KR100922843B1 - Photosensitive resin composition for dielectrics - Google Patents

Photosensitive resin composition for dielectrics Download PDF

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KR100922843B1
KR100922843B1 KR1020070130379A KR20070130379A KR100922843B1 KR 100922843 B1 KR100922843 B1 KR 100922843B1 KR 1020070130379 A KR1020070130379 A KR 1020070130379A KR 20070130379 A KR20070130379 A KR 20070130379A KR 100922843 B1 KR100922843 B1 KR 100922843B1
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acrylate
photosensitive resin
resin composition
insulating film
acid
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KR20090062899A (en
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신동주
오희영
최정식
이천석
한규석
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제일모직주식회사
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • G03F7/023Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/133345Insulating layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • G03F7/0226Quinonediazides characterised by the non-macromolecular additives
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs

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Abstract

본 발명은, 절연막 형성용 감광성 수지 조성물에 관한 것으로서, 상기 감광성 수지 조성물은 (A)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물, ⅱ) 에폭시기 함유 불포화 화합물, 및 ⅲ) 올레핀계 불포화 화합물을 불포화 단량체로 하는 아크릴계 공중합체; (B) 퀴논디아지드 화합물; (C) p-톨루엔 설폰산/피리딘 염; 및 (D) 용매를 포함한다.The present invention relates to a photosensitive resin composition for forming an insulating film, wherein the photosensitive resin composition comprises (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) olefinic unsaturated Acrylic copolymer which makes a compound an unsaturated monomer; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) a solvent.

유기 절연막, 감광성 수지, 저장안정성, p-톨루엔 설폰산/피리딘 염 Organic insulating film, photosensitive resin, storage stability, p-toluene sulfonic acid / pyridine salt

Description

절연막 형성용 감광성 수지 조성물{PHOTOSENSITIVE RESIN COMPOSITION FOR DIELECTRICS}Photosensitive resin composition for insulating film formation {PHOTOSENSITIVE RESIN COMPOSITION FOR DIELECTRICS}

본 발명은 절연막 형성용 감광성 수지 조성물에 관한 것으로서, 보다 상세하게는 투과율, 절연성, 고내열성 등의 성능이 우수하며, 특히 고감도, 고잔막률, 및 저장안정성을 향상시킨 절연막 형성용 감광성 수지 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming an insulating film, and more particularly, to a photosensitive resin composition for forming an insulating film having excellent performances such as transmittance, insulation, and high heat resistance, and particularly improving high sensitivity, high residual film rate, and storage stability. will be.

기존 층간절연막은 바인더(Binder), 광반응 화합물(photoactive compound:PAC), 및 용매(solvent)로 이루어져 있으며, 바인더로서 아크릴계열의 수지를 사용해왔다. 그러나, 상기와 같은 유기막 조성물의 경우 추가적인 고감도 및 고잔막률 특성개선에 한계를 가진다. 또한, 에폭시 아크릴레이트계 수지를 사용함에 따라 저장안정성 측면의 문제도 가져왔다. The existing interlayer insulating film is composed of a binder, a photoactive compound (PAC), and a solvent, and an acrylic resin has been used as a binder. However, in the case of the organic film composition as described above, there is a limit to further high sensitivity and high residual film rate characteristics. In addition, the use of epoxy acrylate-based resins also brought about problems in terms of storage stability.

본 발명은 투과율, 절연성, 고내열성 등의 성능이 우수하며, 특히 고감도, 고잔막률, 및 저장안정성을 향상시킨 절연막 형성용 감광성 수지 조성물을 제공하는 것이다.The present invention is excellent in the performance of transmittance, insulation, high heat resistance and the like, and particularly to provide a photosensitive resin composition for forming an insulating film with improved high sensitivity, high residual film rate, and storage stability.

다만, 본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 또 다른 기술적 과제들은 아래의 기재로부터 당업자들에게 명확히 이해될 수 있을 것이다.However, the technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems will be clearly understood by those skilled in the art from the following description.

상기 목적을 달성하기 위하여, 본 발명의 일 구현예에 따르면, (A)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물, ⅱ) 에폭시기 함유 불포화 화합물, 및 ⅲ) 올레핀계 불포화 화합물을 불포화 단량체로 하는 아크릴계 공중합체; (B) 퀴논디아지드 화합물; (C) p-톨루엔 설폰산/피리딘 염; 및 (D) 용매를 포함하는 절연막 형성용 감광성 수지 조성물이 제공된다. In order to achieve the above object, according to one embodiment of the present invention, (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixture thereof, ii) epoxy group-containing unsaturated compound, and iii) unsaturated olefinically unsaturated compound Acrylic copolymer made into a monomer; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) there is provided a photosensitive resin composition for forming an insulating film comprising a solvent.

본 발명의 다른 일 구현예에 따르면, 상기 절연막 형성용 감광성 수지 조성물로 제조되는 절연막을 포함하는 액정 디스플레이 장치가 제공된다.According to another embodiment of the present invention, a liquid crystal display device including an insulating film made of the photosensitive resin composition for forming an insulating film is provided.

기타, 본 발명의 구현예들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Other details of the embodiments of the present invention are included in the following detailed description.

본 발명에 따른 절연막 형성용 감광성 수지 조성물은 투과율, 절연성, 고내열성 등의 성능이 우수하며, 특히 향상된 고감도, 고잔막률 및 저장안정성을 나타낸다.The photosensitive resin composition for forming an insulating film according to the present invention has excellent performances such as transmittance, insulation, and high heat resistance, and particularly shows improved high sensitivity, high residual film rate, and storage stability.

이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것이고, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구 항의 범주에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is only defined by the scope of the claims to be described later.

본 발명의 일 구현예에 따른 절연막 형성용 감광성 수지 조성물은, (A)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물, ⅱ) 에폭시기 함유 불포화 화합물 및 ⅲ) 올레핀계 불포화 화합물을 불포화 단량체로 하는 아크릴계 공중합체; (B) 퀴논디아지드 화합물; (C) p-톨루엔 설폰산/피리딘 염; 및 (D) 용매를 포함한다.In the photosensitive resin composition for forming an insulating film according to an embodiment of the present invention, (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound and iii) an olefinically unsaturated compound Acrylic copolymer made into; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) a solvent.

이하, 본 발명의 일 구현예에 따른 절연막 형성용 감광성 수지 조성물의 각 성분에 대하여 구체적으로 살펴본다.Hereinafter, each component of the photosensitive resin composition for forming an insulating film according to an embodiment of the present invention will be described in detail.

(A) 아크릴계 공중합체(A) Acrylic Copolymer

상기 아크릴계 공중합체는 (A)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물, ⅱ) 에폭시기 함유 불포화 화합물, 및 ⅲ) 올레핀계 불포화 화합물을 불포화 단량체로 하는 아크릴계 공중합체이다.The acrylic copolymer is an acrylic copolymer comprising (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) an olefinic unsaturated compound as an unsaturated monomer.

ⅰ) 상기 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물Iii) said unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof

상기 ⅰ) 상기 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물로는 아크릴산, 메타크릴산 등의 불포화 모노카르본산류; 말레인산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 등의 불포화 디카르본산류; 이들 산의 무수물; 또는 이들의 조합 등을 사용할 수 있다. 바람직하게는 아크릴산, 메타크릴산, 또는 이들의 조합을 사용하는 것이 공중합 반응성과 알칼리 수용액에 대한 용해성이 우수한 장점이 있다.(Iii) unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid as the unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these acids; Or combinations thereof. Preferably using acrylic acid, methacrylic acid, or a combination thereof has the advantage of excellent copolymerization reactivity and solubility in aqueous alkali solution.

