KR100457693B1 - Radiation curable composition comprising at least five kinds of polyfunctional acryl monomers containing at least three kinds of acrylate compounds - Google Patents
Radiation curable composition comprising at least five kinds of polyfunctional acryl monomers containing at least three kinds of acrylate compounds Download PDFInfo
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- KR100457693B1 KR100457693B1 KR1019970018769A KR19970018769A KR100457693B1 KR 100457693 B1 KR100457693 B1 KR 100457693B1 KR 1019970018769 A KR1019970018769 A KR 1019970018769A KR 19970018769 A KR19970018769 A KR 19970018769A KR 100457693 B1 KR100457693 B1 KR 100457693B1
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- KR
- South Korea
- Prior art keywords
- acrylate
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- radiation curable
- photocurable composition
- curable composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 title claims abstract description 19
- -1 acryl Chemical group 0.000 title claims abstract description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 5
- 230000005855 radiation Effects 0.000 title abstract 4
- 229920005596 polymer binder Polymers 0.000 claims abstract description 8
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 8
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 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 6
- 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 claims abstract description 6
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 claims abstract description 5
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims abstract description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- FCCCBUZZVMFQBE-UHFFFAOYSA-N C(C=C)(=O)OC(C(C1=CC=CC=C1)(OCC)OCC)(C)OC(C=C)=O Chemical compound C(C=C)(=O)OC(C(C1=CC=CC=C1)(OCC)OCC)(C)OC(C=C)=O FCCCBUZZVMFQBE-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
본 발명은 해상도 및 텐팅성이 개선된 광경화성 조성물에 관한 것으로, 보다 상세하게는 인쇄회로기판 제작시 사용되는 드라이 필름 포토레지스터에 사용되는 광경화성 조성물에 관한 것이다.The present invention relates to a photocurable composition having improved resolution and tentability, and more particularly, to a photocurable composition used in a dry film photoresist used in manufacturing a printed circuit board.
일반적으로 광경화성 조성물은 인쇄회로기판, 프린트 배선판, 금속릴리프사형성 등의 미세가공에 사용되는 것으로, 아크릴계 공중합체를 결합지지체로하여 광중합모노머, 광개시제, 광증감제, 발색제, 가소제, 열안정제 등을 조합하여 제조한다.In general, photocurable compositions are used for microfabrication of printed circuit boards, printed wiring boards, metal relief yarns, and the like, and photopolymerization monomers, photoinitiators, photo-sensitizers, colorants, plasticizers, thermal stabilizers, etc., using an acrylic copolymer as a bonding support. It is prepared by combining.
예를 들면 광경화성 조성물을 폴리에틸렌테레프탈레이트 필름위에 임의의 두께로 적층하고, 이를 폴리에틸렌 필름으로 보호 적층시킨 드라이 필름 포토레지스트를 만들어 인쇄회로기판 제작에 사용한다.For example, the photocurable composition is laminated on a polyethylene terephthalate film in an arbitrary thickness, and a dry film photoresist obtained by protecting and laminating it with a polyethylene film is used to prepare a printed circuit board.
이때에 드라이 필름 포토레지스트를 동장적층판(CCLS)에 라미네이션 시킨 후 고압수은등 하에서 감광층을 노광한 후 폴리에틸렌테레프탈레이트 필름을 벗겨내고 포토레지스트의 미노광 부분을 알카리 수용액으로 씻겨낼 때 해상도 부족으로 인하여 미세회로 제품의 생산이 불가능하고, 또한 현상시 동판의 구멍을 막고 있는 감광층의 텐팅성 부족으로 제품 생산시 불량율 증가 및 생산성 저하의 문제를 초래하였다.At this time, after laminating the dry film photoresist to CCLS, exposing the photosensitive layer under high pressure mercury lamp, peeling off the polyethylene terephthalate film and washing the unexposed part of the photoresist with alkaline aqueous solution The production of circuit products is impossible, and the lack of tentability of the photosensitive layer blocking the holes of the copper plate during development has caused problems of increased defective rate and reduced productivity.
