KR100579832B1 - Photo Resist Composition For Spinless Coating - Google Patents

Photo Resist Composition For Spinless Coating Download PDF

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KR100579832B1
KR100579832B1 KR1020030035442A KR20030035442A KR100579832B1 KR 100579832 B1 KR100579832 B1 KR 100579832B1 KR 1020030035442 A KR1020030035442 A KR 1020030035442A KR 20030035442 A KR20030035442 A KR 20030035442A KR 100579832 B1 KR100579832 B1 KR 100579832B1
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group
methyl
methacrylate
good good
acrylate
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KR1020030035442A
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KR20040104053A (en
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배유리
김영근
최숙영
차혁진
이재환
이근주
류미선
서현진
우승우
우제선
유권일
이수현
정용만
최범영
한철
김웅
정낙칠
홍성재
김민지
최영수
정상협
최재록
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주식회사 삼양이엠에스
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Priority to KR1020030035442A priority Critical patent/KR100579832B1/en
Priority to TW093115695A priority patent/TWI266952B/en
Priority to PCT/KR2004/001301 priority patent/WO2004107053A1/en
Priority to PCT/KR2004/001300 priority patent/WO2004107052A1/en
Priority to TW093115691A priority patent/TWI274962B/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
    • G03F7/038—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/027—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
    • G03F7/027—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
    • G03F7/16—Coating processes; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Paints Or Removers (AREA)

Abstract

본 발명은 스핀리스 코팅용 포토레지스트 조성물에 관한 것으로서, 아크릴계 바인더 수지 5 내지 40 중량부, 에틸렌성 불포화 결합을 갖는 다기능 모노머 2 내지 200 중량부, 광개시제 0.005 내지 20 중량부, 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.01 내지 3 중량부 및 불소계 또는 실리콘계 계면활성제 0.01 내지 3 중량부를 함유하는 조성물로서, 점도가 2 내지 20 cps가 되도록 용매가 첨가된다. 본 발명에 따른 포토레지스트 조성물은 스핀리스 코팅에 의해 기재 위에 유기절연막 등의 막 형성시, 얼룩이 없는 균일한 코팅막을 형성할 수 있을 뿐만 아니라, 코팅막의 에지 프로파일(edge profile) 콘트롤도 용이하다.The present invention relates to a photoresist composition for spinless coating, comprising 5 to 40 parts by weight of an acrylic binder resin, 2 to 200 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond, 0.005 to 20 parts by weight of a photoinitiator, an epoxy group or an amine group. A composition containing 0.01 to 3 parts by weight of a silicone compound and 0.01 to 3 parts by weight of a fluorine or silicone surfactant, wherein a solvent is added so as to have a viscosity of 2 to 20 cps. The photoresist composition according to the present invention can not only form a uniform coating film without spots when forming an organic insulating film or the like on a substrate by spinless coating, but also easily control the edge profile of the coating film.

스핀리스 코팅, 포토레지스트, 다기능 모노머, 실리콘계 화합물Spinless Coating, Photoresist, Multifunctional Monomer, Silicone Compound

Description

스핀리스 코팅용 포토레지스트 조성물{Photo Resist Composition For Spinless Coating}Photo Resist Composition For Spinless Coating

본 발명은 스핀리스 코팅용 포토레지스트 조성물에 관한 것으로, 보다 상세하게는 스핀리스 코팅에 의해 기재 위에 유기절연막 등의 막 형성시, 얼룩이 없는 균일한 코팅막을 형성할 수 있을 뿐만 아니라, 코팅막의 에지 프로파일(edge profile) 콘트롤도 용이한 스핀리스 코팅용 포토레지스트 조성물에 관한 것이다.The present invention relates to a photoresist composition for spinless coating, and more particularly, when forming an organic insulating film or the like on a substrate by spinless coating, it is possible to form a uniform coating film without spots, as well as an edge profile of the coating film. (Edge profile) relates to a photoresist composition for spinless coating that is easy to control.

액정표시소자(Liquid Crystal Display : 이하, LCD) 등의 표시소자는 대형화 추세에 있으며, 이에 따라 사용되는 기판 역시 사이즈가 대형화되고 있다. 현재, 이미 5세대 기판의 생산라인까지 설치되어 있으며, 크기가 더욱 확대된 6세대 이상의 기판이 계속하여 개발되고 있다. 기판이 점점 대형화됨에 따라, 포토레지스트 조성물을 코팅시 적용되는 코팅방식도 변화를 같이하고 있다. 즉, 4세대 크기의 유리기판에는 포토레지스트 조성물을 슬릿을 통하여 기판 위에 도포한 후 스피닝하는 슬릿 엔드 스핀(slit and spin)이라는 코팅방식이 사용되었으나 기판 크기가 1000mm*1000mm가 넘는 5세대 이상의 기판은 스핀 자체가 어려우므로, 스핀을 행하지 않고 도포공정만으로 끝내는 스핀리스 코팅(spinless coating) 방식을 사용하고 있다. 이와 같이 기판의 대형화에 따라 코팅방식이 변화됨에 따라, 사용되는 포토레지스트 조성물의 변화 또한 필수적이다. 특히 스핀리스 코팅방식이 대형 기판에 적용될수록, 포토레지스트 조성물로 형성된 코팅막은 균일성(uniformity)이 있어야 하며, 코팅막의 얼룩 또한 없어야 한다. 또한, 스핀리스 코팅시 코팅막의 에지 프로파일(edge profile) 콘트롤도 용이해야 한다.Display devices, such as liquid crystal displays (LCDs), have become larger in size, and thus substrates used have also increased in size. At present, the production line of the fifth generation substrate is already installed, and the sixth generation or more substrates of which size is further expanded are continuously being developed. As the substrate becomes larger in size, the coating method applied when coating the photoresist composition is also changing. In other words, the glass substrate of the 4th generation size used a coating method called a slit end spin (slit and spin) to apply the photoresist composition on the substrate through the slit and then spin, but more than 5 generations of substrates of more than 1000mm * 1000mm Since the spin itself is difficult, the spinless coating method which uses only a coating process without spin is used. As the coating method changes as the substrate is enlarged, a change in the photoresist composition used is also essential. In particular, as the spinless coating method is applied to a large substrate, the coating film formed of the photoresist composition should have uniformity, and there should be no staining of the coating film. In addition, the edge profile of the coating layer during spinless coating should also be easy to control.

