KR20060036577A - Photosensitive resin composition and dry-film photoresist using it - Google Patents
Photosensitive resin composition and dry-film photoresist using it Download PDFInfo
- Publication number
- KR20060036577A KR20060036577A KR1020040085589A KR20040085589A KR20060036577A KR 20060036577 A KR20060036577 A KR 20060036577A KR 1020040085589 A KR1020040085589 A KR 1020040085589A KR 20040085589 A KR20040085589 A KR 20040085589A KR 20060036577 A KR20060036577 A KR 20060036577A
- Authority
- KR
- South Korea
- Prior art keywords
- photosensitive resin
- resin composition
- polymer binder
- film photoresist
- dry film
- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 25
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 229920005596 polymer binder Polymers 0.000 claims abstract description 19
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 239000011147 inorganic material Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000013212 metal-organic material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-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
- 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 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 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
- 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
-
- 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
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Abstract
본 발명은 고분자 결합제, 광중합성 다관능성 단량체 및 광개시제를 포함하는 감광성 수지 조성물에 있어서, 글리시딜 메타크릴레이트를 포함하는 2종 이상의 공중합 화합물로부터 공중합된 공중합체를 고분자 결합제로 사용함으로써 화학적 및 물리적 밀착력이 향상된 드라이필름 포토레지스트를 제조할 수 있도록 한 감광성 수지 조성물을 제공한다.The present invention relates to a photosensitive resin composition comprising a polymer binder, a photopolymerizable polyfunctional monomer and a photoinitiator, wherein the copolymer copolymerized from two or more copolymer compounds including glycidyl methacrylate is used as the polymer binder. Provided is a photosensitive resin composition capable of producing a dry film photoresist with improved adhesion.
Description
본 발명은 감광성 수지 조성물 및 이로부터 제조된 드라이필름 포토레지스트에 관한 것으로서, 인쇄회로기판의 화상형성재료로 사용되는 감광성 수지 조성물과 이로부터 재조되는 드라이필름 포토레지스트에 관한 것이다.The present invention relates to a photosensitive resin composition and a dry film photoresist prepared therefrom, and to a photosensitive resin composition used as an image forming material of a printed circuit board and a dry film photoresist manufactured therefrom.
일반적으로 드라이필름 포토레지스트는 동장적층판상에 적층되는 용도로 많이 사용되는 바, 이에 인쇄회로기판의 제조과정에 관해 살피면 다음과 같다.In general, dry film photoresists are widely used for laminating on copper clad laminates. Thus, the manufacturing process of a printed circuit board is as follows.
PCB의 원판소재인 동장적층판을 라미네이션하기 위해 먼저 전처리 공정을 거친다. 전처리공정은 외층공정에서는 드릴링, 디버링(deburing), 정면 등의 순이며, 내층공정에서는 정면 또는 산세를 거친다. 정면공정에서는 bristle brush 및 jet pumice 공정이 주로 사용되며, 산세는 soft etching 및 5wt% 황산산세를 거친다.In order to laminate copper clad laminate, which is the raw material of PCB, it is first pretreated. The pretreatment process is followed by drilling, deburring, and front in the outer layer process, and the front or pickling in the inner layer process. Bristle brush and jet pumice processes are mainly used in the front process, and pickling is performed through soft etching and 5 wt% sulfate pickling.
전처리 공정을 거친 동장적층판에 회로를 형성시키기 위해서는 일반적으로 동장적층판의 구리층 위에 DFR을 라미네이션한다. 이 공정에서는 라미네이터를 이용하여 DFR의 보호 필름을 벗겨내면서 DFR의 포토레지스트층을 구리표면위에 라미 네이션시킨다. 일반적으로 라미네이션 속도 0.5∼3.5m/min, 온도 100∼130℃, 로울러 압력 가열롤압력 10∼90psi에서 진행한다.In order to form a circuit on a copper clad laminate after a pretreatment process, a DFR is generally laminated on the copper layer of the copper clad laminate. In this process, the photoresist layer of the DFR is laminated on the copper surface while the protective film of the DFR is peeled off 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.