본 발명은 이러한 종래 기술의 문제점을 해결하고자 한 것으로, 그 목적은 해상도와 텐팅성이 향상되어 인쇄회로기판의 미세회로 구현을 가능토록 한 광경화성 조성물을 제공하는 데에 있다.The present invention is to solve the problems of the prior art, an object of the present invention is to provide a photocurable composition that enables the implementation of a fine circuit of a printed circuit board to improve the resolution and tentability.
본 발명은 알카리 수용액으로 드라이 필름을 현상할 때의 해상도 및 텐팅성을 향상시키기 위하여 기존 광경화성 조성물의 성분 중에서 주성분인 고분자 결합제와 감광제, 발색제 및 기타첨가제 등은 변화시키지 않고 다기능성 아크릴모노머를 적어도 5종 이상 사용하였다.In order to improve the resolution and tentability when developing a dry film with an aqueous alkaline solution, the present invention can be performed by using a multi-functional acrylic monomer without changing the polymer binder, photosensitive agent, coloring agent and other additives, which are the main components, among the components of the existing photocurable composition. 5 or more types were used.
즉, 본 발명에 따른 해상도 및 텐팅성이 개선된 광경화성 조성물은 고분자 결합제를 주성분하고 여기에 광경화성 모노머, 광중합개시제 및 기타 발색제, 발색안정제, 밀착촉진제, 열안정제 등의 첨가제를 혼합하여 조성되는 광경화성 조성물에 있어서, 다기능성 아크릴모노머를 5종 이상 함유하되 아크릴레이트 화합물을 적어도 3종 이상 함유토록 한 데에 그 특징이 있다.That is, the photocurable composition having improved resolution and tentability according to the present invention is composed of a polymer binder and a photocurable monomer, a photopolymerization initiator and other coloring agents, color stabilizers, adhesion promoters, thermal stabilizers, etc. The photocurable composition is characterized by containing five or more kinds of multifunctional acrylic monomers and at least three kinds of acrylate compounds.
본 발명에서 고분자 결합제로는 유기고분자, 예를 들면 아크릴계 폴리머, 스티렌계 폴리머, 폴리아세트산비닐, 에틸렌아세트산비닐, 폴리염화비닐, 염화비닐-아세트산비닐 공중합체, 염소화폴리에틸렌, 염소화폴리프로필렌, 염화비닐리덴계 폴리머, 폴리에스테르, 폴리아미드, 폴리우레탄, 폴리비닐아세탈, 알키드수지, 페놀수지, 에폭시수지, 아세트산셀룰로즈, 질산화면, 스티렌-부티렌 공중합체, 스티렌-아크릴로니트릴 공중합체, 염화고무, 말레익안하이드라이드의 비닐공중합체, 방향족술폰아미드포름알데하이드 수지 등을 사용할 수 있다.In the present invention, the polymer binder is an organic polymer such as an acrylic polymer, a styrene polymer, polyvinyl acetate, ethylene vinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride Den-based polymers, polyesters, polyamides, polyurethanes, polyvinyl acetals, alkyd resins, phenolic resins, epoxy resins, cellulose acetates, nitrate screens, styrene-butyrene copolymers, styrene-acrylonitrile copolymers, rubber chlorides, males Ionic hydride vinyl copolymer, aromatic sulfonamide formaldehyde resin, etc. can be used.
