KR100888780B1 - Photo resist composition for column spacer - Google Patents
Photo resist composition for column spacer Download PDFInfo
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- KR100888780B1 KR100888780B1 KR1020020079562A KR20020079562A KR100888780B1 KR 100888780 B1 KR100888780 B1 KR 100888780B1 KR 1020020079562 A KR1020020079562 A KR 1020020079562A KR 20020079562 A KR20020079562 A KR 20020079562A KR 100888780 B1 KR100888780 B1 KR 100888780B1
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08F220/52—Amides or imides
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Abstract
본 발명은 컬럼 스페이서용 광경화형 수지 조성물에 관한 것으로서, 알칼리 가용성 수지, 중합성 화합물, 실리콘계 다관능성 모노머 및 광개시제를 포함하여 내열성이 우수할 뿐만 아니라 액정 표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 평탄성, 해상성, 내용제성 및 패턴 모양이 양호한 수지 조성물을 제공한다.
The present invention relates to a photocurable resin composition for a column spacer, including an alkali-soluble resin, a polymerizable compound, a silicone-based polyfunctional monomer, and a photoinitiator, not only having excellent heat resistance, but also forming a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device. It is possible to provide a resin composition having good flatness, resolution, solvent resistance and pattern shape.
Description
본 발명은 액정 디스플레이 소자에 사용되는 컬럼 스페이서용 광경화형 수지 조성물에 관한 것으로서, 더욱 상세하게는 액정 디스플레이 소자의 컬럼 스페이서 형성시 적절할 두께로 패턴형성이 가능하고 평탄성, 해상성, 잔막률 및 패턴안정성이 우수한 광경화형 수지 조성물에 관한 것이다.The present invention relates to a photocurable resin composition for a column spacer used in a liquid crystal display device, and more particularly, to form a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device, and to have flatness, resolution, residual film ratio, and pattern stability. It is related with this excellent photocurable resin composition.
종래 액정 디스플레이의 셀 갭을 조절하는 기술로는, 2장의 기판 중간에 유리 비드, 플라스틱 비드 등의 구형 스페이서 입자를 살포하고, 이들의 크기에 의해 액정층의 두께를 조절하는 방식이 사용되어져 왔다. 그러나, 이 방법의 문제점으로 첫째, 이들 스페이서 입자는 무작위로 살포되기 때문에 유효 픽셀 내부에 상기의 스페이서가 비치거나 입사광이 산란되어 액정 패널의 콘트라스트 및 개구율을 저하시킨다. 둘째, 액정 주입시 구형의 유리 비드나 부분적으로 가교된 폴리메틸메타크릴레이트 비드의 구형 스페이서는 외부의 충격에 의해 위치가 변하게 되어 화상에 영향을 주기도 한다. 셋째로, 스페이서 입자크기가 분포를 가지므로 갭의 불균일을 야기한다. 또한 패널의 크기가 커지고 고해상도화됨에 따라 이러한 문제점은 극단적으로 보이게 된다. As a technique of adjusting the cell gap of the conventional liquid crystal display, the method of spraying spherical spacer particles, such as glass beads and plastic beads, in the middle of two board | substrates, and adjusting the thickness of a liquid crystal layer by these sizes has been used. However, as a problem with this method, firstly, since these spacer particles are randomly spread, the spacers are reflected inside the effective pixels or the incident light is scattered to lower the contrast and aperture ratio of the liquid crystal panel. Second, spherical glass beads or partially cross-linked spherical spacers of polymethyl methacrylate beads may be changed in position by external impact, thereby affecting the image. Third, because the spacer particle size has a distribution, it causes nonuniformity of the gap. In addition, as panels grow in size and become higher resolution, this problem becomes extreme.
이러한 문제점을 해결하기 위하여 스페이서를 포토리소그래피 방법으로 형성시키는 방법이 제안되었다. 이 방법은 광경화성 조성물을 기판에 도포한 후 소정의 마스크를 통하여 자외선을 조사한 후, 현상하여 노광한 부분만 스페이서로 남는 방법을 통해 컬럼 스페이서를 형성시키는 방법이다. 이 방법의 장점으로는 유효 픽셀 이외의 부분에만 스페이서 형성이 가능하다는 점, 그리고 셀갭의 조절이 도포되는 막 두께의 조절을 통해 가능하다는 점이다.