상기 아크릴계 공중합체는 상기 ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로 유도되는 구성단위를 10 내지 60 중량%로 포함하는 것이 바람직하고, 20 내지 45 중량%로 포함하는 것이 보다 바람직하다. 10 중량% 미만인 경우에는 알칼리 수용액에 용해되기 어려운 문제점이 있어 바람직하지 못하고, 60 중량%를 초과하는 경우에는 알칼리 수용액에 대한 용해성이 지나치게 커지는 문제점이 있어 바람직하지 못하다.The acrylic copolymer preferably contains 10 to 60% by weight, more preferably 20 to 45% by weight, of the structural unit derived from the aforementioned i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof. . If it is less than 10% by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, and if not more than 60% by weight, there is a problem that the solubility in the aqueous alkali solution is too large, which is not preferable.

ⅱ) 에폭시기 함유 불포화 화합물Ii) epoxy group-containing unsaturated compounds

상기 ⅱ) 에폭시기 함유 불포화 화합물로는, 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸 아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸 아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜 등의 아크릴산 글리시딜류; 아크릴산-3,4-에폭시부틸, 메타클리산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸 아크릴산-6,7-에폭시헵틸 등의 아크릴산 에폭시 알킬류; o-비닐벤질 글리시딜 에테르, m-비닐벤질 글리시딜 에테르, p-비닐벤질 글리시딜 에테르 등의 비닐벤질 글리시딜 에테르류; 또는 이들의 조합 등을 사용할 수 있다. 바람직하게는 메타크릴산 글리시딜, 메타크릴산-β-메틸글리시딜, 메타크릴산-6,7-에폭시헵틸, o-비닐벤질 글리시딜 에테르, m-비닐벤질 글리시딜 에테르, p-비닐벤질 글리시딜 에테르, 또는 이들의 조합 등을 사용하는 것이 공중합 반응성 및 얻어진 패턴의 내열성을 높일 수 있어 바람직하다.As said ii) epoxy group containing unsaturated compound, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butyl acrylate, Glycidyl acrylates, such as acrylic acid (beta) -methylglycidyl, methacrylic acid (beta) -methylglycidyl, acrylic acid (beta) -ethylglycidyl, and methacrylic acid (beta) -ethylglycidyl; Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylic acid-6,7-epoxy Acrylic acid epoxy alkyls such as heptyl; vinyl benzyl glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; Or combinations thereof. Preferably methacrylic acid glycidyl, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, It is preferable to use p-vinylbenzyl glycidyl ether or a combination thereof in order to improve the copolymerization reactivity and the heat resistance of the obtained pattern.

본 발명의 아크릴계 공중합체는 상기 ⅱ) 에폭시기 함유 불포화 화합물로부 터 유도되는 구성단위를 5 내지 40 중량%로 포함하고, 10 내지 25 중량%로 포함하는 것이 보다 바람직하다. 5 중량% 미만인 경우에는 패턴의 내열성이 현저히 저하되는 문제점이 있어 바람직하지 못하고, 40 중량%를 초과하는 경우에는 공중합체의 보존안정성이 저하되는 문제점이 있어 바람직하지 못하다.The acrylic copolymer of the present invention preferably contains 5 to 40 wt% of the structural unit derived from the ii) epoxy group-containing unsaturated compound, and more preferably 10 to 25 wt%. If it is less than 5% by weight, there is a problem that the heat resistance of the pattern is considerably lowered, and it is not preferable. If it exceeds 40% by weight, there is a problem that the storage stability of the copolymer is lowered, which is not preferable.

ⅲ) 올레핀계 불포화 화합물Iii) olefinically unsaturated compounds

상기 ⅲ) 올레핀계 불포화 화합물로는, 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸메타크릴레이트, sec-부틸메타크릴레이트, tert-부틸메타크릴레이트, 메틸아크릴레이트, 이소프로필아크릴레이트, 시크로헥실메타크릴레이트, 2-메틸시클로헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸아크릴레이트, 1-아다만틸메타크릴레이트, 디시클로펜타닐옥시에틸 메타크릴레이트, 이소보닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시에틸아크릴레이트, 스티렌, α-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 비닐 톨루엔, p-메톡시스티렌, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔, 또는 이들의 조합 등을 사용할 수 있다. 바람직하게는 스티렌, 디시클로펜타닐메타크릴레이트, p-메톡시스티렌, 또는 이들의 조합 등을 사용하는 것이 공중합 반응성 및 알칼리 수용액에 대한 용해성이 우수한 장점이 있다.(Iii) Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acryl Rate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate Latex, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl arc Latex, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, or these Can be used. Preferably, styrene, dicyclopentanyl methacrylate, p-methoxy styrene, or a combination thereof is used to have excellent copolymerization reactivity and solubility in aqueous alkali solution.

본 발명의 아크릴계 공중합체는 상기 ⅲ) 올레핀계 불포화 화합물로부터 유도되는 구성단위를 20 내지 85 중량%로 포함하는 것이 바람직하고, 35 내지 50 중량%로 포함하는 것이 보다 바람직하다. 20 중량% 미만인 경우에는 아크릴계 공중 합체의 보존성이 저하되는 문제점이 있어 바람직하지 못하고, 85 중량%를 초과하는 경우에는 아크릴계 공중합체가 알칼리 수용액에 용해되기 어려워 바람직하지 못하다.The acrylic copolymer of the present invention preferably contains 20 to 85% by weight, more preferably 35 to 50% by weight, of the structural unit derived from the aforementioned iv) olefinically unsaturated compound. 20 wt% If less than this, there is a problem that the preservation of the acrylic copolymer is lowered, which is not preferable. If it exceeds 85% by weight, the acrylic copolymer is difficult to dissolve in an aqueous alkali solution, which is not preferable.

상기 아크릴계 공중합체는, 상기 ⅰ) 내지 ⅲ)의 불포화 단량체들을 용매 및 중합개시제의 존재하에서 라디칼 중합하여 제조될 수 있다.The acrylic copolymer may be prepared by radical polymerization of unsaturated monomers of (i) to (i) in the presence of a solvent and a polymerization initiator.