특히 본 발명의 실시예에서는 고분자결합제로 아크릴산 10wt%, 메타크릴산 15wt%, 메틸메타크릴레이트 60wt%, 및 2-에틸헥실아크릴레이트 15wt%를 조합하여 제조한 아크릴공중합체를 사용하였다. 그러나 이는 본 발명의 이해를 돕기 위한 방법일뿐 본 발명이 이에 한정되는 것은 아니다. 또한 본 발명의 목적을 벗어나지 않는 범위에서 메틸아크릴레이트, 스타이렌, 2-페녹시메틸아크릴레이트, 2-페녹시에틸아크릴레이트, 말레이산, 말레이산무수물, 비닐아세테이트 등의 조합으로 제조된 아크릴공중합체를 사용할 수도 있다.In particular, in the embodiment of the present invention, an acrylic copolymer prepared by combining 10 wt% acrylic acid, 15 wt% methacrylic acid, 60 wt% methyl methacrylate, and 15 wt% 2-ethylhexyl acrylate as a polymer binder was used. However, this is only a method for helping understanding of the present invention, but the present invention is not limited thereto. Also in the range without departing from the object of the present invention, the acrylic air prepared by the combination of methyl acrylate, styrene, 2-phenoxymethyl acrylate, 2-phenoxyethyl acrylate, maleic acid, maleic anhydride, vinyl acetate, etc. Coalescing may also be used.
이러한 고분자결합제는 감광층의 물리적 지지 열할을 함과 동시에 밀착력과 텐팅성 등의 특성을 부여한다.Such polymer binders impart physical support deterioration of the photosensitive layer and at the same time provide properties such as adhesion and tentability.
다기능성 아크릴모노머는 광중합개시제에 의해 광중합을 하는 모노머로서 2개 이상의 반응기를 갖는 다관능성 아크릴계 화합물을 주로 사용한다. 이로는 폴리에틸렌 글리콜 디메타크릴레이트(PEGD), 프로폭시레이티드 트리메틸올 프로판 트리아크릴레이트(PTPA), 에폭시레이티드 트리메틸올 프로판 트리아크릴레이트(ETPA), 네오펜틸 글리콜 디메타크릴레이트(NPGD), 페녹시 에틸 아크릴레이트(PNEA), 2-하이드록시-3-페녹시-프로필 아크릴레이트(HPPA), 페놀 에톡시레이트 아크릴레이트(PPEA), 노닐페놀 폴리프로폭시레이트 아크릴레이트(NPPA), 트리메틸올프로판 폴리프로폭시레이티드 트리아크릴레이트(TPPA), 베타-메타크릴오일 옥시에틸 하이드로겐 석시네이트(MOHS), 메타크릴옥시 폴리에톡시 프로판(MAPP), 비스-아크릴옥시 디에톡시 페닐 프로판(ADPP) 등을 사용할 수 있다.The multifunctional acrylic monomer mainly uses a polyfunctional acrylic compound having two or more reactors as a monomer for photopolymerization by a photopolymerization initiator. These include polyethylene glycol dimethacrylate (PEGD), propoxylated trimethylol propane triacrylate (PTPA), epoxidized trimethylol propane triacrylate (ETPA), neopentyl glycol dimethacrylate (NPGD), Phenoxy ethyl acrylate (PNEA), 2-hydroxy-3-phenoxy-propyl acrylate (HPPA), phenol ethoxylate acrylate (PPEA), nonylphenol polypropoxylate acrylate (NPPA), trimethylol Propane polypropoxylated triacrylate (TPPA), beta-methacryloyl oxyethyl hydrogen succinate (MOHS), methacryloxy polyethoxy propane (MAPP), bis-acryloxy diethoxy phenyl propane (ADPP) Etc. can be used.
특히, 다기능성 아크릴모노머중 MAPP를 2∼3wt%로 함유되도록 하는 것이 바람직하며, 그 이유는 MAPP가 2wt% 이하로 함유되면 해상도가 떨어지고, MAPP가 3wt% 이상으로 함유되면 해상도 및 텐팅성이 나빠지기 때문이다.Particularly, it is preferable to contain 2 to 3 wt% of MAPP in the multifunctional acrylic monomer. The reason is that when MAPP is contained in 2 wt% or less, the resolution is lowered. When MAPP is contained in 3 wt% or more, the resolution and tentability are poor. Because it falls out.
그리고 그 외에도자외선 빛에 의해 여기되어 반응을 개시하는 광개시제, 감광제, 발색제 및 기타첨가제 등은 기존의 광경화성 조성물과 같은 것을 사용한다.In addition, photoinitiators, photosensitizers, colorants, and other additives that are excited by ultraviolet light to initiate a reaction use the same photocurable composition as the conventional photocurable composition.
