KR100731327B1 - Negative photoresist composition - Google Patents

Negative photoresist composition Download PDF

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KR100731327B1
KR100731327B1 KR1020050128008A KR20050128008A KR100731327B1 KR 100731327 B1 KR100731327 B1 KR 100731327B1 KR 1020050128008 A KR1020050128008 A KR 1020050128008A KR 20050128008 A KR20050128008 A KR 20050128008A KR 100731327 B1 KR100731327 B1 KR 100731327B1
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South Korea
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meth
acrylate
group
methyl
ether
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KR1020050128008A
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Korean (ko)
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류미선
문봉석
김선호
이광용
우승우
신대호
조행규
이갑성
김영회
변원수
김석근
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주식회사 삼양이엠에스
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Priority to KR1020050128008A priority Critical patent/KR100731327B1/en
Priority to JP2006344999A priority patent/JP4469365B2/en
Priority to TW095148307A priority patent/TWI330759B/en
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Priority to JP2009167254A priority patent/JP4672789B2/en

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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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0295—Photolytic halogen 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
    • G03F7/032—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
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties

Abstract

A negative photoresist composition is provided to show excellent thermal resistance as well as good physical properties such as UV transmittivity, remaining rate, pattern stability and chemical resistance, and to be useful in formation of patterns. The negative photoresist composition comprises 3-50 wt% of any one binder resin selected from the group consisting of a resin represented by the formula(1), a resin represented by the formula(2) and a mixture thereof, 2-40 wt% of a multivalent acrylic monomer, 0.01-10 wt% of a photoinitiator and 10-94 wt% of an organic solvent. In the formulae(1) and (2), each R1, R2, R3, R5, R6, R7 and R9 is independently H or methyl group, each R4 and R8 is independently an epoxy group-containing C1-C10 alkyl group or cycloalkyl group, R10 is any one selected from the group consisting of a C1-C14 carboxylic acid, alkoxycarbonyl and aromatic compound, each x, y, l, m and n is a molar ratio of each polymeric unit, wherein the x is 0.02-0.80, y is 0.20-0.98, l is 0.02-0.70, m is 0.05-0.60, and n is 0.01-0.60. Each binder resin is a random copolymer.

Description

음성 포토레지스트 조성물{Negative Photoresist Composition} Negative Photoresist Composition

본 발명은 액정표시소자에 사용되는 음성 포토레지스트 조성물에 관한 것으로서, 보다 상세하게는 TFT-LCD와 같은 액정표시소자의 유기 절연막, R.G.B., 블랙 메트릭스, 포토 스페이서, UV 오버코트 등 형성시 알칼리 현상액으로 현상되어 패턴 형성이 가능한 음성 포토레지스트 조성물에 관한 것이다.The present invention relates to a negative photoresist composition used in a liquid crystal display device, and more particularly, to an organic developer, RGB, black matrix, photo spacer, UV overcoat, etc. of a liquid crystal display device such as a TFT-LCD. The present invention relates to a negative photoresist composition capable of forming a pattern.

액정표시소자의 유기 절연막, R.G.B., 블랙 메트릭스, 포토 스페이서, UV 오버코트 등에 사용되는 패턴을 형성하기 위해서 감광성 재료가 사용되고 있다. 이러한 패턴 제조공정에 사용되는 감광성 수지는 평탄성과 투과성 등의 기본적인 물성 외에, 특히 내열성이 우수한 재료가 요구된다. Photosensitive materials are used to form patterns used in organic insulating films, R.G.B., black matrices, photo spacers, UV overcoats, and the like of liquid crystal display devices. The photosensitive resin used in such a pattern manufacturing process requires a material having excellent heat resistance, in addition to basic physical properties such as flatness and permeability.

현재 액정표시소자의 유기 절연막 등의 패턴 형성에 사용되는 레지스트 조성물은 바인더 수지로서 아크릴계 감광성 수지를 사용하는데, 이러한 아크릴계 감광성 수지는 220℃ 이하의 공정에서는 visible 영역에서 90% 이상의 높은 투과도를 나타내는 반면, 220℃ 이상의 고온 공정에서는 열 안정성이 취약하다. 따라서, 열에 의해 수지의 일부가 분해되고, 이로 인해 visible 영역에서의 투과도가 감소하는 경향이 있다. 또한, 고온 공정 중에 분해된 분자들에 의해 액정이 오염되고, 메 탈 및 무기물과의 접착력이 약화되는 등의 많은 문제가 발생한다. Currently, the resist composition used for forming a pattern of an organic insulating film or the like of a liquid crystal display device uses an acrylic photosensitive resin as a binder resin. The acrylic photosensitive resin has a high transmittance of 90% or more in the visible region in a process of 220 ° C. or lower, Thermal stability is weak in high temperature processes of 220 ° C or higher. Therefore, part of the resin is decomposed by heat, which tends to reduce the transmittance in the visible region. In addition, the liquid crystals are contaminated by molecules decomposed during the high temperature process, and many problems occur such as weakening of adhesion to metals and inorganic materials.

따라서, 본 발명이 이루고자 하는 기술적 과제는 상기 문제점을 해결하기 위하여 안출한 것으로서, 내열성이 우수할 뿐만 아니라 UV 투과율, 잔막율, 패턴 안정성 및 내화학성 등 기본 물성이 양호하여, 액정표시소자의 유기 절연막, R.G.B., 블랙 메트릭스, 포토 스페이서, UV 오버코트 등의 제조에 유용하게 사용될 수 있는, 수계 현상액에서 현상이 가능한 음성 포토레지스트 조성물을 제공하는데 있다.Therefore, the technical problem to be solved by the present invention is to solve the above problems, not only excellent heat resistance, but also good basic physical properties such as UV transmittance, residual film rate, pattern stability and chemical resistance, and thus the organic insulating film of the liquid crystal display device. To provide a negative photoresist composition that can be developed in an aqueous developer, which can be usefully used in the preparation of RGB, black matrix, photo spacer, UV overcoat, and the like.

상기 기술적 과제를 해결하기 위하여 본 발명에 따른 음성 포토레지스트 조성물은 하기 일반식 1로 표시되는 수지, 하기 일반식 2로 표시되는 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 바인더 수지 3 내지 50 중량%, 다가 아크릴 모노머 2 내지 40 중량%, 광개시제 0.01 내지 10 중량% 및 유기용매 10 내지 94중량%를 함유한다. In order to solve the above technical problem, the negative photoresist composition according to the present invention may be any one binder resin selected from the group consisting of a resin represented by the following general formula 1, a resin represented by the following general formula 2, and a mixture thereof: % By weight, 2 to 40% by weight polyvalent acrylic monomer, 0.01 to 10% by weight photoinitiator and 10 to 94% by weight organic solvent.