In order to solve this problem, a method of forming a spacer by a photolithography method has been proposed. This method is a method of forming a column spacer by applying a photocurable composition to a substrate, irradiating ultraviolet rays through a predetermined mask, and then developing and exposing only the exposed portions as spacers. The advantage of this method is that the spacer can be formed only in the portion other than the effective pixel, and the control of the cell gap is possible through the adjustment of the film thickness applied.
이에, 본 발명은 상기와 같은 액정 디스플레이 소자의 컬럼 스페이서를 형성하는 경우에 있어서 패턴 후 두께 균일도가 있으며 고감도이며 진상이 없는 현상성과 내용제성을 갖는 우수한 광경화형 수지 조성물을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide an excellent photocurable resin composition having a thickness uniformity after patterning, high sensitivity, no developing phase and solvent resistance when forming the column spacer of the liquid crystal display device as described above. .
상기와 같은 목적을 달성하기 위한 본 발명의 컬럼 스페이서용 광경화형 수지 조성물은 알칼리 가용성 수지 10∼70중량%, 중합성 화합물 10∼50중량%, 실리콘계 다관능성 모노머 0.1∼20중량% 및 광개시제 1∼15중량%를 포함하는 것임을 그 특징으로 한다.
The photocurable resin composition for a column spacer of the present invention for achieving the above object is 10 to 70% by weight of alkali-soluble resin, 10 to 50% by weight of a polymerizable compound, 0.1 to 20% by weight of a silicone-based multifunctional monomer and 1 to 1 photoinitiator. It is characterized by containing 15% by weight.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다. The present invention will be described in more detail as follows.
본 발명에 따른 컬럼 스페이서용 광경화형 수지 조성물은 알칼리 가용성 수지, 다관능성 모노머, 실리콘계 다관능성 모노머 및 광개시제를 포함하는 바, 이하에서 각 구성요소를 구체적으로 살핀다. The photocurable resin composition for a column spacer according to the present invention includes an alkali-soluble resin, a polyfunctional monomer, a silicone-based polyfunctional monomer, and a photoinitiator, and specifically looks for each component below.
1)알칼리 가용성 수지1) alkali soluble resin
본 발명에서 알카리 가용성 수지는 a-1)불포화 카르복시산 및/또는 불포화 카르복시산 무수물(이하, 화합물 a-1이라 함), a-2)에폭시기 함유 불포화 화합물(이하, 화합물 a-2라 함), a-3)상기 a-1) 및 a-2) 이외의 올레핀계 불포화 화합물(이하, 화합물 a-3라 함)로부터 제조된 공중합체이다.In the present invention, the alkali-soluble resin is a-1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter referred to as compound a-1), a-2) epoxy group-containing unsaturated compound (hereinafter referred to as compound a-2), a -3) copolymers prepared from olefinically unsaturated compounds (hereinafter referred to as compound a-3) other than a-1) and a-2).
화합물 a-1의 구체적인 예로서는, 아크릴산, 크로톤산, 이타콘산, 말레산, 푸마르산, 시트라콘산, 메사콘산 및 이들 디카르복시산의 무수물을 들 수 있다. 이중, 아크릴산, 메타크릴산, 무수 말레산 등이 공중합 반응성, 내열성 및 입수가 용이한 점에서 바람직하게 사용된다. 이러한 화합물 a-1은 단독 또는 조합해서 사용할 수 있다.Specific examples of the compound a-1 include acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and anhydrides of these dicarboxylic acids. Acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds a-1 can be used individually or in combination.
화합물 a-2의 구체적인 예로는, 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸 아크릴산 글리시딜, α-n-프로필 아크릴산 글리시딜, α-n-부틸 아크릴산 글리시딜, 아크릴산-3,4-에폭시 부틸, 메타크릴산-3,4-에폭시 부틸, 아크릴산-6,7-에폭시 헵틸, 메타크릴산-6,7-에폭시 헵틸, α-에틸 아크릴산-6,7-에폭시 헵틸, o-비닐 벤질 글리시딜 에테르, m-비닐 벤질 글리시딜 에테르, p-비닐 벤질 글리시딜 에테르 등이 공중합 반응성 및 얻어지는 보호막의 내열성, 경도를 높인다는 점에서 바람직하게 사용된다. 이러한 화합물 a-2는 단독으로 또는 조합해서 사용할 수 있 다. Specific examples of the compound a-2 include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy heptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds a-2 can be used alone or in combination.