상기 공중합체의 제조에 사용되는 용매로는, 메탄올, 테트라히드로퓨란, 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 프로필렌글리콜 모노메틸에테르 아세테이트, 메틸세로솔브아세테이트, 에틸세로솔브아세테이트, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르,에틸렌글리콜 디메틸에테르, 에틸렌글리콜 디에틸에테르, 에틸렌글리콜 메틸에틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 프로필에테르, 프로필렌글리콜 부틸에테르, 프로필렌글리콜 메틸에틸아세테이트, 프로필렌 글리콜 에틸에테르아세테이트, 프로필렌글리콜 프로필에테르아세테이트, 프로필렌글리콜 부틸에테르아세테이트, 프로필렌글리콜 메틸에틸프로피오네이트, 프로필렌글리콜 에틸에테르프로피오네이트, 프로필렌글리콜 프로필에테르프로피오네이트, 프로필렌글리콜 부틸에테르프로피오네이트, 톨루엔, 크실렌, 메틸에틸케톤, 시클로헥사논, 4-히드록시 4-메틸 2-펜타논, 초산메틸, 초산에틸, 초산프로필, 초산부틸, 2-히드록시 프로피온산에틸, 2-히드록시 2-메틸프로피온산메틸, 2-히드록시 2-메틸프로피온산에틸, 히드록시 초산메틸, 히드록시 초산에틸, 히드록시 초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시 프로피온산메틸, 3-히드록시 프로피온산에틸, 3-히드록시프로피온산 프 로필, 3-히드록시 프로피온산 부틸, 2-히드록시 3-메틸부탄산메틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산프로필, 메톡시초산부틸, 에톡시초산메틸, 메톡시초산에틸, 에톡시초산프로필, 에톡시초산부틸, 프로폭시초산메틸, 프로폭시초산에틸, 프로폭시초산프로필, 프로폭시초산부틸, 부톡시초산 메틸, 부톡시초산에틸, 부톡시초산 프로필, 부톡시초산 부틸, 2-메톡시프로피온산 메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산 프로필, 2-메톡시프로피온산 부틸, 2-에톡시프로피온산 메틸, 2-에톡시프로피온산 에틸, 2-에톡시프로피온산 프로필, 2-에톡시프로피온산 부틸, 2-부톡시프로피온산 메틸, 2-부톡시프로피온산 에틸, 2-부톡시프로피온산프로필, 2-부톡시프로피온산 부틸, 3-메톡시프로피온산 메틸, 3-메톡시프로피온산 에틸, 3-메톡시프로피온산 프로필, 3-메톡시프로피온산 부틸, 3-에톡시프로피온산 메틸, 3-에톡시프로피온산 에틸, 3-에톡시프로피온산 프로필, 3-에톡시프로피온산 부틸, 3-프로폭시프로피온산 메틸, 3-프로폭시프로피온산 에틸, 3-프로폭시프로피온산 프로필, 3-프로폭시프로피온산 부틸, 3-부톡시프로피온산메틸, 3-부톡시프로피온산 에틸, 3-부톡시프로피온산 프로필, 3-부톡시프로피온산 부틸 등의 에테르류, 또는 이들의 조합 등을 들 수 있다.Examples of the solvent used for the preparation of the copolymer include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Methyl vertical solvent acetate, ethyl vertical solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monoethyl ether, propylene glycol propyl Ether, propylene glycol butyl ether, propylene glycol methyl ethyl acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol propyl Ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, acetate Pill, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy ethyl 2-methylpropionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, Ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionic acid butyl, 2-hydroxy 3-methyl butanoate, meth Methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl methoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, prop Propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Propyl, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate propyl, 3-propoxypropionic acid propyl, 3-butyl propoxypropionate, 3-butoxypropionate, And ethers such as 3-butoxypropionate ethyl, 3-butoxypropionic acid propyl, and 3-butoxypropionate butyl, and combinations thereof.

또한, 상기 중합개시제로는 라디칼 중합 개시제를 사용할 수 있다. 상기 라디칼 중합 개시제로 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(4-메톡시 2,4-디메틸발레로니트릴), 1,1'-아조비스(시클로헥산-1-카르보니트릴)디메틸 2,2'-아조비스이소부틸레이트 등을 사용할 수 있다.In addition, a radical polymerization initiator may be used as the polymerization initiator. 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2,4 as the radical polymerization initiator -Dimethylvaleronitrile), 1,1'- azobis (cyclohexane-1-carbonitrile) dimethyl 2,2'- azobisisobutylate, etc. can be used.

상기 A) 아크릴계 공중합체는 폴리스티렌 환산 중량평균분자량(Mw)이 3,000 내지 25,000인 것이 바람직하고, 5,000 내지 15,000인 것이 보다 바람직하다. 3,000 미만인 경우에는 현상성 및 잔막률이 저하되거나, 패턴 형성, 내열성, 접착력 등이 저하되는 문제점이 있어 바람직하지 못하고, 25,000을 초과하는 경우에는 감도의 저하와 패턴 형상 불량, 투과도 감소 등의 문제점이 있어 바람직하지 못하다.It is preferable that the weight average molecular weight (Mw) of polystyrene conversion of the said A) acrylic copolymer is 3,000-25,000, and it is more preferable that it is 5,000-15,000. If it is less than 3,000, there is a problem in that developability and residual film rate are lowered, or pattern formation, heat resistance, adhesive strength, etc. are deteriorated. It is not desirable.

(B) 퀴논디아지드 화합물(B) quinonediazide compound

상기 퀴논디아지드 화합물은 감광성 화합물로서, 나프토퀴논디아지드 술폰산 할로겐 화합물과 페놀계 화합물을 약염기 하에 반응시켜 제조할 수 있다. The quinonediazide compound is a photosensitive compound, and may be prepared by reacting a naphthoquinone diazide sulfonic acid halogen compound and a phenolic compound under a weak base.

상기 퀴논디아지드 화합물의 합성시 에스테르화도는 45 내지 90%인 것이 바람직하다. 에스테르화도가 45% 미만인 경우에는 잔막률이 급격히 저하되고 감도 이상이 발생할 우려가 있어 바람직하지 않고, 90%를 초과하는 경우에는 보관 안정성이 저하될 우려가 있어 바람직하지 않다.In the synthesis of the quinonediazide compound, the degree of esterification is preferably 45 to 90%. If the degree of esterification is less than 45%, the residual film ratio may be drastically lowered and sensitivity abnormality may occur. If the esterification degree is higher than 90%, the storage stability may decrease, which is not preferable.

상기 퀴논디아지드 화합물은 예를 들면, 1,2-퀴논디아지드 화합물, 1,4-퀴논디아지드 화합물 등이 있으나, 반드시 이에 한정되지는 않는다.The quinonediazide compound includes, for example, 1,2-quinonediazide compound, 1,4-quinonediazide compound, and the like, but is not necessarily limited thereto.

바람직하게는 1,2-퀴논디아지드 화합물을 사용하는 것이 좋고, 1,2-퀴논디아지드 화합물중에서도 1,2-퀴논디아지드 4-술폰산에스테르, 1,2-퀴논디아지드 5-술폰산에스테르, 1,2-퀴논디아지드 6-술폰산에스테르, 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 사용하는 것이 보다 바람직하다.Preferably, a 1, 2- quinone diazide compound is used, and a 1, 2- quinone diazide 4- sulfonic acid ester, a 1, 2- quinone diazide 5- sulfonic acid ester among the 1, 2- quinone diazide compounds, It is more preferable to use those selected from the group consisting of 1,2-quinonediazide 6-sulfonic acid ester, and mixtures thereof.

상기 퀴논디아지드 화합물은 상기 (A)의 아크릴계 공중합체 100 중량부에 대하여 5 내지 80 중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 5 내지 50중량부, 보다 더 바람직하게는 10 내지 40 중량부로 포함될 수 있다. 그 함량이 5 중량부 미만인 경우에는 노광부와 비노광부의 용해도의 차가 작아져 패턴 형성이 곤란하고, 80 중량부를 초과하는 경우에는 단시간의 빛이 조사될 때 미반응의 퀴논디아지드 화합물이 다량 잔존하여 알칼리 수용액에의 용해도가 지나치게 낮아지기 때문에 현상이 어렵다는 문제점이 있다.The quinonediazide compound is preferably included in an amount of 5 to 80 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 10 to 40 parts by weight, based on 100 parts by weight of the acrylic copolymer of (A). May be included. If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed parts becomes small, and if it exceeds 80 parts by weight, a large amount of unreacted quinonediazide compound remains when light is irradiated for a short time. There is a problem that development is difficult because the solubility in an aqueous alkali solution is too low.