<일반식 1><Formula 1>

Figure 112005075405314-pat00001
Figure 112005075405314-pat00001

상기 일반식 1에서, R1, R2 및 R3는 각각 서로 독립적으로 H 또는 메틸기이 고, R4는 에폭시기를 포함하는 탄소원자수가 1 ~ 10인 알킬기 또는 시클로알킬기이고, x와 y는 각 중합단위의 몰비로서 x는 0.02~0.80, y는 0.20~0.98이다. 상기 일반식 1의 바인더 수지는 각 중합단위의 배열순서에 구속되지 않는 랜덤 공중합체여도 좋다.In Formula 1, R 1 , R 2 and R 3 are each independently H or a methyl group, R 4 is an alkyl or cycloalkyl group having 1 to 10 carbon atoms including an epoxy group, and x and y are each polymerized. As molar ratio of a unit, x is 0.02-0.80 and y is 0.20-0.98. The binder resin of the general formula (1) may be a random copolymer that is not bound by the sequence of the polymerized units.

<일반식 2><Formula 2>

Figure 112005075405314-pat00002
Figure 112005075405314-pat00002

상기 일반식 2에서, R5, R6, R7 및 R9는 각각 서로 독립적으로 H 또는 메틸기이고, R8은 에폭시기를 포함하는 탄소원자수가 1 ~ 10인 알킬기 또는 시클로알킬 기이고, R10은 탄소원자수가 1 ~ 14인 카르복실산, 알콕시카르보닐 및 방향족 화합물로 이루어진 그룹으로부터 선택된 어느 하나이고, l, m, n은 각 중합단위의 몰비로서 l은 0.02~0.70, m은 0.05~0.60 및 n은 0.01~0.60이다. 상기 일반식 2의 바인더 수지는 각 중합단위의 배열순서에 구속되지 않는 랜덤 공중합체여도 좋다.In Formula 2, R 5 , R 6 , R 7 and R 9 are each independently H or a methyl group, R 8 is an alkyl group or cycloalkyl group having 1 to 10 carbon atoms including an epoxy group, R 10 is a carboxylic acid having 1 to 14 carbon atoms, Any one selected from the group consisting of alkoxycarbonyl and an aromatic compound, l, m, n is the molar ratio of each polymerized unit, l is 0.02 to 0.70, m is 0.05 to 0.60 and n is 0.01 to 0.60. The binder resin of the general formula (2) may be a random copolymer that is not bound by the sequence of the polymerized units.

본 발명에 따른 음성 포토레지스트 조성물에 있어서, 상기 일반식 1 또는 일반식 2로 표시되는 바인더 수지는 내열성이 우수하여 220℃ 이상의 고온 공정에서도 거의 분해가 되지 않아 액정오염을 최소화 할 수 있고, 고온 경화 후에도 고투과율을 유지할 수 있다. 또한, 수계 알카리 현상에 필요한 작용기로서 아크릴산 대 신에 산도가 낮은 말레이미드기를 포함하고 있으므로, 레지스트의 수계 알카리 현상성이 우수하며, 상온 보관시 저장안정성이 우수한 장점이 있다.In the negative photoresist composition according to the present invention, the binder resin represented by the general formula (1) or the general formula (2) is excellent in heat resistance and hardly decomposes even at a high temperature process of 220 ° C. or higher, thereby minimizing liquid crystal contamination, and curing at high temperature. High transmittance can be maintained afterwards. In addition, since the functional group necessary for developing the aqueous alkali includes a maleic acid group having a low acidity instead of acrylic acid, the aqueous alkali developability of the resist is excellent, and storage stability at room temperature is excellent.

일반식 1과 일반식 2에서, R4와 R8은 에폭시기를 포함하는 작용기로서, 글리시딜, 3,4-에폭시부틸, 2,3-에폭시시클로헥실, 3,4-에폭시시클로헥실, 2-글리시딜옥시-1-프로필, 3-메틸옥세탄-3-메틸, 3-에틸옥세탄-3-메틸, 6,7-에폭시헵틸 등을 들 수 있고, 일반식 2의 R10의 예로는 카르복실산, 메톡시카르보닐, 에톡시카르보닐, 프로폭시카르보닐, 이소프로폭시카르보닐, 부톡시카르보닐, t- 부톡시카르보닐, 펜톡시카르보닐, 핵실옥시카르보닐, 시클로핵실옥시카르보닐, 옥틸옥시카르보닐, 데실옥시카르보닐, 도데실옥시카르보닐, 테트라데실옥시카르보닐, 아다만틸옥시카르보닐, 2-메틸아다만틸옥시카르보닐, γ-부틸로락톤옥시카르보닐, 디사이클로펜타닐옥시카르보닐, 디사이클로펜테닐옥시카르보닐, 디사이클로펜타닐-1-에틸옥시카르보닐, 디사이클로펜테닐-1-에틸옥시카르보닐, 이소보닐옥시카르보닐, 히드록시에틸옥시카르보닐, 디메틸아미노에틸옥시카르보닐, 페닐, 벤질옥시카르보닐, 4-히드록시페닐, 4-아세톡시페닐, 메톡시, 에톡시, 페닐옥시 등을 예시할 수 있다. In the general formulas (1) and (2), R 4 and R 8 are functional groups containing an epoxy group, and glycidyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, 2 -Glycidyloxy-1-propyl, 3-methyloxetane-3-methyl, 3-ethyloxetane-3-methyl, 6,7-epoxyheptyl, and the like, and examples of R 10 in General Formula 2 Is carboxylic acid, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, nucleosiloxycarbonyl, cyclonuclear Oxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, tetradecyloxycarbonyl, adamantyloxycarbonyl, 2-methyladamantyloxycarbonyl, γ-butyrolactone Oxycarbonyl, dicyclopentanyloxycarbonyl, dicyclopentenyloxycarbonyl, dicyclopentanyl-1-ethyloxycarbonyl, dicyclopente Neyl-1-ethyloxycarbonyl, isobornyloxycarbonyl, hydroxyethyloxycarbonyl, dimethylaminoethyloxycarbonyl, phenyl, benzyloxycarbonyl, 4-hydroxyphenyl, 4-acetoxyphenyl, methoxy , Ethoxy, phenyloxy and the like can be exemplified.

한편, R10을 갖는 반복단위는 (메타)아크릴산, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 핵실(메타)아크릴레이트, 시클로핵실(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 데실(메타)아크릴레이트, 도데실(메타)아크릴레이트, 테트라데실(메타)아크릴레이 트, 아다만틸(메타)아크릴레이트, 2-메틸아다만틸(메타)아크릴레이트, γ-부틸로락톤(메타)아크릴레이트, 디사이클로펜타닐(메타)아크릴레이트, 디사이클로펜테닐(메타)아크릴레이트, 디사이클로펜타닐-1-에틸(메타)아크릴레이트, 디사이클로펜테닐-1-에틸(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, (α-메틸)스틸렌, 벤질(메타)아크릴레이트, (α-메틸)히드록시스틸렌, (α-메틸)아세톡시스틸렌, 메틸비닐에테르, 에틸비닐에테르, 페닐비닐에테르 등을 공중합하여 수지에 도입할 수 있다. On the other hand, the repeating unit having R 10 is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, nuclear chamber (meth) acrylate, cyclonuclear chamber (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) Acrylate, tetradecyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, γ-butylolactone (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl-1-ethyl (meth) acrylate, dicyclopentenyl-1-ethyl (meth) acrylate, isobornyl (meth) acrylate, hydroxy Ethyl (meth) acrylate, dimethyla Noethyl (meth) acrylate, (α-methyl) styrene, benzyl (meth) acrylate, (α-methyl) hydroxystyrene, (α-methyl) acetoxystyrene, methylvinylether, ethylvinylether, phenylvinyl Ether etc. can be copolymerized and introduce | transduced into resin.