한편, 화합물 a-3으로부터 유도된 구성단위를 10∼70중량%, 바람직하게는 20∼50중량% 함유하고 있다. 이 구성단위가 10중량% 미만인 경우는 알칼리 가용성 수지의 보존안전성이 저하되는 경향이 있고, 70중량%를 초과하는 경우에는 알칼리 가용성 수지의 알칼리 가용성, 내열성, 표면경도가 저하되는 경향이 있다. 화합물 a-3의 구체적인 예로는, 메틸 메타크릴레이트, 에틸 메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, t-부틸 메타크릴레이트 등의 메타크릴산 알킬 에스테르; 메틸 아크릴레이트, 이소프로필 아크릴레이트 등의 아크릴산 알킬 에스테르; 시클로헥실 메타크릴레이트, 2-메틸 시클로헥실 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, 디시클로펜테닐옥시에틸 메타크릴레이트, 이소보로닐 메타크릴레이트 등의 메타크릴산 시클로알킬 에스테르; 시클로헥실 아크릴레이트, 2-메틸 시클로헥실 아크릴레이트, 디시클로펜테닐 아크릴레이트, 디시클로펜테닐옥시에틸 아크릴레이트, 이소보로닐 아크릴레이트 등의 아크릴산 시클로알킬 에스테르; 페닐 메타크릴레이트, 벤질 메타크릴레이트 등의 메타크릴산 아릴 에스테르; 페닐 아크릴레이트, 벤질 아크릴레이트 등의 아크릴산 아릴 에스테르; 말레산 디에틸, 프마르산 디에틸, 이타콘산 디에틸 등의 디카르복시산 디에스테르; 2-히드록시 에틸 메타크릴레이트, 2-히드록시 프로필 메타크릴레이트 등의 히드록시알킬 에스테르; 및 스티렌, o-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐 톨루엔, p-메톡시 스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화 비닐, 염화 비닐리덴, 아크릴 아미드, 메타크릴 아미드, 초산 비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디 엔 등을 들 수 있다. 이중 스티렌, t-부틸 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, p-메톡시 스티렌, 2-메틸 시클로헥실 아크릴레이트, 1,3-부타디엔 등이 공중합 반응성 및 내열성의 관점에서 바람직하다. 이러한 화합물 a-3은 단독으로 또는 조합하여 사용할 수 있다.On the other hand, 10 to 70% by weight, preferably 20 to 50% by weight of the structural unit derived from compound a-3 is contained. When this structural unit is less than 10 weight%, the storage stability of alkali-soluble resin tends to fall, and when it exceeds 70 weight%, alkali solubility, heat resistance, and surface hardness of alkali-soluble resin tend to fall. Specific examples of the compound a-3 include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fmarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate; And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Dual styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene and the like are preferred in view of copolymerization reactivity and heat resistance. These compounds a-3 can be used alone or in combination.
상기와 같은 화합물 a-1, a-2 및 a-3으로부터 얻어진 알칼리 가용성 수지는 카르복실기 및/또는 카르복시산 무수물기 및 에폭시기를 갖고 있으며, 특별한 경화제를 병용하지 않더라도 가열에 의하여 용이하게 경화시키는 것이 가능하고, 알칼리 수용액에 가용성이다. 또한 상기 알칼리 가용성 수지의 분자량 및 그 분포는, 알칼리 수용액에 가용성이고 본 발명의 조성물 용액을 균일하게 도포하는 일이 가능한 한 특정한 값으로 한정되는 것은 아니다. Alkali-soluble resins obtained from the above compounds a-1, a-2 and a-3 have a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating even without using a special curing agent. Soluble in aqueous alkali solution. In addition, the molecular weight of the said alkali-soluble resin and its distribution are not so limited to a specific value as long as it is soluble in aqueous alkali solution and can apply | coat uniformly the composition solution of this invention.
알칼리 가용성 수지의 합성에 사용할 수 있는 용매로는, 메틸알코올, 에틸알코올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로필렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등이 바람직하다.As a solvent which can be used for synthesis | combination of alkali-soluble resin, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Preferred are propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like.