(C) p-톨루엔 설폰산/피리딘 염(C) p-toluene sulfonic acid / pyridine salt

상기 p-톨루엔 설폰산/피리딘 염(p-toluene sulfonic acid/pyridine salts:PPTS)은 종래의 에폭시기 함유 불포화 화합물을 대체하는 것으로서, 내열성을 유지하면서도, 저감도화 및 잔막률 감소를 방지하는 역할을 한다. The p-toluene sulfonic acid / pyridine salts (PPTS) is to replace the conventional epoxy group-containing unsaturated compound, while maintaining the heat resistance, it serves to prevent the reduction of the reduction and residual film rate .

상기 p-톨루엔 설폰산/피리딘 염은, 노광시 자체적으로 산을 발생시켜 아크릴계 수지의 용해도를 촉진시키는 역할과, 저분자량으로 존재하면서 스톤웰(stone well) 효과로 용해성을 증진시키는 효과 및 감도를 상승시키는 고감도화 효과를 나타낸다. The p-toluene sulfonic acid / pyridine salt has a role of promoting acid solubility of the acrylic resin by generating an acid itself upon exposure, and having a low molecular weight effect to enhance solubility with a stone well effect. It shows an increasing sensitivity.

상기 p-톨루엔 설폰산/피리딘 염은 고감도를 이룸에도 불구하고 잔막률을 유지시킬 수 있다. 따라서, 고분자와 저분자간의 비율에 따른 잔막률 변화(잔막률을 향상시키면 감도가 느려지는 현상)의 문제점을 해결할 수 있다.The p-toluene sulfonic acid / pyridine salt can maintain the residual film rate despite high sensitivity. Therefore, it is possible to solve the problem of the residual film rate change according to the ratio between the polymer and the low molecule (a phenomenon in which the sensitivity becomes slow when the residual film rate is improved).

상기 p-톨루엔 설폰산/피리딘 염은 (A)의 아크릴계 공중합체 100 중량부에 대하여, 0.1 내지 30 중량부로 사용될 수 있다. 0.1 중량부 미만인 경우에는 고감도 및 잔막률 유지가 불가능한 문제점이 있으며, 30 중량부를 초과하여 사용하더라도 잔막률 및 감도는 더 이상 상승하지 않는다.The p-toluene sulfonic acid / pyridine salt may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer of (A). If it is less than 0.1 parts by weight, there is a problem that it is impossible to maintain high sensitivity and residual film rate, and even when used in excess of 30 parts by weight, the residual film rate and sensitivity do not increase any more.

(D) 용매(D) solvent

상기 용매로는 메탄올, 에탄올 등의 알코올류; 테트라히드로퓨란 등의 에테르류; 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르 아세테이트류; 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜디메틸에테르 등의 디에틸렌글리콜류; 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필레글리콜부틸에테르 등의 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜부틸에테르아세테이트 등의 프로필렌글리콜알킬에테르아세테이트류; 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜부틸에테르프로피오네이트 등의 프로필렌글리콜알킬에테르아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 메틸에틸케톤, 시클로헥사논, 4-히드록시 4-메틸 2-펜타논 등의 케톤류; 초산메틸, 초산에틸, 초산프로필, 초산부틸, 2-히드록시 프로피온산 에틸, 2-히드록시 2-메틸프로피온산 메틸, 2-히드록시 2-메틸프로피온산 에틸, 히드록시 초산 메틸, 히드록시초산에틸, 히드록시초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시프로피온산 메틸, 3-히드록시프로피온산에틸, 3-히드록시프로피온산프로필, 3-히드록시프로피온산 부틸, 2-히드록시 3-메틸부탄산 메틸, 메톡시초산 메틸, 메톡시초산 에틸, 메톡시초산 프로필, 메녹시초산 부틸, 에톡시 초산 메틸, 에톡시 초산 에틸, 에톡시 초산 프로필, 에톡시 초산 부틸, 프로폭시초산 메틸. 프로폭시초산 에틸, 프로폭시초산 프로필, 프로폭시초산 부틸, 부톡시초산메틸, 부톡시초산 에틸, 부톡시초산 프로필, 부톡시초산 부틸, 2-메톡시프로피온산 메틸, 2-메톡시프로피온산 에틸, 2-메톡시프로피온산 프로필, 2-메톡시프로피온산 부틸, 2-에톡시프로피온산 메틸2-에톡시프로피온산 에틸, 2-에톡시프로피온산 프로필, 2-에톡시프로피온산 부틸, 2-부톡시프로피온산 메틸, 2-부톡시프로피온산 에틸, 2-부톡시프로피온산 프로필, 2-부톡시프로피온산 부틸, 3-메톡시프로피온산 메틸, 3-메톡시프로피온산 에틸, 3-메톡시프로피온산 프로필, 3-메톡시프로피온산 부틸, 3-에톡시프로피온산 메틸, 3-에톡시프로피온산 에틸, 3-에톡시프로피온산 프로필, 3-에톡시프로피온산 부틸, 3-프로폭시프로피온산 메틸, 3-프로폭시프로피온산 에틸, 3-프로폭시프로피온산 프로필, 3-프로폭시프로피온산 부틸, 3-부톡시프로피온산 메틸, 3-부톡시프로피온산 에틸, 3-부톡시프로피온산 프로필, 3-부톡시프로피온산 부틸 등의 에스테르류, 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 사용할 수 있다. 이 중에서도, 용해성, 각 성분과의 반응성, 및 도포막 형성이 용이한 글리콜에테르류, 에틸렌글리콜알킬에테르아세테이트류, 디에틸렌글리콜류, 및 이들의 혼합물로 이루어진 군에서 선택되는 것이 보다 바람직하다.As said solvent, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propyl glycol glycol ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, 2-hydroxy ethyl 2-methylpropionate, methyl hydroxy acetate, ethyl hydroxyacetate, hydroxy Butyl oxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3- Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate. Ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate 2-ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-part Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionic acid, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Esters such as propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and mixtures thereof Can be used. Among these, it is more preferable to select from the group which consists of solubility, reactivity with each component, and the easily formed coating film, glycol ether, ethylene glycol alkyl ether acetates, diethylene glycol, and mixtures thereof.

상기 용매는 감광성 수지 조성물내 잔부로 포함될 수 있는데, 바람직하게는 감광성 수지 조성물내 고형분 함량이 10 내지 60 중량%가 되도록 포함될 수 있으며, 보다 바람직하게는 10 내지 50중량%, 보다 더 바람직하게는 15 내지 30 중량%가 되도록 포함될 수 있다. 감광성 수지 조성물내 고형분 함량이 10 중량% 미만일 경우에는 코팅 평탄성의 저하 및 코팅 두께가 얇아질 우려가 있고, 60 중량%를 초과하면 코팅장비에 무리를 줄 수 있다는 문제점이 있다.The solvent may be included as the remainder in the photosensitive resin composition, preferably may be included so that the solids content in the photosensitive resin composition is 10 to 60% by weight, more preferably 10 to 50% by weight, even more preferably 15 To 30% by weight. When the solid content in the photosensitive resin composition is less than 10% by weight, there is a concern that the coating flatness may decrease and the thickness of the coating may become thin.

(E) 기타 첨가제(E) other additives

상기 절연막 형성용 감광성 수지 조성물은 (A) 내지 (D) 성분 외에, 필요에 따라 에폭시 수지, 접착제, 아크릴화합물, 또는 계면활성제를 더욱 포함할 수 있다. The photosensitive resin composition for forming an insulating film may further include an epoxy resin, an adhesive, an acrylic compound, or a surfactant as needed, in addition to the components (A) to (D).