상기 일반식 1 또는 일반식 2의 바인더 수지는 중합단위의 배열순서에 구속되지 않는 랜덤 공중합체여도 좋으며, 전술한 범위 내에서 R1~R10의 종류를 변화시킨 혼합물의 형태로 사용할 수 있음은 물론이다.The binder resin of Formula 1 or Formula 2 may be a random copolymer that is not bound to the sequence of the polymerization unit, it can be used in the form of a mixture in which the type of R 1 ~ R 10 changed within the above range Of course.

상기 일반식 1 또는 일반식 2로 표시되는 바인더 수지의 평균 분자량은 2,000 내지 300,000, 분산도는 1.0 내지 10.0인 것을 사용하는 것이 바람직하며, 평균 분자량 4,000 내지 100,000이고, 분산도는 1.5 내지 3.0인 것을 사용하는 것이 더욱 바람직하다.It is preferable to use the average molecular weight of the binder resin represented by the general formula 1 or formula 2 is 2,000 to 300,000, the dispersion degree is 1.0 to 10.0, the average molecular weight is 4,000 to 100,000, the dispersion degree is 1.5 to 3.0 It is more preferable to use.

또한, 본 발명의 음성 포토레지스트 조성물은 다가 아크릴 모노머를 함유한다. 2개 이상의 아크릴기를 갖는 중합성 화합물인 다가 아크릴 모노머는 음성 포토레지스트의 내열성과 패턴안정성을 유지할 수 있도록 기능한다. 다가 아크릴 모노머의 예로는 에틸렌옥사이드기의 수가 2 내지 20인 폴리에틸렌글리콜디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 20인 폴리프로필렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 비스페놀 A 디글리시딜에테르아크릴산 부가물, 에틸이소시아눌릭산트리(메타)아크릴레이트, β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트부가물 등의 이소시아네이트와의 부가물, 트리메틸올프로판트리(메타)아크릴레이트, 테트라메틸올메탄테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트로 이루어진 군으로부터 선택된 다가 알콜과 α,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물 트리메틸올프로판트리글리시딜에테르아크릴산 부가물, 우레탄기를 갖는 2가 내지 6가 히드록시 화합물의 (메타)아크릴산 부가물(일본국 신나카무라사의 U series, UA series) 및 3-히드록시-2,2-디메틸프로필산-2-프로펜에스터와 2-옥세파논 중합체의 에스테르 축합체(일본국 일본화약의 KAYARAD HX-220) 등을 들 수 있는데, 이들을 각각 단독으로 또는 둘 이상을 혼합하여 사용할 수 있다. In addition, the negative photoresist composition of the present invention contains a polyvalent acrylic monomer. The polyhydric acrylic monomer, which is a polymerizable compound having two or more acrylic groups, functions to maintain heat resistance and pattern stability of the negative photoresist. Examples of the polyhydric acrylic monomers include polyethylene glycol di (meth) acrylate having 2 to 20 ethylene oxide groups, ethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acryl having 2 to 20 propylene oxide groups. Rate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether acrylic acid adduct, ethyl isocyanuric acid tri (meth) acrylate, β-hydroxyethyl ( Phthalic acid diester of meta) acrylate, addition product with isocyanate, such as toluene diisocyanate addition product of (beta) -hydroxyethyl (meth) acrylate, trimethylol propane tri (meth) acrylate, tetramethylol methane tetra (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Compound trimethylol obtained by esterifying a polyhydric alcohol selected from the group consisting of thritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol tri (meth) acrylate with α, β-unsaturated carboxylic acid Propanetriglycidyl ether acrylic acid adduct, (meth) acrylic acid adduct of the dihydric to hexavalent hydroxy compound having a urethane group (U series, UA series from Shin-Nakamura, Japan) and 3-hydroxy-2,2-dimethyl Ester condensates of propyl acid-2-propene ester and 2-oxepanone polymer (KAYARAD HX-220 from Nippon Kayaku Co., Ltd.), and the like, may be used alone or in combination of two or more thereof.

또한, 본 발명의 음성 포토레지스트 조성물에 함유되는 광개시제로는 음성 포토레지스트 조성물에 사용되는 통상적인 광개시제를 사용할 수 있다. 통상적으로 아세토페논계나 벤조페논계를 사용하는데, 광개시제 자체가 색을 가지면 투명성을 저하시키는 작용을 하므로 노광시 사용하는 파장대에서 적절한 감도를 갖고 광개시제 자체에 색을 갖지 않는 것을 사용하는 것이 바람직하다. 일반적으로 아크릴계 다기능 모노머를 사용하는 가교 반응의 광개시제는 사용하는 자외선의 파장에 맞추어서 사용되는데 310∼450nm의 파장 영역에서 라디칼을 발생하는 광개시제를 사용 한다.As the photoinitiator contained in the negative photoresist composition of the present invention, conventional photoinitiators used in the negative photoresist composition may be used. Usually, acetophenone-based or benzophenone-based are used. When the photoinitiator itself has a color, the transparency is lowered. Therefore, it is preferable to use an acetophenone-based or a benzophenone-based one having a suitable sensitivity in the wavelength band used during exposure and having no color in the photoinitiator itself. In general, the photoinitiator of the cross-linking reaction using an acrylic multifunctional monomer is used in accordance with the wavelength of the ultraviolet rays used, a photoinitiator that generates radicals in the wavelength range of 310 ~ 450nm.

상기와 같은 광개시제로는 등의 아세토페논 및 벤조페논계와 트리아진계를 사용하는 것이 바람직하며, 구체적인 예로는 Irgacure 651, Irgacure 907, 벤조페논, 페닐비페닐케톤, 1-히드록시-1-벤조일시클로헥산, 벤질, 벤질디메틸케탈, 1-벤질-1-디메틸아미노-1-(4-모폴리노-벤조일)프로판, 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판, 치오잔톤(thioxanthone), 1-클로로-4-프록시치오잔톤, 이소프로필치오잔톤, 디에틸치오잔톤, 에틸안트라퀴논, 4-벤조일-4-메틸디페닐설파이드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 벤조일포름산메틸, 1,7-비스(9-아크리디닐)헵탄, 9-n-부틸-3,6-비스 (2-모폴리노-이소부틸로일)카바졸, 2-메틸-4,6-비스 (트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스 (트리클로로메틸)-s-트리아진 등이 있다. 이러한 광개시제는 투명성을 높이며 dose량을 최소화하기 위한 함량으로서 예를 들어 0.01 내지 10 중량%, 바람직하게는 0.5 내지 7 중량%를 사용하는 것이 보다 효과적이다.As the photoinitiator, it is preferable to use acetophenone, benzophenone series, and triazine series, such as Irgacure 651, Irgacure 907, benzophenone, phenylbiphenyl ketone, and 1-hydroxy-1-benzoylcyclo. Hexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, thioxanthone ( thioxanthone), 1-chloro-4- hydroxy thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl-4-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2- Benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoyl formate, 1,7-bis (9-acridinyl ) Heptane, 9-n-butyl-3,6-bis (2-morpholino-isobutyloyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2 - Carbonyl-4, 6-bis (trichloromethyl) -s- triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s- triazine, etc. There are. Such photoinitiator is more effective to use, for example, 0.01 to 10% by weight, preferably 0.5 to 7% by weight as a content to increase the transparency and minimize the dose.