한편, 알칼리 가용성 수지의 합성에 사용할 수 있는 중합개시제로는 일반적으로 라디칼 중합개시제로서 알려진 것이면 어느 것이나 사용할 수 있다. 예를들면, 2,2'-아조비스 이소부티로니트릴, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물; 벤조일 퍼옥 시드, t-부틸 퍼옥시 피바레이트, 1,1'-비스-(t-부틸 퍼옥시)시클로 헥산 등의 유기 과산화물; 및 과산화수소 등을 들 수 있다. 라디칼 중합 개시제로서 과산화물을 이용할 경우에는 과산화물을 환원제와 함께 이용하여 산화환원(redox) 개시제로 사용해도 좋다.In addition, as a polymerization initiator which can be used for the synthesis | combination of alkali-soluble resin, as long as it is generally known as a radical polymerization initiator, any can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2 Azo compounds, such as (4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pibarate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.
이같은 알칼리 가용성 수지의 함량은 전체 광경화형 수지 조성물 중 10∼70중량%인 바, 그 함량이 10중량% 미만이면 원하는 모양의 패턴이 만들어지지 않으며 70중량% 초과할 경우에도 원하는 모양의 패턴이 만들어지지 않는 문제가 있을 수 있다. The content of such alkali-soluble resin is 10 to 70% by weight of the total photocurable resin composition, if the content is less than 10% by weight does not form a pattern of the desired shape, even if it exceeds 70% by weight There may be a problem.
(2)중합성 화합물(2) polymerizable compound
본 발명에서 사용된 중합성 화합물로는 단관능, 2관능, 또는 3관능 이상의 메타크릴레이트가 중합성이 양호하고, 얻어지는 보호막의 내열성, 표면경도가 향상된다는 관점에서 바람직하다.As the polymerizable compound used in the present invention, monofunctional, bifunctional, or trifunctional or higher methacrylate is preferable from the viewpoint of good polymerizability and improved heat resistance and surface hardness of the resulting protective film.
여기서, 단관능 메타크릴레이트의 예로는, 2-히드록시 에틸 메타크릴레이트, 카비톨메타크릴레이트, 이소보닐 메타크릴레이트, 3-메톡시 부틸 메타크릴레이트, 2-메타크릴로일 옥시 에틸 2-히드록시 프로필 프탈레이트 등을 들 수 있다.Here, examples of the monofunctional methacrylate include 2-hydroxy ethyl methacrylate, carbitol methacrylate, isobornyl methacrylate, 3-methoxy butyl methacrylate, 2-methacryloyl oxy ethyl 2 -Hydroxy propyl phthalate, etc. are mentioned.
2관능 메타크릴레이트로는 에틸렌글리콜 메타크릴레이트, 1,6-헥산디올 메타크릴레이트, 1,9-노난디올 메타크릴레이트, 프로필렌글리콜 메타크릴레이트, 테트라에틸렌글리콜 메타크릴레이트, 비스페녹시 에틸알콜 플루오렌 디아크릴레이트 등을 들 수 있다.As bifunctional methacrylate, ethylene glycol methacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol methacrylate, propylene glycol methacrylate, tetraethylene glycol methacrylate, bisphenoxy Ethyl alcohol fluorene diacrylate, etc. are mentioned.
3관능 이상의 메타크릴레이트로는 트리스히드록시에틸이소시아누레이트 트리 메타크릴레이트, 트리메틸프로판 트리메타크릴레이트, 펜타에리쓰리톨 트리메타크릴레이트, 펜타에리쓰리톨 테트라메타크릴레이트, 디펜타에리쓰리톨 헥사메타크릴레이트 등을 들 수 있다.Trifunctional or more than trifunctional methacrylates include trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythr Lithol hexamethacrylate etc. are mentioned.
이러한 단관능, 2관능 또는 3관능 이상의 메타크릴레이트는 단독 또는 조합하여 사용할 수 있다.These monofunctional, bifunctional or trifunctional or higher methacrylates may be used alone or in combination.