따라서, 본 발명이 이루고자 하는 기술적 과제는 스핀리스 코팅에 의해 기재 위에 유기절연막 등의 막 형성시, 얼룩이 없는 균일한 코팅막을 형성할 수 있을 뿐만 아니라, 코팅막의 에지 프로파일(edge profile) 콘트롤도 용이한 스핀리스 코팅용 포토레지스트 조성물을 제공하는데 있다.Accordingly, the technical problem to be achieved by the present invention is not only to form a uniform coating film without spots when forming an organic insulating film or the like on a substrate by spinless coating, but also to easily control the edge profile of the coating film. It is to provide a photoresist composition for spinless coating.

상기 기술적 과제를 달성하기 위하여 본 발명은 아크릴계 바인더 수지 5 내지 40 중량부, 에틸렌성 불포화 결합을 갖는 다기능 모노머 2 내지 200 중량부, 광개시제 0.005 내지 20 중량부, 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.01 내지 3 중량부 및 불소계 또는 실리콘계 계면활성제 0.01 내지 3 중량부를 함유하는 조성물로서, 점도가 2 내지 20 cps가 되도록 용매가 첨가된 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물을 제공한다. 이러한 조성물은 음성의 포토레지스트 조성물로 이용된다.In order to achieve the above technical problem, the present invention provides 5 to 40 parts by weight of an acrylic binder resin, 2 to 200 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond, 0.005 to 20 parts by weight of a photoinitiator, and a silicone-based compound containing 0.01 to amine groups. Provided is a composition containing 3 parts by weight and 0.01 to 3 parts by weight of a fluorine-based or silicon-based surfactant, wherein a solvent is added so as to have a viscosity of 2 to 20 cps. Such compositions are used as negative photoresist compositions.

또한, 본 발명은 아크릴계 바인더 수지, 노볼락 바인더 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 바인더 수지 10 내지 28 중량부, 감광제 4 내지 8 중량부, 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.01 내지 3 중량부 및 불소계 또는 실리콘계 계면활성제 0.01 내지 3 중량부를 함유하는 조성물로서, 점도가 2 내지 20 cps가 되도록 용매가 첨가된 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물을 제공한다. 이러한 조성물은 양성의 포토레지스트 조성물로 이용된다.In addition, the present invention is 10 to 28 parts by weight of a binder resin selected from the group consisting of an acrylic binder resin, a novolak binder resin and mixtures thereof, 4 to 8 parts by weight of a photosensitizer, 0.01 to 3 parts by weight of a silicone compound containing an epoxy group or an amine group And 0.01 to 3 parts by weight of a fluorine-based or silicon-based surfactant, wherein a solvent is added so as to have a viscosity of 2 to 20 cps. Such a composition is used as a positive photoresist composition.

이하, 본 발명에 따른 스핀리스 코팅용 포토레지스트 조성물에 대하여 상세히 설명한다.Hereinafter, the photoresist composition for spinless coating according to the present invention will be described in detail.

본 발명의 스핀리스 코팅용 포토레지스트 조성물은 목적하는 포토레지스트 조성물의 용도 즉, 양성 또는 음성의 종류에 따라 바인더 수지의 종류와 함량을 전술한 조성성분 및 비율로 변화된다.The photoresist composition for spinless coating of the present invention is changed in kind and content of the binder resin according to the use of the desired photoresist composition, i.e., positive or negative, in the above-mentioned composition components and ratios.

음성 포토레지스트 조성물로 이용될 수 있는 본 발명의 스핀리스 코팅용 포토레지스트 조성물은 바인더 수지로서 아크릴계 바인더 수지 5 내지 40 중량부를 함유한다. 아크릴계 바인더 수지로는 하기 일반식 1로 표시되는 수지, 하기 일반식 2로 표시되는 수지를 단독으로 또는 이들을 혼합하여 사용하는 것이 바람직하다.The photoresist composition for spinless coating of the present invention that can be used as a negative photoresist composition contains 5 to 40 parts by weight of an acrylic binder resin as a binder resin. As acrylic binder resin, it is preferable to use resin represented by following General formula (1) and resin represented by following General formula (2) individually or in mixture of these.

<일반식 1><Formula 1>

Figure 112003019822267-pat00001
Figure 112003019822267-pat00001

상기 일반식 1에서, X는 수소원자 또는 메틸기이고, Y1은 탄소원자수가 2 내 지 16인 알킬기 또는 하이드록시알킬기이고, Y2는 하기 화학식(Ⅰ) 내지 화학식(XX)로 표시되는 화합물로부터 선택된 어느 하나이다.In Formula 1, X is a hydrogen atom or a methyl group, Y 1 is an alkyl group or hydroxyalkyl group having 2 to 16 carbon atoms, and Y 2 is a compound represented by the following formula (I) to formula (XX) It is either chosen.

Figure 112003019822267-pat00002
Figure 112003019822267-pat00002

Figure 112003019822267-pat00003
Figure 112003019822267-pat00003

Figure 112003019822267-pat00004
Figure 112003019822267-pat00004

Figure 112003019822267-pat00005
Figure 112003019822267-pat00005

Figure 112003019822267-pat00006
Figure 112003019822267-pat00006

Figure 112003019822267-pat00007
Figure 112003019822267-pat00007

Figure 112003019822267-pat00008
Figure 112003019822267-pat00008

Figure 112003019822267-pat00009
Figure 112003019822267-pat00009

Figure 112003019822267-pat00010
Figure 112003019822267-pat00010

Figure 112003019822267-pat00011
Figure 112003019822267-pat00011

Figure 112003019822267-pat00012
Figure 112003019822267-pat00012

Figure 112003019822267-pat00013
Figure 112003019822267-pat00013

Figure 112003019822267-pat00014
Figure 112003019822267-pat00014

Figure 112003019822267-pat00015
Figure 112003019822267-pat00015

Figure 112003019822267-pat00016
Figure 112003019822267-pat00016

Figure 112003019822267-pat00017
Figure 112003019822267-pat00017

Figure 112003019822267-pat00018
Figure 112003019822267-pat00018

Figure 112003019822267-pat00019
Figure 112003019822267-pat00019

Figure 112003019822267-pat00020
Figure 112003019822267-pat00020

Figure 112003019822267-pat00021
Figure 112003019822267-pat00021

상기 화학식(Ⅰ) 내지 화학식(XX)에서, R1은 수소 또는 메틸기이고, R2는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, R3는 탄소원자수가 1 내지 10인 탄화수소의 잔류 그룹이고, R4는 수소 또는 메틸기이고, R5는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, k는 0 내지 10의 정수이다.In formulas (I) to (XX), R 1 is hydrogen or a methyl group, R 2 is an alkylene group having 1 to 10 carbon atoms, and R 3 is a residual group of hydrocarbon having 1 to 10 carbon atoms R 4 is hydrogen or a methyl group, R 5 is an alkylene group having 1 to 10 carbon atoms, and k is an integer of 0 to 10.