또한, 본 발명의 음성 포토레지스트 조성물에는 필요에 따라 접착보조제로 에폭시기 또는 아민기를 갖는 실리콘계 화합물을 첨가하여 사용할 수 있는데, 이러한 실리콘계 화합물은 ITO 전극과 음성 포토레지스트 조성물과의 접착력을 향상시키며, 경화 후 내열 특성을 증대시킬 수 있다. 이러한 에폭시기 또는 아민기를 갖는 실리콘계 화합물로는 (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥 시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸메톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실레인 및 아미노프로필트리메톡시 실레인 등이 있으며, 이들을 각각 단독으로 또는 이들을 혼합하여 사용할 수 있다. 바람직한 함량은 0.0001 내지 3 중량%이다.In addition, a silicone-based compound having an epoxy group or an amine group may be added to the negative photoresist composition of the present invention as needed as an adhesive aid, and the silicone-based compound may improve adhesion between the ITO electrode and the negative photoresist composition, and after curing Heat resistance characteristics can be improved. As a silicone type compound which has such an epoxy group or an amine group, it is (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxy silane, (3-glycidoxy propyl) methyldimethoxy Silane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxy Butyltrimethoxysilane, 3,4-Epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, aminopropyltrimethoxy silane, and the like, and these may be used alone or in combination. Preferred content is 0.0001 to 3% by weight.

또한, 본 발명의 음성 포토레지스트 조성물에는 필요에 따라 광증감제, 열중합 금지제, 소포제, 레벨링제 등의 상용성이 있는 첨가제를 첨가할 수 있다.In addition, to the negative photoresist composition of the present invention, compatible additives such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, and a leveling agent may be added as necessary.

전술한 성분들에 용매를 가한 음성 포토레지스트 조성물은 기판 위에 스핀코팅한 후 마스크를 이용하여 자외선을 조사하여 알칼리 현상액으로 현상하는 방법을 통하여 패턴을 형성하게 되는데, 용매의 함량은 10 내지 94중량%인 것이 바람직하며, 통상적으로 점도를 1 내지 50 cps 범위가 되도록 용매를 첨가한다. 용매는 바인더 수지, 광개시제 및 기타 첨가물을 첨가 및 혼합하여 용해하고, 우수한 코팅성과 투명한 박막을 얻기 위해 사용되는 것으로서, 바인더 수지, 광개시제 및 기타 화합물과의 상용성을 고려할 때 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸에테르아세테이트 (PGMEA), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포룸아미드 (DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부틸로락톤, 디에틸에테르, 에틸렌글리콜디메틸에테르, 다이글라임(Diglyme), 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄 및 옥탄 중에서 선택된 용매를 단독으로 또는 1종 이상을 혼합한 용매를 사용할 수 있다.The negative photoresist composition in which the solvent is added to the above-mentioned components is formed by spin coating on a substrate and then developing a pattern by irradiating UV with a mask and developing with an alkaline developer. The solvent content is 10 to 94% by weight. It is preferred that the solvent is typically added so that the viscosity is in the range of 1 to 50 cps. The solvent is used to dissolve by adding and mixing binder resin, photoinitiator and other additives, and to obtain excellent coating property and transparent thin film. In consideration of compatibility with binder resin, photoinitiator and other compounds, ethyl acetate, butyl acetate, di Ethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethyl formumamide (DMF), N, N-dimethylacetate Amide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether , Ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl A solvent selected from ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane alone or in mixture of one or more thereof may be used.

이하, 본 발명을 구체적으로 설명하기 위해 실시예 및 비교예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어져서는 안된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되어지는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<실시예 1><Example 1>

자외선 차단막과 교반기가 설치되어 있는 반응혼합조에 하기 표 1에 기재된 성분과 함량에 따라 바인더 수지, 용매, 다가 아크릴 모노머, 광개시제를 첨가하고, 이어서 3-아미노프로필-트리메톡시실레인 (접착보조제) 0.2 중량% 및 FC-430 (3M사, 레벨링제) 0.1 중량%를 순차적으로 첨가하고 교반하여 점도가 약 20cps인 음성 포토레지스트 조성물을 제조하였다. A binder resin, a solvent, a polyhydric acrylic monomer, and a photoinitiator are added to the reaction mixing tank equipped with the ultraviolet blocking film and the stirrer according to the components and contents shown in Table 1 below, followed by 3-aminopropyl-trimethoxysilane (adhesive aid). 0.2% by weight and 0.1% by weight of FC-430 (3M, Leveling Agent) were added sequentially and stirred to prepare a negative photoresist composition having a viscosity of about 20 cps.

<실시예 2 내지 14><Examples 2 to 14>

상기 실시예 1의 조성물의 성분 및 함량을 하기 표 1 및 2에 기재된 조성에 따라서 변화시킨 것을 제외하고는 동일한 방법으로 음성 포토레지스트 조성물을 제조하였다. A negative photoresist composition was prepared in the same manner except that the components and contents of the composition of Example 1 were changed according to the compositions shown in Tables 1 and 2 below.