이와같은 중합성 화합물은 상기 전체 광경화형 수지 조성물 중 10∼50중량%인 바, 그 함량이 10중량% 미만이면 충분히 높은 가교밀도를 갖는 보호막을 얻기 어렵고 보호막의 각종 내성이 저하되는 경우가 있다. 반면 그 함량이 50중량% 초과면 얻어지는 보호막의 알칼리 가용성 및 밀착성이 저하되기 쉽다. Such a polymerizable compound is 10 to 50% by weight in the total photocurable resin composition, when the content is less than 10% by weight, it is difficult to obtain a protective film having a sufficiently high crosslinking density and the various resistances of the protective film may be lowered. On the other hand, when the content is more than 50% by weight, alkali solubility and adhesion of the obtained protective film tend to be lowered.
(3)실리콘계 다관능성 모노머(3) silicone-based polyfunctional monomers
본 발명 광경화형 수지 조성물 중에 포함되는 실리콘계 다관능성 모노머는 중합성이 양호하고, 얻어지는 보호막의 내열성, 복원률을 향상시킨다는 관점에서 바람직하다. The silicone-based polyfunctional monomer contained in the photocurable resin composition of the present invention is preferable from the viewpoint of having good polymerizability and improving heat resistance and recovery rate of the protective film obtained.
구체적인 예로는 디메틸폴리실록산 디메타크릴레이트, 디메틸폴리실록산 디아크릴레이트, 디메틸폴리실록산 메타크릴레이트, 디메틸폴리실록산 아크릴레이트 등을 들 수 있다. 이들은 분자량 1000~10000인 것이 바람직하다. Specific examples include dimethylpolysiloxane dimethacrylate, dimethylpolysiloxane diacrylate, dimethylpolysiloxane methacrylate, dimethylpolysiloxane acrylate and the like. It is preferable that these are molecular weights 1000-10000.
그 함량은 전체 광경화형 수지 조성물 중 0.1∼20중량%로서, 그 함량이 0.1중량% 미만이면 내열성 및 복원률이 떨어지고 20중량% 초과면 현상후의 패턴이 원하는 모양으로 되지 않는 문제가 있을 수 있다. The content is 0.1 to 20% by weight of the total photocurable resin composition, if the content is less than 0.1% by weight may have a problem that the heat resistance and recovery rate is lowered, and if the content exceeds 20% by weight, the pattern after development does not become a desired shape.
(4)광개시제 (4) photoinitiators
본 발명의 광경화형 수지 조성물은 전체 조성 중 1∼15중량% 되도록 광개시제를 포함한다. 그 함량이 1중량% 미만이면 보호막의 감도가 충분하지 않아 현상 공정에서 보호막이 유실되기 쉽고, 현상 공정에서 보호막이 유지된다고 하더라도 충분히 높은 가교밀도를 갖는 보호막을 얻기 어렵다. 광개시제의 함량이 15중량% 초과면 보호막의 내열성, 평탄화성 등이 저하되기 쉽다. The photocurable resin composition of this invention contains a photoinitiator so that it may be 1 to 15weight% of a total composition. If the content is less than 1% by weight, the protective film is insufficient in sensitivity, so that the protective film is easily lost in the developing step, and even if the protective film is maintained in the developing step, it is difficult to obtain a protective film having a sufficiently high crosslink density. When the content of the photoinitiator is more than 15% by weight, the heat resistance, flattening property, etc. of the protective film tend to be lowered.
이같은 광개시제의 예로는 티옥산톤, 2,4-디에틸 티옥산톤, 티옥산톤-4-술폰산, 벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 아세토페논, p-디메틸아미노아세토페논, α,α'-디메톡시아세톡시벤조페논, 2,2'-디메톡시-2-페틸아세토페논, p-메톡시아세토페논, 2-메틸[4-(메틸티오)페닐]-2-모르폴리노-1-프로파논, 2-벤질-2-디에틸아미노-1-(4-모르폴리노페닐)-부탄-1-온 등의 아세톤류; 안트라퀴논, 1,4-나프토퀴논 등의 퀴논류; 페나실 클로라이드, 트리브로모메틸페닐술폰, 트리스(트리클로로메틸)-s-트리아진 등의 할로겐 화합물; 디-t-부틸 퍼옥사이드 등의 과산화물; 2,4,6-트리메틸 벤조일 디페닐 포스핀 옥사이드 등의 아실 포스핀 옥사이드류 등을 들 수 있다. 이러한 광개시제는 단독 또는 조합하여 사용할 수 있다.