<일반식 2><Formula 2>

Figure 112003019822267-pat00022
Figure 112003019822267-pat00022

상기 일반식 2에서, 중합단위 A는 벤질메타아크릴레이트(Benzyl Methacrylate), 스티렌(Styrene), 알파-메틸스티렌(α-methyl styrene), 이소보닐아크릴레이트(isobonyl acrylate) 및 이소보닐메타아크릴레이트(Isobonyl methacrylate), 디사이클로펜타닐아크릴레이트(Dicyclopentanyl acrylate), 디사이클로펜타닐메타아크릴레이트(Dicyclopentanyl methacrylate), 디사이클로펜테닐아크릴레이트(Dicyclopentenyl acrylate), 디사이클로펜테닐메타아크릴레이트 (Dicyclopentenyl methacrylate), 디사이클로펜타닐에틸옥시아크릴레이트 (Dicyclopentanylethyloxy acrylate), 디사이클로펜타닐에틸옥시메타아크릴레이트 (Dicyclopentanylethyloxy methacrylate), 디사이클로펜테닐에틸옥시아크릴레이트 (Dicyclopentenylethyloxy acrylate), 디사이클로펜테닐에틸옥시메타아크릴레이트 (Dicyclopentenylethyloxy methacrylate)로 이루어진 군으로부터 선택된 어느 하나이고, B는 글리시딜 메타아크릴레이트(Glycidyl Methacrylate), 히드록시에틸 메타아크릴레이트(Hydroxymethyl Methacrylate), 디메틸아미노 메타아크릴레이트 (Dimethylamino Methacrylate), 아크릴아미드(Acryl amide)로 이루어진 군으로부터 선택된 어느 하나이고, C는 아크릴산 또는 메타아크릴산이며, 상기 일반식 2의 바인더 수지는 중합단위 A, B 및 C의 배열순서에 구속되지 않는 랜덤 공중합체를 포함한다.In Formula 2, the polymerization unit A is benzyl methacrylate, styrene, alpha-methyl styrene, isobonyl acrylate, and isobornyl methacrylate. Isobonyl methacrylate, Dicyclopentanyl acrylate, Dicyclopentanyl methacrylate, Dicyclopentenyl acrylate, Dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, Dicyclopentanyl methacrylate Dicyclopentanylethyloxy acrylate, Dicyclopentanylethyloxy methacrylate, Dicyclopentenylethyloxy acrylate, Dicyclopentenylethyloxy methacrylate Select from group B is any one selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate, acryl amide One, C is acrylic acid or methacrylic acid, and the binder resin of the general formula (2) includes a random copolymer that is not bound to the sequence of the polymerization units A, B and C.

상기 일반식 1로 표시되는 바인더 수지는 카르복시산이 포함된 모노머와 이중결합을 갖는 모노머의 공중합체로서, 이러한 공중합체를 포함하는 본 발명의 조성물을 도포 후 패턴을 형성하면, 현상 후 잔사 등의 결함이 없고 평탄화율이 매우 우수하다. 즉, 상기 일반식 1의 Y1는 2개 내지 16개의 탄소원자를 갖는 알킬기 또는 하이드록시알킬기로서 접착력의 향상에 도움을 주고, Y2에는 방향족기를 포함하는 아크릴 공중합 수지로 된 종래의 바인더 수지와는 달리 벌키(bulky)한 지환족 구조를 포함하여 잔막율을 높일 뿐만 아니라 유리전이온도가 높으므로 내열성도 우수하다.The binder resin represented by the general formula (1) is a copolymer of a monomer containing a carboxylic acid and a monomer having a double bond, and if a pattern is formed after coating the composition of the present invention comprising such a copolymer, defects such as residue after development It has no flattening rate and is very good. That is, Y 1 of Formula 1 helps to improve adhesion as an alkyl group or a hydroxyalkyl group having 2 to 16 carbon atoms, and Y 2 is different from a conventional binder resin made of an acrylic copolymer resin containing an aromatic group. Unlike the bulky (aliphatic) alicyclic structure to increase the residual film ratio, as well as high glass transition temperature is excellent heat resistance.

또한, 상기 일반식 2로 표시되는 바인더 수지를 사용할 때도 일반식 1로 표시되는 바인더 수지를 사용할 때와 거의 대등한 효과를 나타낸다. 상기 일반식 2로 표시되는 바인더 수지에 있어서, 본 발명의 목적을 저해하지 않는 범위에서 다른 종류의 중합단위 도입이 가능함은 물론이며, 예를 들어 하기 일반식 3의 D와 같이 알킬기의 갯수가 2에서 16인 알킬아크릴레이트 또는 알킬메타아크릴레이트를 더 도입할 수 있다. 이러한 반복단위로는 좀 더 구체적으로 메틸메타크릴레이트, 부틸메타크릴레이트, 라우릴메타크릴레이트, 메틸아크릴레이트, 부틸아크릴레이트, 라우릴아크릴레이트, 스티렌 등을 들 수 있다.Moreover, also when using the binder resin represented by the said General formula (2), it shows the substantially equivalent effect as when using the binder resin represented by General formula (1). In the binder resin represented by the general formula (2), of course, it is possible to introduce other types of polymerized units in a range that does not impair the object of the present invention, for example, the number of alkyl groups as D of the general formula 3 May be further introduced in the alkyl acrylate or alkyl methacrylate of 16. More specifically, the repeating unit may include methyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl acrylate, butyl acrylate, lauryl acrylate, styrene and the like.

<일반식 3><Formula 3>

Figure 112003019822267-pat00023
Figure 112003019822267-pat00023

특히, 상기 일반식 1로 표시되는 바인더 수지와 일반식 2로 표시되는 바인더 수지를 혼합하여 사용하면, 조성물 중의 감광제와 바인더 수지의 상용성이 증가하여 패턴의 내깨짐성을 향상시킬 뿐만 아니라 백화현상(whitening)도 사라지게 된다. In particular, when the binder resin represented by the general formula (1) and the binder resin represented by the general formula (2) are mixed and used, the compatibility of the photosensitizer and the binder resin in the composition may be increased, thereby improving the break resistance of the pattern as well as whitening phenomenon. (whitening) also disappears.