실시예Example 바인더 수지 Binder resin 다가 아크릴모노머 (중량%)Multivalent Acrylic Monomer (wt%) 광개시제 (중량%)Photoinitiator (% by weight) 용매menstruum 1One 일반식 1의 바인더 수지(30) R1 = R2 = 수소 R3= 메틸, R4 = 글리시딜 x=0.4, y=0.6Binder Resin (30) of Formula 1 R1 = R2 = Hydrogen R3 = Methyl, R4 = Glycidyl x = 0.4, y = 0.6 디펜타에리스리톨헥사아크릴레이트 (20)Dipentaerythritol hexaacrylate (20) Irgacure 651 (2) Irgacure 651 (2) PGMEA (to 100)PGMEA (to 100) 22 일반식 1의 바인더 수지(30) R1 = R2 = 수소, R3= 메틸, R4 = 2,3-에폭시시클로헥실 x=0.35, y=0.65Binder Resin (30) of Formula 1 R1 = R2 = Hydrogen, R3 = Methyl, R4 = 2,3-Epoxycyclohexyl x = 0.35, y = 0.65 디펜타에리스리톨펜타아크릴레이트 (10)Dipentaerythritol pentaacrylate (10) Irgacure 907 (2)Irgacure 907 (2) 33 일반식 1의 바인더 수지(30) R1 = R2= R3= 메틸 R4 = 글리시딜 x=0.3, y=0.7Binder Resin (30) of Formula 1 R1 = R2 = R3 = Methyl R4 = Glycidyl x = 0.3, y = 0.7 디에틸렌글리콜디아크릴레이트 (20)Diethylene Glycol Diacrylate (20) 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판 (2)2-morpholinyl-2- (4-methylmercapto) benzoylpropane (2) 44 일반식 1의 바인더 수지(30) R1 = 수소, R2 = R3= 메틸, R4 = 2,3-에폭시시클로헥실 x=0.4, y=0.6Binder Resin (30) of Formula 1 R1 = Hydrogen, R2 = R3 = Methyl, R4 = 2,3-Epoxycyclohexyl x = 0.4, y = 0.6 디펜타에리스리톨헥사/펜타아크릴레이트 (15)Dipentaerythritol hexa / pentaacrylate (15) 4-페녹시벤조일디클로로메탄 (1)4-phenoxybenzoyldichloromethane (1) 55 일반식 2의 바인더 수지(30) R5= R6 = 수소, R7= R9=메틸, R8 = 글리시딜 R10 =메톡시카르보닐 l=0.3, m=0.3, n=0.4Binder Resin (30) of Formula 2 R5 = R6 = Hydrogen, R7 = R9 = Methyl, R8 = Glycidyl R10 = Methoxycarbonyl l = 0.3, m = 0.3, n = 0.4 트리메틸올프로판트리메타아크릴레이트(25)Trimethylolpropane trimethacrylate (25) 1,7-비스(9-아크리디닐)헵탄 (2)1,7-bis (9-acridinyl) heptane (2) 66 일반식 2의 바인더 수지(30) R5= R6 =R9= 수소, R7=메틸, R8 = 글리시딜 R10=페닐 l=0.3, m=0.4, n=0.3Binder Resin (30) of Formula 2 R5 = R6 = R9 = Hydrogen, R7 = Methyl, R8 = Glycidyl R10 = Phenyl l = 0.3, m = 0.4, n = 0.3 펜타에리스리톨트리아크릴레이트 (7)Pentaerythritoltriacrylate (7) 페닐비페닐케톤 (2)Phenylbiphenylketone (2) 77 일반식 2의 바인더 수지(30) R5= R6 = 수소, R7= R9=메틸, R8 = 3,4-에폭시부틸 R10 =벤질옥시카르보닐 l=0.3, m=0.3, n=0.4Binder Resin (30) of Formula 2 R5 = R6 = Hydrogen, R7 = R9 = methyl, R8 = 3,4-epoxybutyl R10 = benzyloxycarbonyl l = 0.3, m = 0.3, n = 0.4 β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르 (20)Phthalate diesters of β-hydroxyethyl (meth) acrylate (20) Irgacure 907 (2)Irgacure 907 (2)

실시예Example 바인더 수지 Binder resin 다가 아크릴모노머 (중량%)Multivalent Acrylic Monomer (wt%) 광개시제 (중량%)Photoinitiator (% by weight) 용매menstruum 88 일반식 2의 바인더 수지(30) R5= 수소, R6 =, R7= R9=메 틸, R8 =3-메틸옥세탄-3-메틸 R10 =시클로헥실옥시카르보 닐 l=0.25, m=0.35, n=0.4Binder Resin (30) of Formula 2 R5 = Hydrogen, R6 =, R7 = R9 = Methyl, R8 = 3-Methyloxetane-3-methyl R10 = Cyclohexyloxycarbonyl l = 0.25, m = 0.35, n = 0.4 테트라메틸올메탄테트라아 크릴레이트 (10)Tetramethylolmethanetetra acrylate (10) 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판 (1)2-morpholinyl-2- (4-methylmercapto) benzoylpropane (1) PGMEA (to 100) PGMEA (to 100) 99 일반식 2의 바인더 수지(30) R5= R6 = R9=메틸, R7= 수소 R8 = 글리시딜 R10 =t-부틸옥시카르보닐 l=0.4, m=0.3, n=0.3Binder Resin (30) of Formula 2 R5 = R6 = R9 = methyl, R7 = hydrogen R8 = glycidyl R10 = t-butyloxycarbonyl l = 0.4, m = 0.3, n = 0.3 트리메틸올프로판디아크릴레이트 (10)Trimethylolpropanediacrylate (10) 1-히드록시-1-벤조일시클로헥산 (2)1-hydroxy-1-benzoylcyclohexane (2) 1010 일반식 2의 바인더 수지(30) R5= R6 = R9= 수소, R7= 메틸, R8 =글리시딜 R10 =γ-부틸로락톤옥시카르보닐 l=0.35, m=0.3, n=0.35Binder Resin (30) of Formula 2 R5 = R6 = R9 = Hydrogen, R7 = Methyl, R8 = Glycidyl R10 = γ-Butyrolactoneoxycarbonyl l = 0.35, m = 0.3, n = 0.35 트리메틸올프로판디아크릴레이트 (10)와 디펜타에리스리톨헥사아크릴레이트 (5)Trimethylolpropanediacrylate (10) and dipentaerythritol hexaacrylate (5) Irgacure 651 (2)Irgacure 651 (2) 1111 일반식 2의 바인더 수지(30) R5= R6 = 수소, R7= R9=메틸, R8 =2,3-에폭시시클로헥실 R10 =디사이클로펜타닐옥시 카르보닐 l=0.3, m=0.3, n=0.4Binder Resin (30) of Formula 2 R5 = R6 = Hydrogen, R7 = R9 = Methyl, R8 = 2,3-epoxycyclohexyl R10 = Dicyclopentanyloxycarbonyl l = 0.3, m = 0.3, n = 0.4 디펜타에리스리톨헥사아크릴레이트 (17)Dipentaerythritol hexaacrylate (17) 이소프로필치오잔톤 (2)Isopropylthioxanthone (2) 1212 일반식 2의 바인더 수지(30) R5= R6 = 수소, R7= R9=메틸, R8 =3-에틸옥세탄-3-메틸 R10 =데실옥시카르보닐 l=0.4, m=0.4, n=0.2Binder Resin (30) of Formula 2 R5 = R6 = Hydrogen, R7 = R9 = methyl, R8 = 3-ethyloxetane-3-methyl R10 = decyloxycarbonyl l = 0.4, m = 0.4, n = 0.2 에틸렌글리콜디아크릴레이트 (20)Ethylene Glycol Diacrylate (20) 디에틸치오잔톤 (1.5)Diethylthioxanthone (1.5) 1313 실시예 1의 바인더수지(10)와 실시예 10의 바인더수지(20)의 혼합물A mixture of the binder resin 10 of Example 1 and the binder resin 20 of Example 10 디펜타에리스리톨펜타아크릴레이트 (15)Dipentaerythritol pentaacrylate (15) 4-벤조일-4-메틸디페닐설파이드 (2)4-benzoyl-4-methyldiphenylsulfide (2) 1414 실시예 1의 바인더수지(10)와 실시예 10의 바인더수지(20)의 혼합물A mixture of the binder resin 10 of Example 1 and the binder resin 20 of Example 10 KAYARAD HX-220KAYARAD HX-220 Irgacure 907 (2)Irgacure 907 (2)