Examples of such photoinitiators include thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethyl Aminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]- Acetones such as 2-morpholino-1-propanone and 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; And acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide. These photoinitiators can be used alone or in combination.
본 발명의 광경화형 수지 조성물은 통상 적당한 용매에 용해시켜 용액상태로 사용된다. 이 용매는 알칼리 가용성 수지, 중합성 화합물, 실리콘계 중합성 모노머 및 광개시제의 각 성분을 균일하게 용해시킬 수 있으며, 어느 한 성분과도 반응하지 않는 것을 사용할 수 있다. The photocurable resin composition of this invention is normally dissolved in a suitable solvent and used in a solution state. This solvent can melt | dissolve each component of alkali-soluble resin, a polymeric compound, a silicone type polymerizable monomer, and a photoinitiator uniformly, and what does not react with any component can be used.
구체적으로는, 메틸알코올, 에틸알코올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로필렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌글리코콜 알킬 에테르 아세테이트류 등을 들 수 있다. 이러한 용매 가운데서 용해성, 각 성분과의 반응성 및 도막 형성의 편리성의 관점에서 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 프로필렌 글리콜 메틸 에테르 아세테이트가 바람직하게 사용된다. Specifically, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And 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. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether acetate are preferably used in view of solubility, reactivity with each component, and convenience of coating film formation.
또한, 상기 용매와 함께 고비등점 용매를 병용한 것도 가능하다. 병용할 수 있는 고비등점 용매로서는 N-메틸 포름아미드, N,N-디메틸 포름아미드, N-메틸 아세트아미드, N,N-디메틸 아세트아미드, N-메틸 피롤리돈, 디메틸 설폭시드, 벤질 에틸 에테르 등을 들 수 있다.Moreover, it is also possible to use a high boiling point solvent together with the said solvent. High boiling point solvents that can be used together include N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide and benzyl ethyl ether. Etc. can be mentioned.
한편, 본 발명의 광경화형 수지 조성물은 본 발명의 목적을 손상시키지 않는 범위에서 필요에 의해 상기 이외의 다른 성분을 함유하고 있어도 좋다.In addition, the photocurable resin composition of this invention may contain other components of that excepting the above as needed in the range which does not impair the objective of this invention.
여기서, 다른 성분으로는 도포성 향상을 위한 계면활성제를 들 수 있다. 계면활성제로는 불소 및 실리콘계 계면활성제를 들 수 있는데, 예를들면 3M사의 FC-129, FC-170C, FC-430, DIC사의 F-172, F-173, F-183, F-470, F-475, 신에츠실리콘사의 KP322, KP323, KP340, KP341 등을 들 수 있다. 이러한 계면활성제는 알칼리 가용성 수지 100중량부에 대하여 바람직하게는 5중량부 이하, 보다 바람직하게는 2중량부 이하의 양으로 사용할 수 있다. 계면활성제의 양이 5중량부를 초과한 경우에는 도포시 거품이 발생하기 쉬워진다. Here, as another component, surfactant for improving applicability | paintability is mentioned. Surfactants include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F -KP322, KP323, KP340, KP341 by Shin-Etsu Silicone, etc. are mentioned. Such surfactant can be used in an amount of preferably 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin. When the amount of the surfactant exceeds 5 parts by weight, bubbles are likely to occur during application.
또 기체와의 밀착성을 향상시키기 위해 접착조제를 사용할 수 있다. 접착조제로는 관능성 실란 커플링제가 바람직하게 사용되는데, 예를들면 트리메톡시 실릴안식향산, γ-메타크릴록시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트 프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란 등을 들 수 있다. 이러한 접착조제는 알칼리 가용성 수지 100중량부에 대하여 20중량부 이하, 바람직하게는 10중량부 이하의 양으로 사용할 수 있다. 접착조제의 양이 20중량부를 초과할 경우에는 내열성이 저하되기 쉽다.Moreover, in order to improve the adhesiveness with gas, an adhesion | attachment adjuvant can be used. As the adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxy silyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate Propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. Such an adhesion aid may be used in an amount of 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin. When the amount of the adhesion aid exceeds 20 parts by weight, the heat resistance tends to be lowered.
상기와 같이 조제된 조성물 용액은 구멍지름 0.1∼5㎛ 정도의 밀리포어 필터 등을 이용하여 여과한 후 사용된다.The composition solution prepared as described above is used after filtration using a Millipore filter having a pore diameter of about 0.1 to 5 μm.