에틸렌성 불포화 결합을 갖는 다기능 모노머로는 에틸렌글리콜디(메타)아크릴레이트, 에틸렌옥사이드기의 수가 2 내지 14인 폴리에틸렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트 디펜타에리스리톨트리(메타)아크릴레이트로 이루어진 군으로부터 선 택된 다가 알콜과 α,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물; 트리메틸올프로판트리글리시딜에테르아크릴산 부가물, 비스페놀 A 디글리시딜에테르아크릴산 부가물 등의 글리시딜기 함유 화합물에 (메타)아크릴산을 부가하여 얻어지는 화합물; β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트부가물 등의 수산기 및 에틸렌성 불포화 결합을 가지는 화합물과 다가 카르복시산과의 에스테르 화합물 또는 폴리이소시아네이트와의 부가물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 (메타)아크릴산알킬에스테르 중에서 선택된 하나 또는 둘 이상을 혼합하여 사용할 수 있으며, 그 함량은 2 내지 200 중량부, 바람직하게는 5 내지 50 중량부이다.Examples of the multifunctional monomer having an ethylenically unsaturated bond include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, trimethylolpropanedi (meth) acrylate, and trimethylolpropane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) acrylate and dipentaerythritol penta (meth) having 2 to 14 propylene oxide groups Acrylate, dipentaerythritol hexa (meth) acrylate compound obtained by esterifying a polyhydric alcohol selected from the group consisting of dipentaerythritol tri (meth) acrylate and α, β-unsaturated carboxylic acid; Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as trimethylolpropanetriglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group and an ethylenically unsaturated bond, such as a phthalic acid diester of β-hydroxyethyl (meth) acrylate, a toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, or a polyhydric carboxylic acid, or Adducts with polyisocyanates; One or two or more selected from (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate can be used in combination. , And the content thereof is 2 to 200 parts by weight, preferably 5 to 50 parts by weight.

이와 같은 에틸렌성 불포화 결합을 갖는 중합성 화합물인 다기능 모노머는 바인더 수지와의 조성비를 본 발명에 따라 적절히 조절함으로써 고내열성, 고투명성, 고평탄화율 및 패턴안정성을 유지할 수 있는 음성 포토레지스트를 제조하는 것이 가능하다.A multifunctional monomer which is a polymerizable compound having such an ethylenically unsaturated bond is used to prepare a negative photoresist capable of maintaining high heat resistance, high transparency, high flattening rate and pattern stability by appropriately adjusting the composition ratio with the binder resin according to the present invention. It is possible.

또한, 광개시제로는 통상적으로 아세토페논계나 벤조페논계를 사용하는데 광개시제 자체가 색을 가지면 투명성을 저하시키는 작용을 하므로 노광시 사용하는 파장대에서 적절한 감도를 갖고 광개시제 자체에 색을 갖지 않는 것을 사용함으로써 고투명성을 실현할 수 있다. 일반적으로 아크릴계 다기능 모노머를 사용하는 가교 반응의 광개시제는 사용하는 자외선의 파장에 맞추어서 사용되는데 가장 널리 사용되는 자외선 파장인 수은 램프는 310∼420nm 영역의 파장을 가지므로 이 파장 영역에서 라디칼을 발생하는 광개시제를 사용한다.As photoinitiators, acetophenone-based or benzophenone-based compounds are generally used. When the photoinitiator itself has a color, it acts to reduce transparency. Therefore, by using a photosensitive initiator having appropriate sensitivity in the wavelength range used and having no color in the photoinitiator itself, High transparency can be achieved. In general, the photoinitiator of the crosslinking reaction using the acrylic multifunctional monomer is used according to the wavelength of the ultraviolet rays used. Since the mercury lamp, which is the most widely used ultraviolet ray, has a wavelength in the range of 310 to 420 nm, photoinitiators that generate radicals in this wavelength range Use

상기와 같은 광개시제로는 Irgacure 369, Irgacure 651, Irgacure 907, TPO, CGI124, EPD/BMS 혼합계 등의 아세토페논 및 벤조페논계와 트리아진계를 사용하는 것이 바람직하다. 예를 들면 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 0.005 내지 20 중량부, 바람직하게는 0.5 내지 10 중량부를 사용하는 것이 보다 효과적이다.As the photoinitiator, it is preferable to use acetophenones such as Irgacure 369, Irgacure 651, Irgacure 907, TPO, CGI124, EPD / BMS mixed system, benzophenone series and triazine system. Benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4- hydroxythioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl 4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxy Cybenzoyldichloromethane, 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-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis ( Trichloromethyl) -s-triazine and the like. Such photoinitiator is more effective to use 0.005 to 20 parts by weight, preferably 0.5 to 10 parts by weight as a content to increase the transparency and minimize the dose.

본 발명의 음성 레지스트 조성물에 함유되는 에폭시기 또는 아민기를 갖는 실리콘계 첨가물은 ITO 전극과 조성물과의 접착력을 향상시키고 경화 후 내열 특성을 향상시킨다. 이러한 실리콘계 화합물로는 (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 아미노프로필트리메톡시 실레인 등이 있으며, 이들을 각각 단독으로 또는 이들을 혼합하여 사용할 수 있는데, 그 함량은 0.01 내지 3 중량부, 바람직하게는 0.05 내지 0.1 중량부이다.The silicone-based additive having an epoxy group or an amine group contained in the negative resist composition of the present invention improves adhesion between the ITO electrode and the composition and improves heat resistance properties after curing. Such silicone compounds include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3- Glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane , 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and amino Propyltrimethoxy silane and the like, each of them may be used alone or in combination thereof, the content is 0.01 to 3 parts by weight, preferably 0.05 to 0.1 parts by weight.

또한, 음성 포토레지스트 조성물에 사용될 수 있는 본 발명의 포토레지스트 조성물은 불소계 또는 실리콘계 계면활성제 0.01 내지 3 중량부를 함유한다. 이와 같은 불소계 또는 실리콘계 계면활성제로는 Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471, F-475(이상, Dainippon Ink & Chemicals)과, FC-170C, FC-430, FC-431(이상, Sumotomo 3M co., Ltd.)과, BYK 306, 307, 310, 331,333 (이상, BYK-Chemie)등의 상품명으로 판매되고 있다.In addition, the photoresist composition of the present invention that can be used in the negative photoresist composition contains 0.01 to 3 parts by weight of a fluorine-based or silicone-based surfactant. Such fluorine-based or silicone-based surfactants include Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471, and F-475 (above Dainippon Ink & Chemicals), FC-170C, FC -430, FC-431 (above, Sumotomo 3M co., Ltd.) and BYK 306, 307, 310, 331,333 (above, BYK-Chemie) are sold.