상기 에폭시 수지는 절연막 형성용 감광성 수지 조성물로부터 얻어지는 패턴의 내열성 및 감도 등을 향상시키기 위해 첨가될 수 있다. 상기 에폭시 수지로는 비스페놀 A형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 환상지방족 에폭시 수지, 글리시딜에스테르형 에폭시 수지, 글리시딜아민형 에폭시 수지, 복소환식 에폭시 수지, (A)의 아크릴계 공중합체와 다른 글리시딜 메타아크릴레이트의 공중합체 또는 중합체, 또는 이들의 조합 등이 있다.The epoxy resin may be added to improve the heat resistance and sensitivity of the pattern obtained from the photosensitive resin composition for forming an insulating film. Examples of the epoxy resins include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and heterocyclic epoxy resins. And copolymers or polymers of acrylic copolymers of (A) with other glycidyl methacrylates, or combinations thereof.

상기 에폭시 수지는 (A)의 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 35 중량부로 사용되는 것이 바람직하다. 35 중량부를 초과하는 경우에는 알칼리 가용성 수지에 대한 상용성이 떨어져 충분한 도포성능을 얻을 수 없는 문제점이 있 어 바람직하지 못하다.It is preferable that the said epoxy resin is used in 0.1-35 weight part with respect to 100 weight part of acrylic copolymers of (A). When it exceeds 35 parts by weight, there is a problem in that the compatibility with alkali-soluble resin is poor, and sufficient coating performance cannot be obtained.

상기 접착제는 기판과의 접착성을 향상시키기 위해 첨가될 수 있다. 상기 접착제로는 카르복실기, 메타크릴기, 이소시아네이트기, 에폭시기 등의 반응성 치환기를 갖는 실란커플링제 등을 들 수 있으며, 구체적 예로는 γ-메타아크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-3,4-에폭시 시클로 헥실 에틸트리메톡시실란 등이 있다. 상기 접착제는 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 30 중량부로 사용되는 것이 바람직하다.The adhesive may be added to improve the adhesion with the substrate. Examples of the adhesive include silane coupling agents having reactive substituents such as carboxyl groups, methacryl groups, isocyanate groups, and epoxy groups, and specific examples include γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and vinyl. Trimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-3,4-epoxy cyclohexyl ethyltrimethoxysilane and the like. The adhesive is preferably used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.

상기 아크릴화합물은 절연막 형성용 감광성 수지 조성물로부터 얻어지는 패턴의 투과율, 내열성, 또는 감도 등을 향상시키기 위해 첨가될 수 있다. 상기 아크릴화합물로는 하기 화학식 1로 표현되는 화합물이 있으며, 이에 한정되는 것은 아니다.The acrylic compound may be added to improve the transmittance, heat resistance, or sensitivity of the pattern obtained from the photosensitive resin composition for forming an insulating film. The acrylic compound includes a compound represented by the following Chemical Formula 1, but is not limited thereto.

[화학식 1][Formula 1]

Figure 112007089836746-pat00001
Figure 112007089836746-pat00001

상기 화학식 1에서, R은 수소, C1 내지 C5의 알킬기, 알콕시기, 및 알카노일기로 이루어진 군에서 선택되는 것이고, 1<a<6이고, a+b=6 이다.In Formula 1, R is selected from hydrogen, an alkyl group of C 1 to C 5 , an alkoxy group, and an alkanoyl group, 1 <a <6, and a + b = 6.

상기 아크릴화합물은 아크릴계 공중합체 100 중량부에 대하여, 0.1 내지 35 중량부로 사용될 수 있으며, 바람직하게는 0.1 내지 20 중량부로 사용될 수 있다. 상기 범위에서는 감도, 내열성 UV 투과율을 향상시킬 수 있어 바람직하다. The acrylic compound may be used in an amount of 0.1 to 35 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the acrylic copolymer. In the said range, since a sensitivity and heat resistant UV transmittance can be improved, it is preferable.

상기 계면활성제는 절연막 형성용 감광성 수지 조성물의 도포성이나 현상성을 향상시키기 위해 첨가될 수 있다. 상기 계면활성제로는 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르, F171, F172, F173(대일본잉크사), FC430, FC431(스미또모트리엠사), KP341(신월화학공업사) 등이 있다. 상기 계면 활성제는 (A)의 아크릴계 공중합체 100 중량부에 대하여 0.0001 내지 2 중량부로 사용되는 것이 바람직하다. 상기 범위에서는 감광성 수지 조성물의 도포성이나 공정진행시의 얼룩특성에 대한 장점이 있어 바람직하다.The surfactant may be added to improve the coatability or developability of the photosensitive resin composition for forming an insulating film. Examples of the surfactants include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (India Nippon Inks Co., Ltd.), FC430, FC431 (Sumitomo Trim Co., Ltd.), KP341 (Shinwol Chemical Co., Ltd.), and the like. . It is preferable that the said surfactant is used 0.0001-2 weight part with respect to 100 weight part of acrylic copolymers of (A). In the above range, there is an advantage of the coating property of the photosensitive resin composition and the staining property at the time of the process progress, and thus it is preferable.

상기한 구성을 갖는 절연막 형성용 감광성 수지 조성물은 0.1 내지 0.2㎛의 밀리포아필터 등으로 여과한 뒤 사용하는 것이 바람직하다. It is preferable to use the photosensitive resin composition for insulating film formation which has the above-mentioned structure after filtering by the Millipore filter of 0.1-0.2 micrometer.

본 발명의 다른 일 구현예에 따르면, 상기 절연막 형성용 감광성 수지 조성물로 제조되는 절연막을 포함하는 액정 디스플레이 장치를 제공한다.According to another embodiment of the present invention, a liquid crystal display device including an insulating film made of the photosensitive resin composition for forming an insulating film is provided.

본 발명의 또 다른 일 구현예에 따르면, 상기 절연막 형성용 감광성 수지 조성물을 기판에 도포한 후, 노광 형상하여 절연막 패턴을 형성하는 공정을 포함하는 액정 디스플레이 장치의 제조 방법을 제공한다.According to another embodiment of the present invention, there is provided a method of manufacturing a liquid crystal display device comprising the step of applying the photosensitive resin composition for forming an insulating film to a substrate, and then forming an insulating film pattern by exposing.

상기 액정 디스플레이 장치의 절연막은 하기와 같은 방법에 의해 제조될 수 있다.The insulating film of the liquid crystal display device may be manufactured by the following method.