이러한 본 발명에 따른 광경화성 조성물은 드라이 필름 포토레지스트를 만드는데 사용되며, 드라이 필름 포토레지스트는 지지체인 폴리에스터(PET) 필름에 광경화성 조성물을 도포한 후 그 위에 폴리에틸렌(PE) 필름으로 보호층을 형성한 것으로 컴퓨터, 전자통신기기 및 민생전자부품에 전기 접속으로 사용되는 인쇄회로기판 제작에 사용된다.The photocurable composition according to the present invention is used to make a dry film photoresist, and the dry film photoresist is applied to the polyester (PET) film as a support and then coated with a protective film with a polyethylene (PE) film thereon. It is used in the manufacture of printed circuit boards that are used as electrical connections to computers, telecommunications equipment and consumer electronic components.
이러한 드라이 필름 포토레지스트는 아크릴모노머 화합물내 아크록시, 메타아크록시, 에폭시, 프로폭시, 메톡시, 페녹시 등의 기(Group)를 적어도 2개 이상 가진 말달 에틸렌성 불포화 화합물이 함유되어 강도 및 현상시간이 향상되면서 알카리 수용액으로 현상한 후 해상도가 향상되어 미세회로 형성을 가능하게 한다.Such dry film photoresists contain maldall ethylenically unsaturated compounds having at least two groups, such as acryoxy, metaacryloxy, epoxy, propoxy, methoxy, phenoxy, etc. in the acrylic monomer compound. As the time is improved, the resolution is improved after developing with an alkaline aqueous solution to enable formation of a microcircuit.
이하 실시예를 통해 상세히 설명하고자 한다.It will be described in detail through the following examples.
실시예 1∼3 및 비교예 1, 2Examples 1-3 and Comparative Examples 1 and 2
고분자 결합제로 아크릴산 10wt%, 메타크릴산 15wt%, 메틸메타크릴레이트 60wt%, 및 2-에틸헥실아크릴레이트 15wt%를 조합하여 제조한 아크릴공중합체(액상, 고형분 50%) 75.0 중량부, 벤조 페논 0.8중량부, 에틸-4-디메틸아미노벤조에이트 0.3중량부, 사비닐그린 3GLS(염료) 0.1중량부, 2,2-디메톡시디페닐에타논 0.5중량부, P-톨루엔술폰산 0.2중량부, 다이아몬드 그린 GH(염료) 0.1중량부로 된 조성에 아래 표1의 다기능성 아크릴모노머를 조합하여 전체가 100중량부가 되도록 메틸에틸케톤을 첨가하여 광경화성 조성물을 제조하였다.75.0 parts by weight of acrylic copolymer (liquid, solid 50%) prepared by combining 10 wt% acrylic acid, 15 wt% methacrylic acid, 60 wt% methyl methacrylate, and 15 wt% 2-ethylhexyl acrylate as a polymer binder, benzophenone 0.8 parts by weight, 0.3 parts by weight of ethyl-4-dimethylaminobenzoate, 0.1 parts by weight of savingreen 3GLS (dye), 0.5 parts by weight of 2,2-dimethoxydiphenylethanone, 0.2 parts by weight of P-toluenesulfonic acid, diamond A photocurable composition was prepared by adding methyl ethyl ketone so that the total amount was 100 parts by weight by combining the multifunctional acrylic monomer shown in Table 1 below with 0.1 parts by weight of green GH (dye).
[표 1]TABLE 1
다기능성 아크릴모노머의 사용량Usage of Multifunctional Acrylic Monomer
상기 각 실시예 및 비교예에서 제조된 광경화성 조성물을 사용하여 공지의 방법으로 드라이 필름 포토레지스트를 만든 후, 이것을 가지고 광경화성 조성물의 물리적 특성을 다음과 같은 방법으로 측정하였다.After the dry film photoresist was made by a known method using the photocurable compositions prepared in the above Examples and Comparative Examples, the physical properties of the photocurable composition were measured by the following method.