양성 포토레지스트 조성물로 이용될 수 있는 본 발명의 스핀리스 코팅용 포토레지스트 조성물은 바인더 수지로서 아크릴계 바인더 수지, 노볼락 바인더 수지 및 이들의 혼합물을 10 내지 28 중량부 함유한다. 아크릴계 바인더 수지는 음성 포토레지스트 조성물에서 기술한 바인더 수지를 사용하는 것이 바람직하며, 노볼락 바인더 수지는 공지된 노볼락 수지를 사용할 수 있는데, 그 합성법은 "Chemistry and Application of Phenolic Resins, Knop A and Scheib, W,; Springer Verlag, new York, 1979 Chapter 4."에 잘 설명되어 있다.The photoresist composition for spinless coating of the present invention which can be used as the positive photoresist composition contains 10 to 28 parts by weight of an acrylic binder resin, a novolak binder resin, and a mixture thereof as a binder resin. As the acrylic binder resin, it is preferable to use the binder resin described in the negative photoresist composition, and the novolak binder resin may use a known novolak resin, and the synthesis method thereof is "Chemistry and Application of Phenolic Resins, Knop A and Scheib. , W ,; Springer Verlag, new York, 1979 Chapter 4. "

또한, 양성 포토레지스트 조성물로 이용될 수 있는 본 발명의 스핀리스 코팅 용 포토레지스트 조성물에는 감광제가 4 내지 8 중량부 함유된다. 감광제로는 2,2',3,4,4'-펜타하이드록시벤조페논, 2,2',3,4,4',5-헥사하이드록시벤조페논, 2,2',3,4,4'-펜타하이드록시디페틸프로판, 2,2',3,4,4',5-펜타하이드록시디페닐프로판, 2,3,4-트리하이드록시벤조페논, 2,3,4-트리하이드록시아세토페논, 2,3,4-트리하이드록시페닐헥실케톤, 2,4,4'-트리하이드록시벤조페논, 2,4,6-트리하이드록시벤조페논, 2,3,4-트리하이드록시-2'-메틸벤조페논, 2,2',4,4'-테트라하이드록시벤조페논, 2,3,4,4'-테트라하이드록시벤조페논 등의 통상적으로 사용되는 감광제를 사용할 수 있다. In addition, the photoresist composition for spinless coating of the present invention that can be used as a positive photoresist composition contains 4 to 8 parts by weight of a photosensitive agent. As the photosensitizer, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,4 ', 5-hexahydroxybenzophenone, 2,2', 3,4, 4'-pentahydroxydipetylpropane, 2,2 ', 3,4,4', 5-pentahydroxydiphenylpropane, 2,3,4-trihydroxybenzophenone, 2,3,4-tri Hydroxyacetophenone, 2,3,4-trihydroxyphenylhexyl ketone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-tri Commonly used photosensitizers such as hydroxy-2'-methylbenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone can be used. have.

또한, 양성 포토레지스트 조성물로 이용될 수 있는 본 발명의 스핀리스 코팅용 포토레지스트 조성물에는 에폭시기 또는 아민기를 갖는 실리콘계 화합물과, 불소계 또는 실리콘계 계면활성제는 각각 0.01 내지 3 중량부가 함유되며, 사용 가능한 종류는 음성 포토레지스트 조성물에서 이미 기술한 바 있다. In addition, the photoresist composition for spinless coating of the present invention that can be used as an amphoteric photoresist composition contains 0.01 to 3 parts by weight of a silicone compound having an epoxy group or an amine group, and a fluorine or silicone surfactant, respectively, It has already been described in the negative photoresist composition.

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

본 발명의 포토레지스트 조성물은 스핀리스 코팅을 위하여 점도를 2 내지 20 cps 범위가 되도록 용매를 첨가하는 것이 바람직하다. 더욱 바람직하게는 점도를 4 내지 7 cps가 되도록 조절하는 것이 코팅 후 박막의 핀홀(pin hole)이 없고 박막의 두께를 조절하는데 보다 유리하다. 이러한 용매로는 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸 에테르아세테이트 (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.In the photoresist composition of the present invention, it is preferable to add a solvent so that the viscosity is in the range of 2 to 20 cps for spinless coating. More preferably, adjusting the viscosity to be 4 to 7 cps is more advantageous for controlling the thickness of the thin film without the pin hole of the thin film after coating. Such solvents include 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, dimethyl form Amide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme , Tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene Solvents selected from glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane alone or in combination 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 ~ 19><Examples 1 to 19>

하기에 기재된 성분과 함량으로 표 1에 따라 음성 포토레지스트 조성물을 제조하였다.A negative photoresist composition was prepared according to Table 1 with the ingredients and contents described below.

아크릴계 바인더 수지 : 10%Acrylic binder resin: 10%

에틸렌성 불포화 결합을 갖는 다기능 모노머 : 10%Multifunctional monomer with ethylenically unsaturated bonds: 10%

Irgacure 369 : 5%Irgacure 369: 5%

(3-글리시드옥시프로필)트리메톡시실레인 : 0.05%(3-glycidoxyoxy) trimethoxysilane: 0.05%

실리콘계 계면활성제 : 0.03%Silicone Surfactant: 0.03%

용매 : 잔량Solvent: remaining amount

아크릴계 바인더 수지는 전술한 일반식 1(일반식 1에서 X는 메틸기이고, Y1은 메틸기이고, Y2가 화학식(II)로서 R1은 메틸기)인 화합물을 사용하였다. 또한, 에틸렌성 불포화 결합을 갖는 다기능 모노머는 dipentaerythritol penta/hexa acrylate(DPHA)를 사용하였고, 실리콘계 계면활성제로는 BYK 307(BYK-Chemie사)을 사용하였다.As the acrylic binder resin, a compound in which General Formula 1 (wherein X is a methyl group, Y 1 is a methyl group, and Y 2 is a general formula (II) as R 1 is a methyl group) was used. In addition, dipentaerythritol penta / hexa acrylate (DPHA) was used as a multifunctional monomer having an ethylenically unsaturated bond, and BYK 307 (BYK-Chemie) was used as a silicone-based surfactant.