라미네이션공정을 거친 인쇄회로기판은 기판의 안정화를 위하여 15분 이상 방치한 후 원하는 회로패턴이 형성된 포토마스크를 이용하여 DFR의 포토레지스트에 대해 노광을 진행한다. 이 과정에서 포토마스크에 자외선을 조사하면 자외선이 조사된 포토레지스트는 조사된 부위에서 함유된 광개시제에 의해 중합이 개시된다. 먼저 초기에는 포토레지스트내의 산소가 소모되고, 다음 활성화된 모노머가 중합되어 가교반응이 일어나고 그 후 많은 양의 모노머가 소모되면서 중합반응이 진행된다. 한편 미노광부위는 가교 반응이 진행되지 않은 상태로 존재하게 된다.After the lamination process, the printed circuit board is left to stand for at least 15 minutes to stabilize the substrate, and then exposed to the photoresist of the DFR using a photomask having a desired circuit pattern. 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 a crosslinking reaction, and then a large amount of monomer is consumed to proceed with the polymerization reaction. On the other hand, the unexposed portion is present in a state where the crosslinking reaction does not proceed.
다음 포토레지스트의 미노광 부분을 제거하는 현상공정을 진행하는데, 알카리 현상성 DFR인 경우 현상액으로 0.8∼1.2wt%의 포타슘카보네이트 및 소듐카보네이트 수용액이 사용된다. 이 공정에서 미노광 부분의 포토레지스트는 현상액내에서 고분자 결합제의 카르복시산과 현상액의 비누화 반응에 의해서 씻겨나가고, 경화된 포토레지스트는 구리표면위에 잔류하게 된다.Next, a development process of removing unexposed portions of the photoresist is performed. In the case of alkaline developable DFR, an aqueous solution of potassium carbonate and sodium carbonate of 0.8 to 1.2 wt% is used as a developer. In this process, the photoresist of the unexposed portion is washed away by the saponification reaction of the developer and the carboxylic acid of the polymer binder in the developer, and the cured photoresist remains on the copper surface.
다음 내층 및 외층 공정에 따라 다른 공정을 거쳐 회로가 형성된다. 내층공정에서는 부식과 박리공정을 통하여 기판상에 회로가 형성되며 외층공정에서는 도금 및 텐팅공정을 거친 후 에칭과 솔더 박리를 진행하고 소정의 회로를 형성시킨다.Next, a circuit is formed through different processes depending on the inner layer and outer layer processes. 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.
일반적인 드라이필름 포토레지스트는 동장적층판상에 라미네이션되어 적층이 되고 자외선에 의해 조사되어 현상과정을 거쳐 화상이 형성된다. 이러한 드라이필 름 포토레지스트를 특수 금속 및 무기 재료에 적용시킬 경우, 동장적층판상에서와 같은 밀착력이 확보되지 못하게 되어 현상액으로 현상과정을 거치는 동안 필름의 하지 부분이 금속 및 무기 재료로부터 이탈되어서 원하는 회로 물성을 확보하기가 어렵다. 따라서, 드라이필름 포토레지스트가 특수 금속 및 무기 재료 적용되려면 금속 및 무기 재료에 대해서 기존의 드라이필름 포토레지스트보다 강한 밀착력을 갖는 조성의 개발이 필요하다.A general dry film photoresist is laminated on a copper clad laminate to be laminated and irradiated with ultraviolet rays to develop an image through a development process. When the dry film photoresist is applied to a special metal and an inorganic material, adhesion as on a copper-clad laminate cannot be secured, and the underlying portion of the film is separated from the metal and inorganic material during the development process with a developer, thereby desired circuit properties. It is difficult to secure. Therefore, in order for the dry film photoresist to be applied to special metal and inorganic materials, it is necessary to develop a composition having stronger adhesion to the metal and inorganic materials than conventional dry film photoresists.
종래의 드라이필름 포토레지스트는 동밀착력을 증가시키면 팽윤성에 의한 해상도 저하를 가져오고 이것은 고밀도화에 걸림돌로 작용되었다. 동과의 밀착력은 하이드로필릭(Hydrophilic)한 구조를 많이 포함함으로 인해 증대되나 이로인한 조성물의 팽윤성을 피할 수 없어 결국 해상도 저하로 이어지게 된다.
In the conventional dry film photoresist, increasing the coherence force brings about a decrease in resolution due to swelling, which is a barrier to densification. Adhesion with copper is increased by including a lot of hydrophilic structure, but the swelling property of the composition can not be avoided, resulting in lower resolution.
본 발명은 종래 조성의 밀착력 문제를 해결하기 위한 것으로, 글리시딜 메타크릴레이트를 포함하는 공중합체를 중합하여 레지스트 조성에 투입함으로써 드라이필름레지스트의 밀착력이 향상되고 타물성은 유지되도록 한데 그 목적이 있다. The present invention is to solve the problem of adhesion of the conventional composition, by polymerizing a copolymer containing glycidyl methacrylate to the resist composition to improve the adhesion of the dry film resist and to maintain the other properties have.