상기 제조된 감광성 수지 조성물을 스프레이법, 롤코터법, 회전도포법 등으 로 기판 표면에 도포한 후, 프리 베이크(pre-bake)로 용매를 제거하여 도포막을 형성한다. 상기 프리 베이크는 70 내지 120℃에서 1 내지 5 분간 실시하는 것이 바람직하다. 이 후, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 원자외선, 전자선, 엑스선 등을 상기 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다. 이때, 사용되는 현상액으로는 알칼리 수용액이 사용될 수 있으며, 구체적으로는 수산화 나트륨, 수산화 칼륨, 탄산 나트륨 등의 무기 알칼리류; 에틸아민, n-프로필아민 등의 1급 아민류; 디에틸아민, n-프로필아민 등의 2급 아민류; 트리메틸아민, 메틸디에틸아민, 디메틸에틸아민, 트리에틸아민 등의 3급 아민류; 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올아민 등의 알콜아민류; 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액; 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 사용할 수 있다. 상기 현상액의 알칼리성 화합물의 농도는 0.1 내지 10%인 것이 바람직하다. 또한, 상기 용매와 함께, 메탄올 에탄올 등과 같은 수용성 유기 용매 또는 계면 활성제를 적정량 첨가하여 사용할 수도 있다. 또한, 상기와 같은 현상액으로 현상한 후 초순수로 30 내지 140초 동안 세정하여, 불필요한 부분을 제거하고 건조하여 패턴을 형성할 수 있으며, 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 110 내지 250℃에서 30 내지 120분간 가열하여 최종 패턴을 얻을 수 있다. After applying the prepared photosensitive resin composition to the surface of the substrate by a spray method, a roll coater method, a rotary coating method, etc., the solvent is removed by pre-baking to form a coating film. It is preferable to perform the said prebaking for 1 to 5 minutes at 70-120 degreeC. Thereafter, visible light, ultraviolet rays, far ultraviolet rays, electron beams, far-ultraviolet rays, electron beams, X-rays, and the like are irradiated to the formed coating film according to a pattern prepared in advance, and developed with a developer to remove an unnecessary portion to form a predetermined pattern. At this time, an aqueous alkali solution may be used as the developing solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; And mixtures thereof. It is preferable that the density | concentration of the alkaline compound of the said developing solution is 0.1 to 10%. In addition, an appropriate amount of a water-soluble organic solvent or a surfactant such as methanol ethanol may be added together with the solvent. In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 140 seconds to remove unnecessary parts and dried to form a pattern, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is The final pattern may be obtained by heating at 110 to 250 ° C. for 30 to 120 minutes by a heating apparatus.

이하 실시예를 들어 본 발명에 대해서 더욱 상세하게 설명할 것이나, 하기의 실시예는 본 발명의 바람직한 실시예일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

<합성예 1>: 아크릴계 공중합체의 제조Synthesis Example 1 Preparation of Acrylic Copolymer

냉각관과 교반기를 구비한 플라스크에, 2,2'-아조비스(2,4-디메틸발레로니트릴) 10 g, 프로필렌글리콜 모노메틸에테르아세테이트 200 g, 메타크릴산 20 g, 스티렌 25 g, 메타아크릴산 글리시딜 10 g, 이소보닐 아크릴레이트 45 g을 넣고, 질소로 치환한 후 서서히 교반을 시작하였다. 이후, 반응 용액을 60℃ 까지 상승시키고 이 온도를 5시간 동안 유지하여 아크릴계 공중합체를 포함하는 중합체를 얻었다. 얻어진 중합체 용액의 고형분 농도는 35 중량%이었고, 중합체에 대하여 GPC(gel permeation chromatography)를 사용하여 측정한 폴리스티렌 환산 중량평균분자량은 10,500이었다.In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 25 g of styrene, meta 10 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including an acrylic copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 10,500.

<합성예 2>: 아크릴계 공중합체의 제조Synthesis Example 2 Preparation of Acrylic Copolymer

냉각관과 교반기를 구비한 플라스크에, 2,2'-아조비스(2,4-디메틸발레로니트릴) 10 g, 프로필렌글리콜 모노메틸에테르아세테이트 200 g, 메타크릴산 20 g, 스티렌 15 g, 메타아크릴산 글리시딜 30 g, 이소보닐 아크릴레이트 45 g을 넣고, 질소로 치환한 후 서서히 교반을 시작하였다. 이 후, 반응 용액을 60℃ 까지 상승시키고, 이 온도를 5시간 동안 유지하여 공중합체를 포함하는 중합체를 얻었다. 얻어진 중합체 용액의 고형분 농도는 35 중량%이었고, 중합체에 대하여 GPC(gel permeation chromatography)를 사용하여 측정한 폴리스티렌 환산 중량평균분자량은 9,500이었다. In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 15 g of styrene, meta 30 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 9,500.

<합성예 3>: 아크릴계 공중합체의 제조Synthesis Example 3 Preparation of Acrylic Copolymer

냉각관과 교반기를 구비한 플라스크에, 2,2'-아조비스(2,4-디메틸발레로니트릴) 10 g, 프로필렌글리콜 모노메틸에테르아세테이트 200 g, 메타크릴산 20 g, 스티렌 30 g, 메타아크릴산 글리시딜 5 g, 이소보닐 아크릴레이트 45 g을 넣고, 질소로 치환한 후 서서히 교반을 시작하였다. 이후, 반응 용액을 60℃ 까지 상승시키고, 이 온도를 5시간 동안 유지하여 공중합체를 포함하는 중합체를 얻었다. 얻어진 중합체 용액의 고형분 농도는 35 중량%이었고, 중합체에 대하여 GPC(gel permeation chromatography)를 사용하여 측정한 폴리스티렌 환산 중량평균분자량은 9,800이었다. In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 30 g of styrene, meta 5 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 9,800.

<합성예 4>: 아크릴계 공중합체의 제조Synthesis Example 4 Preparation of Acrylic Copolymer

냉각관과 교반기를 구비한 플라스크에, 2,2'-아조비스(2,4-디메틸발레로니트릴) 10 g, 프로필렌글리콜 모노메틸에테르아세테이트 200 g, 메타크릴산 15 g, 스티렌 30 g, 메타아크릴산 글리시딜 10 g, 이소보닐 아크릴레이트 45 g를 넣고, 질소로 치환한 후 서서히 교반을 시작하였다. 이 후, 반응 용액을 60℃ 까지 상승시키고, 이 온도를 5시간 동안 유지하여 공중합체를 포함하는 중합체를 얻었다. 얻어진 중합체 용액의 고형분 농도는 35 중량%이었고, 중합체에 대하여 GPC(gel permeation chromatography)를 사용하여 측정한 폴리스티렌 환산 중량평균분자량은 10,300이었다. In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 15 g of methacrylic acid, 30 g of styrene, meta 10 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 10,300.

<합성예 5>: 1,2-퀴논디아지드 화합물의 제조Synthesis Example 5 Preparation of 1,2-quinonediazide Compound

4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1mol 및 1,2-나프토퀴논디아지드-5-술폰산(클로라이드) 2mol을 축합반응시켜 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르를 제조하였다. 1 mol of 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid (chloride ) 2 mol condensation reaction to 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol 1,2-naphthoquinonediazide-5 -Sulfonic acid ester was prepared.

<실시예 1>: 절연막 형성용 감광성 수지 조성물의 제조<Example 1>: Preparation of the photosensitive resin composition for insulating film formation

합성예 1에서 제조된 아크릴계 공중합체 혼합물 용액 100 중량부, 합성예 5에서 제조된 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르 20 중량부, 및 p-톨루엔 설폰산/피리딘 염 5 중량부를 혼합하고, 고형분의 농도가 30 중량%가 되도록 디에틸렌글리콜디메틸에테르에 용해시킨 후 0.2㎛의 밀리포아필터로 여과하여 절연막 형성용 감광성 수지 조성물을 제조하였다.100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 1, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 5 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl was added so that the concentration of solid content was 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

<실시예 2>: 절연막 형성용 감광성 수지 조성물의 제조<Example 2>: Preparation of the photosensitive resin composition for insulating film formation

합성예 2에서 제조된 아크릴계 공중합체 혼합물 용액 100 중량부, 합성예 5에서 제조된 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르 20 중량부, 및 p-톨루엔 설폰산/피리딘 염 2.5 중량부를 혼합하고, 고형분의 농도가 30 중량%가 되도록 디에틸렌글리콜디메틸에테르에 용해시킨 후 0.2㎛의 밀리포아필터로 여과하여 절연막 형성용 감광성 수지 조성물을 제조하였다.100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 2, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester, and 2.5 parts by weight of p-toluene sulfonic acid / pyridine salt, and diethylene glycol dimethyl so that the concentration of solid content is 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