<실시예 20 ~ 51><Examples 20 to 51>

용매로서 DMC를 사용하고, 계면활성제의 종류와 함량을 하기 표 2에 기재된 바와 같이 변화시킨 것을 제외하고는 실시예 1과 동일한 방법으로 음성 포토레지스트 조성물을 제조하였다.A negative photoresist composition was prepared in the same manner as in Example 1, except that DMC was used as a solvent, and the type and content of the surfactant were changed as described in Table 2 below.

<실시예 52 ~ 71><Examples 52 to 71>

하기에 기재된 성분과 함량으로 표 3에 따라 양성 포토레지스트 조성물을 제조하였다.A positive photoresist composition was prepared according to Table 3 with the ingredients and contents described below.

크레졸-포름알데히드 노볼락 : 10%Cresol-formaldehyde novolac: 10%

2,3,4,4'-테트라하이드록시벤조페논의 나프토퀴논-1,2-디아지토-5-황산 에스테르 : 2%Naphthoquinone-1,2-diazito-5-sulfate ester of 2,3,4,4'-tetrahydroxybenzophenone: 2%

불소계 계면활성제 : 0.03%Fluorine-based surfactant: 0.03%

용매 : 잔량Solvent: remaining amount

불소계 계면활성제로는 Megaface F142D(Dainippon Ink & Chemicals사)를 사용하였다.Megaface F142D (Dainippon Ink & Chemicals) was used as the fluorine-based surfactant.

전술한 조성으로 제조한 포토레지스트 조성물의 점도는 약 4 cps였다.The viscosity of the photoresist composition prepared with the above composition was about 4 cps.

실시예에 따른 포토레지스트 조성물의 평가는 실리콘 웨이퍼 또는 크롬 유리 등의 기판 위에서 실시하였으며, 레지스트 조성물의 얼룩특성조사, 평탄성(Uniformity), edge profile 특성을 하기 기준으로 평가하여 그 결과를 표 1 ~ 3에 나타냈다.  Evaluation of the photoresist composition according to the embodiment was carried out on a substrate such as a silicon wafer or chromium glass, and the staining properties, uniformity, and edge profile characteristics of the resist composition were evaluated based on the following criteria. Indicated.

(1) 얼룩특성조사(1) Stain Characteristic Investigation

레지스트 조성물을 실리콘 웨이퍼 위에 스핀리스 코터를 이용하여 도포한 후, 90℃에서 1분간 프리베이크(prebake)한 후, 코팅막이 형광불빛밑에서 육안으로 얼룩이 없으면, '양호' 그렇지 않은 경우를 '불량'으로 판단하였다.After applying the resist composition on a silicon wafer using a spinless coater, prebake at 90 ° C. for 1 minute, and if the coating is visually unstained under fluorescent light, 'good' or 'bad' Judging

(2) Uniformity(2) Uniformity

레지스트 조성물을 실리콘 웨이퍼 위에 스핀리스 코터를 이용하여 도포한 후, 90℃에서 1분간 프리베이크(prebake)한 후 10 포인트를 나토스펙으로 두께를 측정하였다. 코팅막의의 max과 min의 차이가 1000 A을 넘지않으면, '양호' 그렇지 않은 경우를 '불량'으로 판단하였다.The resist composition was applied onto a silicon wafer using a spinless coater, and then prebaked at 90 ° C. for 1 minute, and the thickness of 10 points was measured by NATOSPEC. If the difference between the max and min of the coating film does not exceed 1000 A, 'good' or not was determined as 'bad'.

(3) Edge Profile(3) Edge Profile

레지스트 조성물을 실리콘 웨이퍼 위에 스핀리스 코터를 이용하여 도포한 후, 90℃에서 1분간 프리베이크(prebake)한 후 프로파일러메터(profiler meter)로 에지 부분을 스캔하여, 패턴 사이드 벽(side wall)이 기판에 대하여 55도 이상의 각도로 세워져 있는 것을 '양호'로 하고, 그렇지 않은 경우를 '불량'으로 판단하였다. The resist composition was applied onto a silicon wafer using a spinless coater, then prebaked at 90 ° C. for 1 minute, followed by scanning the edge portion with a profiler meter to form a pattern side wall. It was judged as 'good' to stand at an angle of 55 degrees or more with respect to the substrate, and 'bad' as otherwise.

실시예Example 용매menstruum UniformityUniformity Edge ProfileEdge profile coating 얼룩coating stain II IIII 비율%(I:II)Percentage% (I: II) 1One DMCDMC -- 100:0100: 0 양호Good 양호Good 양호Good 22 DMCDMC NBANBA 90:1090:10 양호Good 양호Good 양호Good 33 DMCDMC NBANBA 80:2080:20 양호Good 양호Good 양호Good 44 DMCDMC NBANBA 70:3070:30 양호Good 양호Good 양호Good 55 DMCDMC MCAMCA 90:1090:10 양호Good 양호Good 양호Good 66 DMCDMC MCAMCA 80:2080:20 양호Good 양호Good 양호Good 77 DMCDMC MCAMCA 70:3070:30 양호Good 양호Good 양호Good 88 DMCDMC CHXCHX 90:1090:10 양호Good 양호Good 양호Good 99 DMCDMC CHXCHX 80:2080:20 양호Good 양호Good 양호Good 1010 DMCDMC CHXCHX 70:3070:30 양호Good 양호Good 양호Good 1111 DMCDMC PGMEAPGMEA 90:1090:10 양호Good 양호Good 양호Good 1212 DMCDMC PGMEAPGMEA 80:2080:20 양호Good 양호Good 양호Good 1313 DMCDMC PGMEAPGMEA 70:3070:30 양호Good 양호Good 양호Good 1414 DMCDMC EEPEEP 90:1090:10 양호Good 양호Good 양호Good 1515 DMCDMC EEPEEP 80:2080:20 양호Good 양호Good 양호Good 1616 DMCDMC EEPEEP 70:3070:30 양호Good 양호Good 양호Good 1717 DMCDMC PGPEPGPE 90:1090:10 양호Good 양호Good 양호Good 1818 DMCDMC PGPEPGPE 80:2080:20 양호Good 양호Good 양호Good 1919 DMCDMC PGPEPGPE 70:3070:30 양호Good 양호Good 양호Good