상기와 같은 목적을 달성하기 위한 본 발명의 감광성 수지 조성물은 고분자 결합제, 광중합성 다관능성 단량체 및 광개시제를 포함하는 것으로서, 상기 고분자 결합제는 글리시딜 메타크릴레이트를 포함하는 2종 이상의 공중합 화합물로부터 공중합된 공중합체인 것임을 그 특징으로 한다.
The photosensitive resin composition of the present invention for achieving the above object includes a polymer binder, a photopolymerizable polyfunctional monomer and a photoinitiator, wherein the polymer binder is copolymerized from two or more copolymer compounds including glycidyl methacrylate. It is characterized by the fact that it is a copolymer.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다. The present invention will be described in more detail as follows.
종래의 인쇄회로 기판용 감광성 수지의 특수 메탈 및 무기 재료에 대한 밀착력을 증가시키기 위해 노력한 결과 감광성 수지 조성물 중 고분자 결합제가 가장 큰 영향을 미침을 발견하였다. 특히 고분자 결합제로서 에폭시기를 함유하고 있는 글리시딜 메타크릴레이트를 타 공중합 화합물과 공중합시켜 얻어진 공중합체를 사용하게 되면 밀착력이 증가함을 확인하였다. Efforts have been made to increase the adhesion of special photosensitive resins for conventional printed circuit boards to special metals and inorganic materials and have found that polymer binders have the greatest effect among photosensitive resin compositions. In particular, when a copolymer obtained by copolymerizing glycidyl methacrylate containing an epoxy group with another copolymer compound was used as the polymer binder, it was confirmed that the adhesion strength increased.
상기 타 공중합 화합물로는 아크릴산 또는 스타이렌, 메틸 메타크릴레이트, 메타크릴산 등이 있다. The other copolymerized compound includes acrylic acid or styrene, methyl methacrylate, methacrylic acid, and the like.
고분자 결합제의 제조시, 글리시딜 메타크릴레이트의 함량은 전체 고분자 결합제 고형분에 대해 10 내지 50중량%가 적당하며, 더욱 좋게는 15 내지 40중량%가 바람직하다. 글리시딜 메타크릴레이트의 함량이 많으면 현상시간이 길어지고 팽윤성이 영향을 받으므로 적정 함량이 중요하다.In preparing the polymer binder, the content of glycidyl methacrylate is suitably 10 to 50% by weight, more preferably 15 to 40% by weight based on the total polymer binder solids. If the content of glycidyl methacrylate is high, the development time is long and the swelling property is affected, so the proper content is important.
글리시딜 메타크릴레이트를 타 공중합 화합물과 공중합하여 만들어진 고분자결합제의 분자량은 중량평균분자량 30,000-250,000이 좋으며 더욱 좋게는 40,000-150,000이다. 본 범위보다 낮은 분자량을 갖는 고분자 결합제는 충분한 텐팅성을 주지 못하며 막형성능, 현상성, 장기보관시의 에지퓨젼 등의 문제를 유발한다. 반면 본 범위보다 높을 경우 현상속도가 급격히 늦어지게 된다.The molecular weight of the polymer binder prepared by copolymerizing glycidyl methacrylate with another copolymer compound has a good weight average molecular weight of 30,000-250,000 and more preferably 40,000-150,000. Polymer binders having a lower molecular weight than this range do not give sufficient tentability and cause problems such as film forming ability, developability, and edge fusion during long-term storage. On the other hand, if it is higher than this range, the developing speed will be drastically slowed down.
그밖에 드라이필름 포토레지스트용 감광성 수지 조성물은 광중합성 다관능성 단량체, 광개시제 등을 포함하는 바, 이는 당업계에 통상의 지식을 가진 자라면 알 수 있는 정도의 것들로서, 특별히 그 함량범위 및 성분이 한정되는 것은 아니다 In addition, the photosensitive resin composition for dry film photoresists includes a photopolymerizable polyfunctional monomer, a photoinitiator, and the like, which are known to those skilled in the art, and the content ranges and components thereof are particularly limited. It doesn't become
본 발명에 따른 감광성 수지 조성물은 증가된 밀착력으로 인해 특수 메탈에 대한 케미칼 밀링(Chemical Milling)용으로 사용될 수 있다. 즉, 본 발명의 드라이필름레지스트는 기존의 드라이 필름에 대한 밀착력이 약한 특수 금속과 무기재료(몰리브텐, 스테인레스강(Stainless Steel), 니켈, 알로이42(니켈/철 합금), 크롬, 아이티오(ITO; 인듐/틴 산화물) 등)에 대한 밀착력이 향상되어, 이들 재료의 포토레지스트로 사용되기에 적당하다. 그 외 내층, 외층, 연성 인쇄회로기판 및 리드프레임(Lead Frame) 등에도 사용할 수 있으며, 증가된 밀착력으로 수율향상이 기대된다.