상기 표 1 및 2에 있어서, PGMEA는 프로필렌글리콜메틸에테르아세테이트 이고, KAYARAD HX-220(3-히드록시-2,2-디메틸프로필산-2-프로펜에스터와 2-옥세파논 중합체의 에스테르 축합체)은 일본화약의 다가 아크릴모노머이다. 일반식 1과 일반식 2의 바인더 수지들의 평균분자량은 약 10,000, 분산도는 2.1 이다.In Tables 1 and 2, PGMEA is propylene glycol methyl ether acetate, and ester axis of KAYARAD HX-220 (3-hydroxy-2,2-dimethylpropyl acid-2-propene ester and 2-oxepanone polymer). Coalescence) is a polyhydric acrylic monomer of Nippon Gunpowder. The average molecular weights of the binder resins of Formulas 1 and 2 are about 10,000, and the dispersion degree is 2.1.

<비교예 1 내지 2><Comparative Examples 1 and 2>

상기 실시예 1의 바인더 수지 대신 하기 일반식 3으로 표시되는 바인더 수지를 표 3에 기재된 조성에 따라서 변화시켜 사용한 것을 제외하고는 동일한 함량과 방법으로 음성 포토레지스트 조성물을 제조하였다.A negative photoresist composition was prepared in the same amount and method except for changing the binder resin represented by the following Formula 3 according to the composition shown in Table 3 instead of the binder resin of Example 1.

<일반식 3><Formula 3>

Figure 112005075405314-pat00003
Figure 112005075405314-pat00003

비교예Comparative example 바인더수지 (30 중량%)Binder Resin (30 wt%) 다기능모노머 (중량%)Multifunctional Monomer (wt%) 실리콘화합물 (중량%)Silicone Compound (wt%) 광개시제 (중량%)Photoinitiator (% by weight) 첨가제 (중량%)Additive (wt%) 용매 (중량%)Solvent (% by weight) 1One 일반식3) o= 0.3, p =0.2, q= 0.53) o = 0.3, p = 0.2, q = 0.5 DPEHA (20)DPEHA (20) APTMS (0.1)APTMS (0.1) Irgacure 651(2)Irgacure 651 (2) FC-430 (0.1)FC-430 (0.1) PGMEA (to 100)PGMEA (to 100) 22 일반식3) o= 0.3, p =0.3, q= 0.43) o = 0.3, p = 0.3, q = 0.4

표 3에서 일반식 3의 바인더 수지들은 평균분자량 10,000, 분산도 2.5 및 산가 100이다. 표 3에서 DPEHA는 디펜타에리스리톨헥사아크릴레이트 이고 APTMS는 아미노페닐트리메톡시실란 이고, PGMEA는 프로필렌글리콜메틸에테르아세테이트이다.In Table 3, the binder resins of the general formula 3 have an average molecular weight of 10,000, a dispersity of 2.5, and an acid value of 100. In Table 3, DPEHA is dipentaerythritol hexaacrylate, APTMS is aminophenyltrimethoxysilane, and PGMEA is propylene glycol methyl ether acetate.

이상의 실시예 및 비교예에 있어서 음성 포토레지스트 조성물의 평가는 실리콘 웨이퍼 또는 유리판 등의 기판 위에서 실시하였으며, 레지스트 조성물의 열적특성조사, 투과율(T%, 400 nm에서), 평탄성(Uniformity), 잔막율, 패턴 형성 등의 성능평가를 실시하였으며, 그 결과를 하기 표 4와 5에 나타냈다.In the above examples and comparative examples, the evaluation of the negative photoresist composition was carried out on a substrate such as a silicon wafer or a glass plate, and the thermal properties of the resist composition were investigated, transmittance (at T%, 400 nm), uniformity, and residual film rate. , Performance evaluation of pattern formation and the like were carried out, and the results are shown in Tables 4 and 5 below.

(1) 열적특성(1) thermal characteristics

음성 포토레지스트 조성물을 기판위에 스핀 코터를 이용하여 800rpm의 속도로 8초간 도포한 후, 100℃에서 1분간 프리베이크(prebake)하고, 365nm 에서 15초간 노광시킨 후, 240℃에서 30분간 포스트베이크(postbake)를 실시하여 레지스트 막을 형성시키고, 이를 오토클레이브(Autoclave)에 넣어 100℃에서 1시간동안 숙성시켰다. 오토클레이브에서 숙성된 시편을 크로스 헤찌 커터(Cross Hatch Cutter)로 기판이 드러나도록 스크레치(Scratch)한 후 접착 테잎으로 부착한 후 탈착하였다. 100 셀 중 80셀이 테잎에 붙어 기판으로부터 탈착되지 않으면 '양호' 그렇지 않은 경우를 '불량'으로 판단하였다.The negative photoresist composition was applied onto the substrate using a spin coater for 8 seconds at a speed of 800 rpm, then prebaked at 100 ° C. for 1 minute, exposed at 365 nm for 15 seconds, and then post-baked at 240 ° C. for 30 minutes. postbake) was carried out to form a resist film, which was placed in an autoclave and aged at 100 ° C for 1 hour. The specimen aged in the autoclave was scratched to expose the substrate with a cross hatch cutter, and then attached with an adhesive tape and then detached. If 80 cells out of 100 cells are attached to the tape and are not detached from the substrate, it is determined as 'good' or 'bad'.

(2) UV투과율(2) UV transmittance

음성 포토레지스트 조성물을 기판 위에 스핀 코터를 이용하여 800rpm의 속도로 8초간 도포한 후, 100℃에서 1분간 프리베이크(prebake)하고, 알칼리 수용액에 60초간 스프레이(spray)현상하고 순수(DI Water)로 60초간 린스 후, 압축공기로 불어내고, 240℃에서 30분간 포스트베이크(postbake)를 실시하여 약 3.5 내지 4.0 마이크로미터(um)의 레지스트 막을 형성하였다. UV는 UV-vis 측정장비를 이용하여 400nm영역의 투과율을 측정하였다. The negative photoresist composition was applied onto the substrate using a spin coater for 8 seconds at a speed of 800 rpm, then prebaked at 100 ° C. for 1 minute, sprayed for 60 seconds in an aqueous alkali solution, and then purified with DI water. After rinsing for 60 seconds in a furnace, it was blown with compressed air and postbaked at 240 ° C. for 30 minutes to form a resist film of about 3.5 to 4.0 micrometers (um). UV was measured for transmittance in the 400nm region using a UV-vis measuring equipment.