실시예Example 계면활성제Surfactants UniformityUniformity Edge ProfileEdge profile coating 얼룩coating stain 종류Kinds 함량content 2020 Megaface F142DMegaface F142D 0.010.01 양호Good 양호Good 양호Good 2121 F142DF142D 22 양호Good 양호Good 양호Good 2222 F172F172 0.010.01 양호Good 양호Good 양호Good 2323 F172F172 22 양호Good 양호Good 양호Good 2424 F-172DF-172D 0.010.01 양호Good 양호Good 양호Good 2525 F-172DF-172D 22 양호Good 양호Good 양호Good 2626 F177-PF177-P 0.010.01 양호Good 양호Good 양호Good 2727 F177-PF177-P 22 양호Good 양호Good 양호Good 2828 R-08R-08 0.010.01 양호Good 양호Good 양호Good 2929 R-08R-08 22 양호Good 양호Good 양호Good 3030 F-470F-470 0.010.01 양호Good 양호Good 양호Good 3131 F-470F-470 22 양호Good 양호Good 양호Good 3232 F-471F-471 0.010.01 양호Good 양호Good 양호Good 3333 F-471F-471 22 양호Good 양호Good 양호Good 3434 F-475F-475 0.010.01 양호Good 양호Good 양호Good 3535 F-475F-475 22 양호Good 양호Good 양호Good 3636 FC-170CFC-170C 0.010.01 양호Good 양호Good 양호Good 3737 FC-170CFC-170C 22 양호Good 양호Good 양호Good 3838 FC-430FC-430 0.010.01 양호Good 양호Good 양호Good 3939 FC-430FC-430 22 양호Good 양호Good 양호Good 4040 FC-431FC-431 0.010.01 양호Good 양호Good 양호Good 4141 FC-431FC-431 22 양호Good 양호Good 양호Good 4242 BYK306BYK306 0.010.01 양호Good 양호Good 양호Good 4343 BYK306BYK306 22 양호Good 양호Good 양호Good 4444 BYK307BYK307 0.010.01 양호Good 양호Good 양호Good 4545 BYK307BYK307 22 양호Good 양호Good 양호Good 4646 BYK310BYK310 0.010.01 양호Good 양호Good 양호Good 4747 BYK310BYK310 22 양호Good 양호Good 양호Good 4848 BYK331BYK331 0.010.01 양호Good 양호Good 양호Good 4949 BYK331BYK331 22 양호Good 양호Good 양호Good 5050 BYK333BYK333 0.010.01 양호Good 양호Good 양호Good 5151 BYK333BYK333 22 양호Good 양호Good 양호Good

실시예Example 용매menstruum UniformityUniformity Edge ProfileEdge profile coating 얼룩coating stain II IIII IIIIII 비율% (I:II:III)Percent% (I: II: III) 5252 PGMEAPGMEA -- -- 100:0:0100: 0: 0 양호Good 양호Good 양호Good 5353 PGMEAPGMEA MCAMCA -- 95:5:095: 5: 0 양호Good 양호Good 양호Good 5454 PGMEAPGMEA MCAMCA -- 90:10:090: 10: 0 양호Good 양호Good 양호Good 5555 PGMEAPGMEA MCAMCA -- 85:15:085: 15: 0 양호Good 양호Good 양호Good 5656 PGMEAPGMEA MCAMCA -- 80:20:080: 20: 0 양호Good 양호Good 양호Good 5757 PGMEAPGMEA MCAMCA -- 70:30:070: 30: 0 양호Good 양호Good 양호Good 5858 PGMEAPGMEA MCAMCA NBANBA 95:5:595: 5: 5 양호Good 양호Good 양호Good 5959 PGMEAPGMEA MCAMCA NBANBA 80:10:10:80:10:10: 양호Good 양호Good 양호Good 6060 PGMEAPGMEA MCAMCA NBANBA 70:15:1570:15:15 양호Good 양호Good 양호Good 6161 DMCDMC -- -- 100:0:0100: 0: 0 양호Good 양호Good 양호Good 6262 DMCDMC NBANBA -- 90:10:090: 10: 0 양호Good 양호Good 양호Good 6363 DMCDMC NBANBA -- 80:20:080: 20: 0 양호Good 양호Good 양호Good 6464 ECaAECaA -- -- 100:0:0100: 0: 0 양호Good 양호Good 양호Good 6565 ECaAECaA NBANBA -- 95:5:095: 5: 0 양호Good 양호Good 양호Good 6666 ECaAECaA NBANBA -- 90:10:090: 10: 0 양호Good 양호Good 양호Good 6767 ECaAECaA NBANBA -- 80:20:080: 20: 0 양호Good 양호Good 양호Good 6868 PGMEAPGMEA EEPEEP -- 90:10:090: 10: 0 양호Good 양호Good 양호Good 6969 PGMEAPGMEA EEPEEP -- 80:20:080: 20: 0 양호Good 양호Good 양호Good 7070 PGMEAPGMEA EEPEEP NBANBA 90:5:590: 5: 5 양호Good 양호Good 양호Good 7171 PGMEAPGMEA EEPEEP NBANBA 80:10:1080:10:10 양호Good 양호Good 양호Good

이상에서 살펴본 바와 같이, 본 발명에 따른 포토레지스트 조성물은 스핀리스 코팅시 얼룩이 없는 균일한 코팅막을 형성할 수 있을 뿐만 아니라, 코팅막의 에지 프로파일(edge profile) 콘트롤도 용이하다.As described above, the photoresist composition according to the present invention can not only form a uniform coating film without spots during spinless coating, but also easily control the edge profile of the coating film.

Claims (7)

