식 받은 영역을 측정하였다. After exposing and developing the dry film with a photomask having a transmittance of 21 steps (Stouffer 21 Step), the eroded area of the remaining resist was measured.
(5) 분자량 분포 (5) molecular weight distribution
Waters 450 GPC를 이용하여 폴리스타이렌 표준 샘플로 측정하였으며, 사용된 컬럼은 Shodex 105, 104, 103 이다. The polystyrene standard samples were measured using Waters 450 GPC and the columns used were Shodex 10 5 , 10 4 , 10 3 .
상기 표 3에서 보는 바와 같이, 감광성 수지 조성물에서 알칼리 가용성 고분자 화합물로 종래 카르복시기 함유 셀룰로오즈 화합물과 본 발명에 따라 제조된 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체를 혼합 사용하여 제조된 드라이 필름 레지스트는 세선밀착력이 증가되고, 해상도, 내샌드성 및 내알칼리 약품성이 종래 카르복시기 함유 셀룰로오즈 화합물을 단독으로 사용한 비교예에 비해 우수하다.As shown in Table 3, the photosensitive resin composition is prepared from a conventional carboxyl group-containing cellulose compound and a urethane acrylate compound, (meth) acrylic acid, and at least one polar group-containing compound prepared according to the present invention as an alkali-soluble polymer compound. The dry film resists prepared by mixing the prepared copolymers have increased fine wire adhesion, and have better resolution, sand resistance, and alkali chemical resistance than the comparative examples in which conventional carboxyl group-containing cellulose compounds are used alone.
이상에서 상세히 설명한 바와 같이, 알칼리 가용성 고분자 화합물로 카르복 시기 함유 셀룰로오즈 화합물; 및 우레탄 아크릴레이트 화합물, (메타)아크릴산, 및 1종 이상의 극성기를 함유한 화합물로부터 제조된 공중합체를 혼합 사용한 샌드블라스트 레지스트용 감광성 수지 조성물로부터 제조된 드라이 필름 포토레지스트는 샌드블라스트의 탄성과 유연성이 우수하고, 현상액에 대한 내알칼리 약품성과 세선밀착력이 우수하다. As described above in detail, an alkali-soluble polymer compound includes a carboxyl group-containing cellulose compound; And a dry film photoresist prepared from a photosensitive resin composition for sandblast resists using a mixture of a urethane acrylate compound, (meth) acrylic acid, and a copolymer prepared from a compound containing at least one polar group. It is excellent in alkali chemicals and fine wire adhesion to developer.
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| KR20200001490U (en) * | 2018-12-26 | 2020-07-06 | 미쓰비시 세이시 가부시키가이샤 | Photo-sensitive resin structure for sandblasting |
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| KR20200001490U (en) * | 2018-12-26 | 2020-07-06 | 미쓰비시 세이시 가부시키가이샤 | Photo-sensitive resin structure for sandblasting |
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