<실시예 3>: 절연막 형성용 감광성 수지 조성물의 제조<Example 3>: Preparation of the photosensitive resin composition for insulating film formation

합성예 3에서 제조된 아크릴계 공중합체 혼합물 용액 100 중량부, 합성예 5에서 제조된 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르 20 중량부, 및 p-톨루엔 설폰산/피리딘 염 10 중량부를 혼합하고, 고형분의 농도가 30 중량부가 되도록 디에틸렌글리콜디메틸에테르에 용해시킨 후 0.2㎛의 밀리포아필터로 여과하여 절연막 형성용 감광성 수지 조성물을 제조하였다.100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 3, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 10 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl ether was added so that the concentration of solid content was 30 parts by weight. After melt | dissolving in, it filtered by the 0.2 micrometer millipore filter and prepared the photosensitive resin composition for insulating film formation.

<실시예 4>: 절연막 형성용 감광성 수지 조성물의 제조<Example 4>: Preparation of the photosensitive resin composition for insulating film formation

합성예 4에서 제조된 아크릴계 공중합체 혼합물 용액 100 중량부, 합성예 5에서 제조된 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르 20 중량부, 및 p-톨루엔 설폰산/피리딘 염 5 중량부를 혼합하고, 고형분의 농도가 30 중량%가 되도록 디에틸렌글리콜디메틸에테르에 용해시킨 후 0.2㎛의 밀리포아필터로 여과하여 절연막 형성용 감광성 수지 조성물을 제조하였다.100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 4, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 5 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl was added so that the concentration of solid content was 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

<비교예 1>: 절연막 형성용 감광성 수지 조성물의 제조Comparative Example 1 Preparation of Photosensitive Resin Composition for Insulating Film Formation

합성예 1에서 제조된 아크릴계 공중합체 혼합물 용액 100 중량부, 합성예 5에서 제조된 4,4'-(1-(4-(1-(4-히드록시페닐)-1-메틸에틸)페닐)에틸리덴)비스페놀 1,2-나프토퀴논디아지드-5-술폰산에스테르 20 중량부를 혼합하고, 고형분의 농도가 30 중량%가 되도록 디에틸렌글리콜디메틸에테르에 용해시킨 후 0.2㎛의 밀리포아필터로 여과하여 절연막 형성용 감광성 수지 조성물을 제조하였다.100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 1, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester was mixed, dissolved in diethylene glycol dimethyl ether so that the concentration of solid content was 30% by weight, and filtered through a 0.2 μm Millipore filter. Thus, the photosensitive resin composition for insulating film formation was produced.

감도, 잔막률, 해상도, 내열성, 및 저장안정성 측정Measurement of sensitivity, residual film rate, resolution, heat resistance, and storage stability

상기 실시예 1 내지 4 및 비교예 1에서 제조된 절연막 형성용 감광성 수지 조성물에 대하여, 감도, 잔막률, 해상도, 내열성, 및 저장안정성을 측정하기 위하여, 다음과 같은 방법으로 패턴막을 제조하였다. With respect to the photosensitive resin composition for forming an insulating film prepared in Examples 1 to 4 and Comparative Example 1, a pattern film was prepared by the following method in order to measure sensitivity, residual film ratio, resolution, heat resistance, and storage stability.

패턴막의 제조Production of pattern film

글래스(glass) 기판상에 스핀코터(spin coater)를 사용하여 감광성 수지 조성물을 도포한 뒤, 90℃로 2 분간 핫플레이트(hot-plate)상에서 프리 베이크하여 막을 형성하였다. 상기에서 얻어진 막에, 소정 패턴 마스크를 사용하여 365nm에서의 강도가 15.0mW/cm3인 자외선을 15초간 조사하였다. 이후, 0.38%의 테트라메틸 암모늄히드록시드 수용액으로 25℃로 130초 동안 현상한 후, 초순수로 2분간 세정하였다. 이후, 상기에서 형성된 패턴에 365nm에서의 강도가 15.0mW/cm3인 자외선을 40초간 조사한 뒤, 오븐 속에서 220℃로 60분간 가열하여 경화시켜 패턴막을 얻었다.After the photosensitive resin composition was applied on a glass substrate using a spin coater, a film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. The film obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15.0 mW / cm <3> for 15 second using the predetermined | prescribed pattern mask. Thereafter, the solution was developed at 25 ° C. for 130 seconds with 0.38% aqueous tetramethyl ammonium hydroxide solution, and then washed with ultrapure water for 2 minutes. Thereafter, the pattern formed above was irradiated with ultraviolet light having an intensity of 15.0 mW / cm 3 at 365 nm for 40 seconds, and then heated to 220 ° C. for 60 minutes in an oven to obtain a pattern film.

1) 감도: 패턴이 형성되는 최소 노광량으로 감도를 측정하였다.1) Sensitivity: The sensitivity was measured at the minimum exposure amount at which the pattern is formed.

2) 잔막률: 글래스(glass) 기판상에 감광성 수지 조성물을 스핀 코터를 사용하여 도포하고, 프리 베이크(pre-bake)한 후의 막의 두께와 포스트 베이크(post-bake)를 통해 용매를 제거힌 후 형성된 막의 두께를 측정하고, 프리 베이크 후의 막의 두께에 대한 용매 제거 후 막의 두께 비를 계산하여 잔막률(%)을 구하였다.2) Residual film rate: After the photosensitive resin composition is coated on a glass substrate by using a spin coater, the solvent is removed by pre-baking the thickness of the film and post-bake. The thickness of the formed film was measured, and the residual film ratio (%) was calculated by calculating the thickness ratio of the film after solvent removal to the thickness of the film after prebaking.

3) 해상도: 상기 패턴막에 대하여, 형성된 최소 크기를 기준으로 하였다.3) Resolution: Based on the minimum size formed for the patterned film.

4) 내열성: 상기 패턴막에 대하여, 패턴의 상, 하, 및 좌, 우의 폭을 측정하여 각이 5 내지 10°인 경우는 ○, 10°이상인 경우는 △, 0 내지 5°인 경우는 ×로 표시하였다. 4) Heat resistance: With respect to the pattern film, the widths of the upper, lower, left and right sides of the pattern were measured, and the angle was 5 ° to 10 °, △, 10 ° or more, △, and 0 to 5 °. Marked as.

5) 저장안정성 : 23℃ 및 40%의 습도를 유지하는 크린룸에 패턴막을 3 주간 1일 단위로 방치시킨 후, 감도(mJ/cm2) 및 잔막률(%) 변화를 체크하였다. 이때, 3 주간의 변화율이 10% 미만인 경우는 ○, 10 내지 20%인 경우는 △, 20%를 넘는 경우는 ×로 표시하였다.5) Storage stability: After leaving the pattern film in a clean room maintained at 23 ° C. and 40% humidity for 3 weeks, the change of sensitivity (mJ / cm 2 ) and residual film rate (%) was checked. At this time, when the change rate of 3 weeks is less than 10%, (circle), when 10 to 20%, and when more than 20% is indicated by x.