The photosensitive resin composition according to the present invention can be used for chemical milling for special metals due to the increased adhesion. That is, the dry film resist of the present invention is a special metal and an inorganic material (molybdenum, stainless steel, nickel, alloy 42 (nickel / iron alloy), chromium, IoT that has a weak adhesion to the existing dry film) (ITO; indium / tin oxide) and the like have improved adhesion, and are suitable for use as photoresist of these materials. In addition, it can be used for inner layer, outer layer, flexible printed circuit board, lead frame, etc., and yield improvement is expected due to increased adhesion.
다음 실시예에 의해 본 발명을 보다 상세하게 설명하고자 한다. 본 실시예는 이해를 돕기 위한 것이며 본 발명이 여기에 한정하는 것은 아니다.The following examples illustrate the present invention in more detail. This embodiment is for the purpose of understanding and the present invention is not limited thereto.
실시예 1 내지 6 및 비교예Examples 1-6 and Comparative Examples
하기 표 1과 같은 공중합 화합물을 표 1 기재의 함량으로 라디칼 공중합시켜 하기 표 1의 분자량으로 얻어진 고분자 결합제, 기타 광개시제 및 광중합성 단량체를 다음 표 2와 같은 조성으로 조액하여 실시예 1 내지 6 및 비교예의 감광성 수지 조성물을 제조하였다. 그리고, 상기 실시예 1 내지 6 및 비교예의 조성물을 폴리에틸렌테레프탈레이트 필름 위에 건조후 30㎛ 두께가 되도록 코팅하고 건조하였다. 건조 후 보호필름으로 폴리에틸렌 필름을 라미네이션하여 드라이필름 포토레지스트를 제조하였다. Table 1 is a copolymer of a compound as shown in Table 1 to radically copolymerize the polymer binder, other photoinitiator and photopolymerizable monomer obtained at the molecular weight of Table 1 to the composition shown in Table 2 below Examples 1 to 6 and comparison The photosensitive resin composition of the example was manufactured. In addition, the compositions of Examples 1 to 6 and Comparative Examples were coated on a polyethylene terephthalate film and dried to have a thickness of 30 μm. After drying, the polyethylene film was laminated with a protective film to prepare a dry film photoresist.
상기 조성에 의해 제조한 감광성 수지 조성물을 다음과 같은 공정을 거쳐 평가하였다.The photosensitive resin composition manufactured by the said composition was evaluated through the following processes.
(1)라미네이션(1) Lamination
감광성 수지 조성물로부터 제작되어진 드라이필름 포토레지스트를 브러시(Brush) 연마 처리되어진 1.6mm 두께의 동장적층판에 기판예열 롤 온도 120℃, 라미네이터 롤온도 115℃, 롤압력 4.0kgf/㎠, 그리고 롤속도 2.5m/min의 조건으로 HAKUTO MACH 610i를 이용하여 라미네이션하였다.The dry film photoresist fabricated from the photosensitive resin composition was subjected to a brush polishing process on a 1.6 mm thick copper clad laminate, and the substrate preheat roll temperature was 120 ° C., the laminator roll temperature was 115 ° C., the roll pressure was 4.0 kgf / cm 2, And it laminated using the HAKUTO MACH 610i on the conditions of the roll speed 2.5m / min.
(2)현상 및 해상도(2) Developing and resolution
동장적층판에 라미네이션한 드라이필름 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. 동장적층판 상의 미노광 부위의 드라이필름 포토레지스트가 현상액에 완전히 씻겨지기까지 소요된 시간을 초시계를 이용하여 측정하였으며(최소현상시간) 제품 평가시는 브레이크 포인트 50%로 고정하였다(최소현상시간의 2배).The dry film photoresist laminated on the copper clad laminate was allowed to stand for 20 minutes after irradiating ultraviolet rays at an exposure dose of 40 mJ using a Perkin-Elmer ™ OB7120 (parallel light exposure machine) using a photomask for circuit evaluation. 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 of the unexposed area on the copper clad laminate to be completely washed in the developer was measured by using a stopwatch (minimum development time). When evaluating the product, the break point was fixed at 50% (2 of the minimum development time). ship).