(3) 잔막율(3) residual film rate

음성 포토레지스트 조성물을 기판 위에 스핀 코팅하고, 200℃에서 30분간 프리베이크(Pre-Bake) 한 후 막의 두께와 240℃에서 30분간 포스트베이크(Post-Bake)한 후막의 두께 비율(%)을 측정하였다.Spin-coating the negative photoresist composition on the substrate, measuring the thickness of the film after pre-baking at 200 ° C. for 30 minutes and the thickness ratio (%) of the thick film which was post-baked at 240 ° C. for 30 minutes. It was.

(4) 패턴 형성(4) pattern formation

음성 포토레지스트 패턴을 형성한 실리콘 웨이퍼를 홀(Hole) 패턴의 수직방향에서부터 절단하고, 패턴의 단면 방향에서 전자주사현미경으로 관찰한 결과를 나타냈다. 패턴 사이드 벽(side wall)이 기판에 대하여 55도 이상의 각도로 세워져 있고, 막이 감소되지 않은 것을 '양호'로 하고, 막의 감소가 인정된 것을 '막감(膜減)'으로 판정하였다.The silicon wafer in which the negative photoresist pattern was formed was cut from the vertical direction of the hole pattern, and the result which observed with the electron scanning microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.

(5) 내화학성(5) chemical resistance

음성 포토레지스트 조성물을 기판 위에 스핀 코터를 이용하여 도포한 후, 프리베이크(prebake) 및 포스트베이크(postbake) 등의 공정을 거쳐 형성된 레지스트 막을 스트리퍼(Stripper), 에천트(Etchant) 용액에 40℃에서 10분 동안 담근 후 레지스트 막의 투과율 및 두께의 변화가 있는지 살펴보았다. 투과율 및 두께의 변화가 없을 때 '양호'로 하고, 투과율 및 두께의 변화가 있으면 '불량'으로 판정하였다.After the negative photoresist composition was applied onto the substrate using a spin coater, a resist film formed through a process such as prebake and postbake was applied to a stripper or etchant at 40 ° C. After soaking for 10 minutes, the change in the transmittance and thickness of the resist film was examined. When there was no change in transmittance and thickness, it was set as 'good', and when there was a change in transmittance and thickness, it was determined as 'poor'.

실시예Example AdhesionAdhesion UV 투과율 (400nm) (%)UV transmittance (400nm) (%) 잔막율 (%)Residual Rate (%) 패턴형성Pattern formation 내화학성Chemical resistance 1One 양호Good 9898 9595 양호Good 양호Good 22 양호Good 9898 9595 양호Good 양호Good 33 양호Good 9696 9595 양호Good 양호Good 44 양호Good 9696 9696 양호Good 양호Good 55 양호Good 9797 9797 양호Good 양호Good 66 양호Good 9797 9696 양호Good 양호Good 77 양호Good 9696 9595 양호Good 양호Good 88 양호Good 9696 9696 양호Good 양호Good 99 양호Good 9797 9595 양호Good 양호Good 1010 양호Good 9797 9696 양호Good 양호Good 1111 양호Good 9797 9797 양호Good 양호Good 1212 양호Good 9797 9696 양호Good 양호Good 1313 양호Good 9797 9595 양호Good 양호Good 1414 양호Good 9797 9696 양호Good 양호Good

비교예Comparative example AdhesionAdhesion UV 투과율 (400nm) (%)UV transmittance (400nm) (%) 잔막율 (%)Residual Rate (%) 패턴형성Pattern formation 내화학성Chemical resistance 1One 불량Bad 9393 9090 막감Film 불량Bad 22 불량 Bad 9292 9191 막감Film 불량Bad

표 4 및 5의 결과에서 알 수 있듯이, 본 발명의 음성 포토레지스트 조성물은 종래의 음성 포토레지스트 조성물과는 달리 내열성이 우수할 뿐만 아니라, 메탈 및 무기물과의 접착력, UV투과율, 잔막율, 평탄성 및 패턴안정성이 매우 우수함을 알 수 있다.As can be seen from the results of Tables 4 and 5, the negative photoresist composition of the present invention, unlike the conventional negative photoresist composition, is not only excellent in heat resistance, but also has adhesion to metals and inorganic materials, UV transmittance, residual film ratio, flatness and It can be seen that the pattern stability is very excellent.

이상에서 살펴본 바와 같이 본 발명에 따른 음성 포토레지스트 조성물은 내열성이 우수할 뿐만 아니라, 평탄성 및 패턴안정성이 매우 양호하다. 또한, 투과율이 우수하여 백라이트(back light)의 밝기의 조절이 가능하여 배터리 효율을 증가시킬수 있고, 색감이상, 색차계 변화에 대한 영향을 최소화할 수 있다. 또한, 본 발명의 음성 포토레지스트 조성물은 본 발명에서 정해진 범위 내에서 바인더 수지의 구조 및 조성비를 변화시키면 요구되는 특정의 물성을 갖는 레지스트로서 용이하게 제조될 수 있다.As described above, the negative photoresist composition according to the present invention not only has excellent heat resistance, but also has excellent flatness and pattern stability. In addition, the transmittance is excellent, it is possible to control the brightness of the backlight (back light) to increase the battery efficiency, it is possible to minimize the effects on color abnormality, color difference change. In addition, the negative photoresist composition of the present invention can be easily prepared as a resist having specific physical properties required by changing the structure and composition ratio of the binder resin within the range defined in the present invention.

본 명세서에 기재된 실시예에 기재된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Configurations described in the embodiments described herein are only one of the most preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, and various equivalents and modifications that may be substituted for them at the time of the present application It should be understood that there may be

Claims (6)