[표 1]TABLE 1

구분division 감도 (mJ/cm2) Sensitivity (mJ / cm 2 ) 잔막률 (%)Residual Rate (%) 해상도resolution 내열성Heat resistance 저장안정성 Storage stability 실시예 1Example 1 185185 9494 3㎛3㎛ 실시예 2Example 2 215215 9393 3㎛3㎛ 실시예 3Example 3 150150 9292 3㎛3㎛ 실시예 4Example 4 170170 9191 3㎛3㎛ 비교예 1Comparative Example 1 250250 9090 4㎛4㎛ ××

상기 표 1을 살펴보면, 본 발명의 절연막 형성용 감광성 수지 조성물로부터 제조된 패턴은 저장안정성, 내열성, 및 해상도가 비교예 1에 비하여 월등히 우수하였으며, 특히 감도 대비 우수한 잔막률을 확보할 수 있음을 확인할 수 있었다.Looking at the Table 1, the pattern prepared from the photosensitive resin composition for forming an insulating film of the present invention is excellent in storage stability, heat resistance, and resolution compared to Comparative Example 1, it can be confirmed that particularly excellent residual film ratio compared to the sensitivity Could.

Claims (11)

(A)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물, ⅱ) 에폭시기 함유 불포화 화합물 및 ⅲ) 올레핀계 불포화 화합물을 불포화 단량체로 하는 아크릴계 공중합체; (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof, ii) an epoxy copolymer containing an epoxy group-containing unsaturated compound and iii) an olefinically unsaturated compound as an unsaturated monomer; (B) 퀴논디아지드 화합물; (B) quinonediazide compounds; (C) p-톨루엔 설폰산/피리딘 염; 및 (C) p-toluene sulfonic acid / pyridine salt; And (D) 용매(D) solvent 를 포함하는 절연막 형성용 감광성 수지 조성물.Photosensitive resin composition for insulating film formation containing a. 제1항에 있어서,The method of claim 1, 상기 조성물은, (A) 아크릴계 공중합체 100 중량부에 대하여, The composition is based on 100 parts by weight of the (A) acrylic copolymer, (B) 퀴논디아지드 화합물을 5 내지 80 중량부로 포함하고, (B) 5 to 80 parts by weight of a quinonediazide compound, (C) p-톨루엔 설폰산/피리딘 염을 0.1 내지 30 중량부로 포함하는 (C) 0.1 to 30 parts by weight of p-toluene sulfonic acid / pyridine salt 것인 절연막 형성용 감광성 수지 조성물.The photosensitive resin composition for insulating film formation. 제2항에 있어서,The method of claim 2, 상기 조성물은 고형분의 함량이 10 내지 60 중량%인 것인 절연막 형성용 감 광성 수지 조성물.The composition is a photosensitive resin composition for forming an insulating film, the solid content is 10 to 60% by weight. 제1항에 있어서, The method of claim 1, 상기 (A) 아크릴계 공중합체는 The (A) acrylic copolymer is ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로 유도되는 구성단위 10 내지 60 중량%, ⅱ) 에폭시기 함유 불포화 화합물로부터 유도되는 구성단위 5 내지 40 중량%, 및 ⅲ) 올레핀계 불포화 화합물로부터 유도되는 구성단위 20 내지 85 중량%를 포함하는 공중합체인 절연막 형성용 감광성 수지 조성물.Iii) from 10 to 60% by weight of structural units derived from unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof, ii) from 5 to 40% by weight of structural units derived from epoxy-containing unsaturated compounds, and iii) from olefinically unsaturated compounds. The photosensitive resin composition for insulating film formation which is a copolymer containing 20 to 85 weight% of derived structural units. 제1항에 있어서,The method of claim 1, 상기 불포화 카르본산 및 불포화 카르본산 무수물은, 아크릴산, 메타크릴산 , 말레인산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산, 이들 산의 무수물, 및 이들의 조합으로 이루어진 군에서 선택되는 것인 절연막 형성용 감광성 수지 조성물.The unsaturated carboxylic acid and unsaturated carboxylic anhydride are formed of an insulating film that is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these acids, and combinations thereof. Photosensitive resin composition for. 제1항에 있어서,The method of claim 1, 상기 에폭시기 함유 불포화 화합물은 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸 아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸 아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타클리산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸 아크릴산-6,7-에폭시헵틸, o-비닐벤질 글리시딜 에테르, m-비닐벤질 글리시딜 에테르, p-비닐벤질 글리시딜 에테르, 및 이들의 조합으로 이루어진 군에서 선택되는 것인 절연막 형성용 감광성 수지 조성물.The epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, glycidyl acrylate-β- Methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3 , 4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl A photosensitive resin composition for forming an insulating film, which is selected from the group consisting of benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and combinations thereof. 제1항에 있어서,The method of claim 1, 상기 올레핀계 불포화 화합물은 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 시클로헥실 메타크릴레이트, 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시에틸아크릴레이트, 스티렌, α-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐톨루엔, p-메톡시 스티렌, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔, 및 이들의 조합으로 이루어진 군에서 선택되는 것인 절연막 형성용 감광성 수지 조성물.The olefinically unsaturated compound is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate Latex, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-a Monomethyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, phenyl methacryl Latex, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate Rate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and these The photosensitive resin composition for insulating film formation is selected from the group consisting of. 제1항에 있어서, The method of claim 1, 상기 (A) 아크릴계 공중합체는 폴리스티렌 환산 중량평균분자량(Mw)이 3,000 내지 25,000인 것인 절연막 형성용 감광성 수지 조성물.Said (A) acrylic copolymer has a polystyrene reduced weight average molecular weight (Mw) of 3,000-25,000, The photosensitive resin composition for insulating film formation. 제1항에 있어서,The method of claim 1, 상기 (B) 퀴논디아지드 화합물은 1,2-퀴논디아지드 4-술폰산에스테르, 1,2-퀴논디아지드 5-술폰산에스테르, 1,2-퀴논디아지드 6-술폰산에스테르, 및 이들의 조합으로 이루어진 군에서 선택되는 것인 절연막 형성용 감광성 수지 조성물.The (B) quinone diazide compound is 1,2-quinone diazide 4-sulfonic acid ester, 1,2-quinone diazide 5-sulfonic acid ester, 1,2-quinone diazide 6-sulfonic acid ester, and combinations thereof The photosensitive resin composition for insulating film formation chosen from the group which consists of. 제1항에 있어서,The method of claim 1, 상기 절연막 형성용 감광성 수지 조성물은 에폭시 수지, 접착제, 아크릴 화합물, 계면 활성제, 및 이들의 조합으로 이루어진 군에서 선택되는 첨가제를 더 포함하는 것인 감광성 수지 조성물.The photosensitive resin composition for forming an insulating film further comprises an additive selected from the group consisting of an epoxy resin, an adhesive, an acrylic compound, a surfactant, and a combination thereof. 제1항 내지 제10항 중 선택되는 어느 한 항에 따른 절연막 형성용 감광성 수지 조성물로 제조되는 절연막을 포함하는 액정 디스플레이 장치.A liquid crystal display device comprising an insulating film made of the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 10.
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KR20220091270A (en) 2020-12-23 2022-06-30 동우 화인켐 주식회사 Photosensitive resin composition, photocurable pattern and display device formed from the same

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CN113219690A (en) * 2020-02-05 2021-08-06 Jsr株式会社 Liquid crystal display element and method for manufacturing the same, radiation-sensitive composition, interlayer insulating film and method for manufacturing the same

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KR20220091270A (en) 2020-12-23 2022-06-30 동우 화인켐 주식회사 Photosensitive resin composition, photocurable pattern and display device formed from the same

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