감도Sensitivity
동판에 드라이 필름을 라미네이션시킨 후 합지된 동판위에 감도측정용 포토마스크를 올린 후 자외선으로 노광 및 탄산나트륨 용액으로 현상시킨 다음 동판위에 나타난 감도를 측정하였다.After laminating a dry film on the copper plate, a photomask for sensitivity measurement was placed on the laminated copper plate, and then exposed to ultraviolet light and developed with sodium carbonate solution, and then the sensitivity shown on the copper plate was measured.
해상도resolution
동판에 드라이 필름을 라미네이션시킨 후 합지된 동판위에 해상도측정용 포토마스크를 올린 후 자외선으로 노광 및 탄산나트륨 용액으로 현상시킨 다음 동판위에 나타난 해상도를 측정하였다.After laminating a dry film on the copper plate, a photomask for measuring the resolution was placed on the laminated copper plate, exposed to ultraviolet rays and developed with sodium carbonate solution, and the resolution shown on the copper plate was measured.
현상시간Developing time
동판에 드라이 필름을 라미네이션 시킨 후 합지된 동판을 탄산나트륨 용액에 현상시킬 때 현상 완료시간을 측정하였다.After completion of laminating the dry film on the copper plate, the development completion time was measured when the laminated copper plate was developed in a sodium carbonate solution.
텐팅성Tentability
구멍이 나 있는 동판에 드라이 필름을 합지시킨 후 합지된 동판의 구멍위에 덮힌 필름의 강도를 필름의 인장강도 측정용 인스트론을 이용하여 측정하였다.After laminating the dry film to the perforated copper plate, the strength of the film covered on the hole of the laminated copper plate was measured using an instron for measuring the tensile strength of the film.
[표 2]TABLE 2
물리적 특성 평가Physical property evaluation
표 2를 참조해 보면, 본 발명에 실시예에서 제조된 광경화성 조성물을 사용한 경우의 모두 해상도는 90㎛ 이하, 현상시간 45초 이하인데 반해, 기존의 광경화성 조성물을 사용한 경우에는 해상도는 110㎛ 이하, 현상시간 55초 이하임을 알 수 있다.Referring to Table 2, the resolution in the case of using the photocurable composition prepared in Example in the present invention is 90 µm or less and the development time of 45 seconds or less, whereas in the case of using the conventional photocurable composition, the resolution is 110 µm. It can be seen that the development time is 55 seconds or less.
이상에서 상세히 설명한 바와 같이, 본 발명에서는 광경화성 조성물에 다기능성 아크릴모노머를 5종 이상 함유시키되 아크릴레이트 화합물을 적어도 3종 이상 함유토록 하여 해상도 및 텐팅성을 향상시킴으로써 인쇄회로기판의 미세회로의 구현을 가능토록 하였다.As described in detail above, in the present invention, the photocurable composition contains five or more kinds of multifunctional acrylic monomers, but includes at least three kinds of acrylate compounds to improve the resolution and the tentability, thereby realizing the microcircuits of the printed circuit board. Was made possible.
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| US4942112A (en) * | 1988-01-15 | 1990-07-17 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions and elements for refractive index imaging |
| US5013631A (en) * | 1989-03-03 | 1991-05-07 | Westinghouse Electric Corp. | Ultraviolet curable conformal coatings |
| US5346805A (en) * | 1990-11-01 | 1994-09-13 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
| KR950012136A (en) * | 1993-10-20 | 1995-05-16 | 하기주 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942112A (en) * | 1988-01-15 | 1990-07-17 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions and elements for refractive index imaging |
| US5013631A (en) * | 1989-03-03 | 1991-05-07 | Westinghouse Electric Corp. | Ultraviolet curable conformal coatings |
| US5346805A (en) * | 1990-11-01 | 1994-09-13 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
| KR950012136A (en) * | 1993-10-20 | 1995-05-16 | 하기주 | Photosensitive resin composition |
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