하기 일반식 1로 표시되는 수지, 하기 일반식 2로 표시되는 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 바인더 수지 3 내지 50 중량%, 다가 아크릴 모노머 2 내지 40 중량%, 광개시제 0.01 내지 10 중량% 및 유기용매 10 내지 94중량%를 함유하는 것을 특징으로 하는 음성 포토레지스트 조성물; 3 to 50% by weight of any one binder resin selected from the group consisting of a resin represented by the following general formula (1), a resin represented by the following general formula (2) and mixtures thereof, 2 to 40% by weight of a polyvalent acrylic monomer, 0.01 to 10 photoinitiator Negative photoresist composition, characterized in that it comprises 10% by weight to 94% by weight of an organic solvent; <일반식 1><Formula 1>
Figure 112007014239886-pat00004
Figure 112007014239886-pat00004
 상기 일반식 1에서, R1, R2 및 R3는 각각 서로 독립적으로 H 또는 메틸기이고, R4는 에폭시기를 포함하는 탄소원자수가 1 ~ 10인 알킬기 또는 시클로알킬기이고, x와 y는 각 중합단위의 몰비로서 x는 0.02~0.80, y는 0.20~0.98이다. 상기 일반식 1의 바인더 수지는 각 중합단위의 배열순서에 구속되지 않는 랜덤 공중합체여도 좋다.In Formula 1, R 1 , R 2, and R 3 are each independently H or a methyl group, R 4 is an alkyl group or cycloalkyl group having 1 to 10 carbon atoms including an epoxy group, and x and y are each polymerized. As molar ratio of a unit, x is 0.02-0.80 and y is 0.20-0.98. The binder resin of the general formula (1) may be a random copolymer that is not bound by the sequence of the polymerized units. <일반식 2><Formula 2>
Figure 112007014239886-pat00005
Figure 112007014239886-pat00005
 상기 일반식 2에서, R5, R6, R7 및 R9는 각각 서로 독립적으로 H 또는 메틸기이고, R8은 에폭시기를 포함하는 탄소원자수가 1 ~ 10인 알킬기 또는 시클로알킬 기이고, R10은 탄소원자수가 1 ~ 14인 카르복실산, 알콕시카르보닐 및 방향족 화합물로 이루어진 그룹으로부터 선택된 어느 하나이고, l, m, n은 각 중합단위의 몰비로서 l은 0.02~0.70, m은 0.05~0.60 및 n은 0.01~0.60이다. 상기 일반식 2의 바인더 수지는 각 중합단위의 배열순서에 구속되지 않는 랜덤 공중합체여도 좋다.In Formula 2, R 5 , R 6 , R 7 and R 9 are each independently H or a methyl group, R 8 is an alkyl group or cycloalkyl group having 1 to 10 carbon atoms including an epoxy group, R 10 is a carboxylic acid having 1 to 14 carbon atoms, Any one selected from the group consisting of alkoxycarbonyl and an aromatic compound, l, m, n is the molar ratio of each polymerized unit, l is 0.02 to 0.70, m is 0.05 to 0.60 and n is 0.01 to 0.60. The binder resin of the general formula (2) may be a random copolymer that is not bound by the sequence of the polymerized units. 제1항에 있어서, 상기 일반식 1로 표시되는 바인더 수지의 평균 분자량이 2,000 내지 300,000이고, 분산도는 1.0 내지 10.0인 것을 특징으로 하는 음성 포토레지스트 조성물.The negative photoresist composition of claim 1, wherein an average molecular weight of the binder resin represented by Formula 1 is 2,000 to 300,000, and a dispersion degree is 1.0 to 10.0. 제1항에 있어서, 상기 다가 아크릴 모노머는 에틸렌옥사이드기의 수가 2 내지 20인 폴리에틸렌글리콜디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 20인 폴리프로필렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 비스페놀 A 디글리시딜에테르아크릴산 부가물, 에틸이소시아눌릭산트리(메타)아크릴레이트, β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물, 트리메틸올프로판트리(메타)아크릴레이트, 테트라메틸올메탄테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 트리메틸올프로판트리글리시딜에테르아크릴산 부가물, 우레탄기를 갖는 2가 내지 6가 히드록시 화합물의 (메타)아크릴산 부가물 및 3-히드록시-2,2-디메틸프로필산-2-프로펜에스터와 2-옥세파논 중합체의 에스테르 축합체로 이루어진 군으로부터 선택된 어느 하나 이상을 포함하는 것을 특징으로 하는 음성 포토레지스트 조성물.The polypropylene glycol according to claim 1, wherein the polyhydric acrylic monomer is polyethylene glycol di (meth) acrylate having 2 to 20 ethylene oxide groups, ethylene glycol di (meth) acrylate and 2 to 20 polypropylene glycol groups. Di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether acrylic acid adduct, ethyl isocyanuric acid tri (meth) acrylate, β Phthalic acid diester of -hydroxyethyl (meth) acrylate, toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylic Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylic acid of a divalent to hexavalent hydroxy compound having a acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropanetriglycidyl ether acrylic acid adduct, and a urethane group Negative photoresist composition comprising at least one selected from the group consisting of adducts and ester condensates of 3-hydroxy-2,2-dimethylpropyl acid-2-propene ester and 2-oxepanone polymer . 제1항에 있어서, 상기 유기용매는 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포룸아미드 (DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부틸로락톤, 디에틸에테르, 에틸렌글리콜디메틸에테르, 다이글라임(Diglyme), 테트라하이드 로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄 및 옥탄으로 이루어진 군으로부터 선택된 어느 하나 이상을 포함하는 것을 특징으로 하는 음성 포토레지스트 조성물.The method of claim 1, wherein the organic solvent is ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, Propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, Cyclohexanone, dimethylformumamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, Diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl Termini, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, negative photoresist composition comprising at least one selected from the group consisting of heptane and octane. 제1항에 있어서, 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.0001 내지 3 중량%를 더 포함하는 것을 특징으로 하는 음성 포토레지스트 조성물. The negative photoresist composition of claim 1, further comprising 0.0001 to 3% by weight of a silicon-based compound including an epoxy group or an amine group. 제5항에 있어서, 상기 에폭시기 또는 아민기를 포함하는 실리콘계 화합물은 (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸메톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실레인 및 아미노프로필 트리메톡시실레인으로 이루어진 군으로부터 선택된 어느 하나 이상을 포함하는 것을 특징으로 하는 음성 포토레지스트 조성물.The method of claim 5, wherein the silicon-based compound containing an epoxy group or an amine group is (3-glycidoxyoxy) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxy Propyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyl triethoxy silane and aminopropyl trimethoxy silane comprising any one or more selected from the group consisting of.
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JP2010015156A (en) * 2005-12-22 2010-01-21 Samyang Ems Co Ltd Negative photoresist composition
JP4672789B2 (en) * 2005-12-22 2011-04-20 サムヤンイーエムエス カンパニー．，リミテッド． Negative photoresist composition
KR101099691B1 (en) 2008-04-07 2011-12-28 주식회사 삼양이엠에스 Negative Resist Composition
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KR20190058445A (en) * 2016-09-30 2019-05-29 도레이 카부시키가이샤 DEVICE AND DISPLAY DEVICE HAVING A NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, CURED FILM, CURED FILM AND METHOD FOR MANUFACTURING THE SAME
KR102492113B1 (en) * 2016-09-30 2023-01-25 도레이 카부시키가이샤 Negative photosensitive resin composition, cured film, element and display device provided with cured film, and manufacturing method thereof
KR20180084460A (en) 2017-01-17 2018-07-25 주식회사 트리엘 NOVEL COMPOUND having VINYLPHENYLOXY moiety AND PHOTOSENSITIVE PHOTORESIST COMPOSITION INCLUDING THE SAME
KR20180109770A (en) 2018-06-07 2018-10-08 주식회사 트리엘 PHOTORESIST COMPOSITION INCLUDING COMPOUND having VINYLPHENYLOXY moiety
KR20180084716A (en) 2018-07-17 2018-07-25 주식회사 트리엘 NOVEL COMPOUND having VINYLPHENYLOXY moiety AND PHOTOSENSITIVE PHOTORESIST COMPOSITION INCLUDING THE SAME
CN115894083A (en) * 2022-07-29 2023-04-04 广东环波新材料有限责任公司 Preparation method and application of negative photosensitive black electronic device
CN115894083B (en) * 2022-07-29 2024-04-09 广东环波新材料有限责任公司 Preparation method and application of negative photosensitive type black electronic device

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JP2010015156A (en) 2010-01-21

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