삭제delete 아크릴계 바인더 수지, 노볼락 바인더 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 바인더 수지 10 내지 28 중량부, 감광제 4 내지 8 중량부, 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.01 내지 3 중량부 및 불소계 또는 실리콘계 계면활성제 0.01 내지 3 중량부를 함유하는 조성물로서, 점도가 2 내지 20 cps가 되도록 용매가 첨가된 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물.10 to 28 parts by weight of a binder resin selected from the group consisting of acrylic binder resins, novolac binder resins and mixtures thereof, 4 to 8 parts by weight of a photosensitizer, 0.01 to 3 parts by weight of a silicone compound containing an epoxy group or an amine group and a fluorine or silicone interface A composition containing 0.01 to 3 parts by weight of an active agent, wherein a solvent is added so as to have a viscosity of 2 to 20 cps. 제2항에 있어서, 상기 아크릴계 바인더 수지는 하기 일반식 1로 표시되는 수지, 하기 일반식 2로 표시되는 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물. The photoresist for spinless coating according to claim 2, wherein the acrylic binder resin is any one 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. Composition. <일반식 1><Formula 1>
Figure 112005065723091-pat00024
Figure 112005065723091-pat00024
 상기 일반식 1에서, X는 수소원자 또는 메틸기이고, Y1은 탄소원자수가 2 내지 16인 알킬기 또는 하이드록시알킬기이고, Y2는 하기 화학식(Ⅰ) 내지 화학식(XX)로 표시되는 화합물로부터 선택된 어느 하나임;In Formula 1, X is a hydrogen atom or a methyl group, Y 1 is an alkyl group or hydroxyalkyl group having 2 to 16 carbon atoms, Y 2 is selected from compounds represented by the following formula (I) to formula (XX) Which one;
Figure 112005065723091-pat00025
Figure 112005065723091-pat00025
Figure 112005065723091-pat00026
Figure 112005065723091-pat00026
Figure 112005065723091-pat00027
Figure 112005065723091-pat00027
Figure 112005065723091-pat00028
Figure 112005065723091-pat00028
Figure 112005065723091-pat00029
Figure 112005065723091-pat00029
Figure 112005065723091-pat00030
Figure 112005065723091-pat00030
Figure 112005065723091-pat00031
Figure 112005065723091-pat00031
Figure 112005065723091-pat00032
Figure 112005065723091-pat00032
Figure 112005065723091-pat00033
Figure 112005065723091-pat00033
Figure 112005065723091-pat00034
Figure 112005065723091-pat00034
Figure 112005065723091-pat00035
Figure 112005065723091-pat00035
Figure 112005065723091-pat00036
Figure 112005065723091-pat00036
Figure 112005065723091-pat00037
Figure 112005065723091-pat00037
Figure 112005065723091-pat00038
Figure 112005065723091-pat00038
Figure 112005065723091-pat00039
Figure 112005065723091-pat00039
Figure 112005065723091-pat00040
Figure 112005065723091-pat00040
Figure 112005065723091-pat00041
Figure 112005065723091-pat00041
Figure 112005065723091-pat00042
Figure 112005065723091-pat00042
Figure 112005065723091-pat00043
Figure 112005065723091-pat00043
Figure 112005065723091-pat00044
Figure 112005065723091-pat00044
 상기 화학식(Ⅰ) 내지 화학식(XX)에서, R1은 수소 또는 메틸기이고, R2는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, R3는 탄소원자수가 1 내지 10인 탄화수소의 잔류 그룹이고, R4는 수소 또는 메틸기이고, R5는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, k는 0 내지 10의 정수이고;In formulas (I) to (XX), R 1 is hydrogen or a methyl group, R 2 is an alkylene group having 1 to 10 carbon atoms, and R 3 is a residual group of hydrocarbon having 1 to 10 carbon atoms R 4 is hydrogen or a methyl group, R 5 is an alkylene group having 1 to 10 carbon atoms, and k is an integer of 0 to 10; <일반식 2><Formula 2>
Figure 112005065723091-pat00045
Figure 112005065723091-pat00045
 상기 일반식 2에서, 중합단위 A는 벤질메타아크릴레이트(Benzyl Methacrylate), 스티렌(Styrene), 알파-메틸스티렌(α-methyl styrene), 이소보닐아크릴레이트(isobonyl acrylate) 및 이소보닐메타아크릴레이트(Isobonyl methacrylate), 디사이클로펜타닐아크릴레이트(Dicyclopentanyl acrylate), 디사이클로펜타닐메타아크릴레이트(Dicyclopentanyl methacrylate), 디사이클로펜테닐아크릴레이트(Dicyclopentenyl acrylate), 디사이클로펜테닐메타아크릴레이트 (Dicyclopentenyl methacrylate), 디사이클로펜타닐에틸옥시아크릴레이트 (Dicyclopentanylethyloxy acrylate), 디사이클로펜타닐에틸옥시메타아크릴레이트 (Dicyclopentanylethyloxy methacrylate), 디사이클로펜테닐에틸옥시아크릴레이트 (Dicyclopentenylethyloxy acrylate), 디사이클로펜테닐에틸옥시메타아크릴레이트 (Dicyclopentenylethyloxy methacrylate)로 이루어진 군으로부터 선택된 어느 하나이고, B는 글리시딜 메타아크릴레이트(Glycidyl Methacrylate), 히드록시에틸 메타아크릴레이트(Hydroxymethyl Methacrylate), 디메틸아미노 메타아크릴레이트 (Dimethylamino Methacrylate), 아크릴아미드(Acryl amide)로 이루어진 군으로부터 선택된 어느 하나이고, C는 아크릴산 또는 메타아크릴산이며, 상기 일반식 2의 바인더 수지는 중합단위 A, B 및 C의 배열순서에 구속되지 않는 랜덤 공중합체를 포함한다.In Formula 2, the polymerization unit A is benzyl methacrylate, styrene, alpha-methyl styrene, isobonyl acrylate, and isobornyl methacrylate. Isobonyl methacrylate, Dicyclopentanyl acrylate, Dicyclopentanyl methacrylate, Dicyclopentenyl acrylate, Dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, Dicyclopentanyl methacrylate Dicyclopentanylethyloxy acrylate, Dicyclopentanylethyloxy methacrylate, Dicyclopentenylethyloxy acrylate, Dicyclopentenylethyloxy methacrylate Selected from the group consisting of B is any one selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate, acryl amide One, C is acrylic acid or methacrylic acid, and the binder resin of the general formula (2) includes a random copolymer that is not bound to the sequence of the polymerization units A, B and C. 삭제delete 제2항에 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 스핀리스 코팅용 포토레지스트 조성물. According to claim 2, wherein the silicon-based compound containing an epoxy group or an amine group is (3-glycidoxy propyl) 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 a photoresist composition for spinless coating. 제2항에 있어서, 상기 용매는 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 옥탄으로 이루어진 군으로부터 선택된 어느 하나 이상을 포함하는 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물.The method of claim 2, wherein the 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, cyclo Hexanone, dimethylformumamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, di Diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether And diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane. 제2항에 있어서, 상기 불소계 또는 실리콘계 계면활성제 수지는 Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471, F-475(이상, Dainippon Ink & Chemicals), FC-170C, FC-430, FC-431(이상, Sumotomo 3M co., Ltd.), BYK 306, 307, 310, 331,333 (이상, BYK-Chemie) 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 스핀리스 코팅용 포토레지스트 조성물. According to claim 2, wherein the fluorine-based or silicone-based surfactant resin is Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471, F-475 (above, Dainippon Ink & Chemicals), FC Any one selected from the group consisting of -170C, FC-430, FC-431 (or more, Sumotomo 3M co., Ltd.), BYK 306, 307, 310, 331,333 (or more, BYK-Chemie) and mixtures thereof A photoresist composition for spinless coating, characterized in that.
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