(3)연필경도(3) pencil hardness
현상기를 통과하여 제조된 시료에서 독립세선을 연필경도계를 이용하여 평가하였다. 연필경도평가는 Imoto사의 기기를 사용하였으며, 하중 100g, 연필 2B, 속도 40mm/min의 조건으로 평가하였다.Independent thin wires were evaluated by using a pencil hardness tester in a sample prepared by passing through a developer. Pencil hardness was evaluated using Imoto's equipment, under the conditions of load 100g, pencil 2B, speed 40mm / min.
(4)분자량 분포(4) Molecular weight distribution
Waters 450 GPC를 이용하여 폴리스타이렌을 스텐다드로 측정하였다. 칼람은 Shodex 105, 104, 103을 사용하였다.Polystyrene was measured by standard using Waters 450 GPC. The column used Shodex 10 5 , 10 4 , 10 3 .
상기 실시예 및 비교예에서 제조한 감광성 수지 조성물의 물성을 다음 표 3에 나타내었다. Physical properties of the photosensitive resin composition prepared in Examples and Comparative Examples are shown in Table 3 below.
이상의 실시예들과 비교예를 통한 본 발명의 결과, 비교예에 비하여 밀착력이 증가하고 연필 경도 값이 우수하였다.
As a result of the present invention through the above examples and comparative examples, the adhesion was increased and the pencil hardness value was superior to the comparative example.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 글리시딜 메타크릴레이트를 적용한 드라이필름 포토레지스트는 화학적 및 물리적 밀착력이 향상되었는 바, 화학적 밀착력은 현상액 및 에칭액등에 대한 내성이 증가됨을 의미하며, 물리적 밀착력은 공정상 받게 되는 긁힘, 구동롤에 의한 손상 등을 의미한다. 이러한 밀착력의 증가는 곧 공정안정성의 향상으로 나타나게 된다. 이로 인해 기존 대비 수율이 상승하게 된다. 또한 기존 드라이 필름으로는 내성이 부족했던 특수 금속에 대한 에칭 레지스트로서의 역할이 가능하여, 몰리브덴, 스테인레스강(Stainless Steel), 니켈, 알로이42(니켈/철 합금), 크롬, 아이티오(ITO; 인듐/틴 산화물) 등에 잘 적용되어 케미칼 밀링(Chemical Milling)용으로의 용도가 증대될 것으로 판 단된다.As described in detail above, the dry film photoresist to which glycidyl methacrylate is applied according to the present invention has improved chemical and physical adhesion, and the chemical adhesion means increased resistance to developer and etching solution, and physical adhesion. Means the scratches received during the process, the damage caused by the driving roll. This increase in adhesion results in an improvement in process stability. As a result, the yield is increased compared to the existing one. It can also serve as an etch resist for special metals that lacked resistance in conventional dry films, such as molybdenum, stainless steel, nickel, alloy 42 (nickel / iron alloy), chromium, and ITO (ITO). / Tin oxides), etc., is expected to increase its use for chemical milling.
Claims (5)
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| KR1020040085589A KR20060036577A (en) | 2004-10-26 | 2004-10-26 | Photosensitive resin composition and dry-film photoresist using it |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150075033A (en) * | 2013-12-24 | 2015-07-02 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Dry Film Photoresist |
| WO2015099371A1 (en) * | 2013-12-24 | 2015-07-02 | 코오롱인더스트리 주식회사 | Photosensitive resin composition for dry film photoresist |
-
2004
- 2004-10-26 KR KR1020040085589A patent/KR20060036577A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150075033A (en) * | 2013-12-24 | 2015-07-02 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Dry Film Photoresist |
| WO2015099371A1 (en) * | 2013-12-24 | 2015-07-02 | 코오롱인더스트리 주식회사 | Photosensitive resin composition for dry film photoresist |
| CN105849640A (en) * | 2013-12-24 | 2016-08-10 | 可隆工业株式会社 | Photosensitive resin composition for dry film photoresist |
| CN105849640B (en) * | 2013-12-24 | 2019-11-26 | 可隆工业株式会社 | The photosensitive resin composition of dry film photoresist |
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