본 발명의 감광성 수지 조성물을 바탕기판에 도포하고, 60∼100℃에서 1∼10분간 건조시킨 후, 소정 형태의 마스크를 얻어진 도막 위에 놓은 상태에서 200∼500nm의 자외선 또는 가시광선을 300mJ/㎠ 이하로 조사하고, 알칼리 수용액을 현상액으로 이용하여 불필요한 부분을 용해, 제거하여 노광된 부위만을 잔존시켜 패턴을 형성시킨 후, 오븐에서 150∼300℃로 10∼100분간 처리한 것에 의하여 목적하는 컬럼 스페이서를 얻을 수 있다.
The photosensitive resin composition of this invention was apply | coated to a base substrate, and it dried for 1 to 10 minutes at 60-100 degreeC, and the ultraviolet-ray or visible ray of 200-500 nm or less is 300mJ / cm <2> or less in the state which put the mask of a predetermined form on the obtained coating film. Irradiated with an aqueous solution of alkali, and dissolved and removed unnecessary portions, leaving only the exposed portions to form a pattern, and then treating the resultant column spacer at 150 to 300 DEG C for 10 to 100 minutes. You can get it.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
제조예 1: 알칼리 가용성 수지 A-1의 제조Preparation Example 1 Preparation of Alkali Soluble Resin A-1
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중 량부를 디에틸렌글리콜 메틸 에테르 200중량부에 녹였다. 계속해서 스티렌 20중량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작하였다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체(이하, 알칼리 가용성 수지 A-1이라 함)를 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol methyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing a copolymer (hereinafter referred to as alkali soluble resin A-1). Solid content concentration of the obtained polymer solution was 33 weight%.
제조예 2: 알칼리 가용성 수지 A-2의 제조Preparation Example 2 Preparation of Alkali Soluble Resin A-2
상기 제조예 1과 동일한 방법으로 중합체 용액을 제조하되, 다만 스티렌 20중량부 대신에 벤질메타크릴레이트 20중량부를 사용하였다. 얻어진 중합체 용액의 고형분 농도는 33%이었다. 이를 알칼리 가용성 수지 A-2라 하였다. A polymer solution was prepared in the same manner as in Preparation Example 1, except that 20 parts by weight of benzyl methacrylate was used instead of 20 parts by weight of styrene. Solid content concentration of the obtained polymer solution was 33%. This was called alkali-soluble resin A-2.
제조예 3: 알칼리 가용성 수지 A-3의 제조Preparation Example 3 Preparation of Alkali Soluble Resin A-3
상기 제조예 1과 동일한 방법으로 중합체 용액을 제조하되, 다만 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부 대신 디시클로펜타닐 메타크릴레이트 10중량부를 사용하였다. 얻어진 중합체 용액의 고형분 농도는 33%이었다. 이를 알칼리 가용성 수지 A-3라 하였다. A polymer solution was prepared in the same manner as in Preparation Example 1, except that 10 parts by weight of dicyclopentanyl methacrylate was used instead of 10 parts by weight of dicyclopentenyloxyethyl methacrylate. Solid content concentration of the obtained polymer solution was 33%. This was called alkali-soluble resin A-3.
실시예 1∼6 및 비교예 1∼2Examples 1-6 and Comparative Examples 1-2
교반기가 있는 혼합조에 다음 표 1과 같은 조성 및 함량에 따라 알칼리가용성 수지, 중합성 화합물, 실리콘계 다관능성 모노머, 광개시제, 실란 커플링제와 열중합 방지제, 계면활성제를 순차적으로 첨가하여 프로필렌글리콜 메틸에테르아세테이트에 용해시킨 후 고형분 농도가 30중량%가 되도록 하였다. 그 후 구멍지름 0.45㎛의 필터로 여과하여 광경화형 수지 조성물을 제조하였다. Propylene glycol methyl ether acetate was added to the mixing vessel with a stirrer by sequentially adding an alkali-soluble resin, a polymerizable compound, a silicone-based polyfunctional monomer, a photoinitiator, a silane coupling agent, a thermal polymerization inhibitor and a surfactant according to the composition and content shown in Table 1 below. After dissolving in, the solid content concentration was 30% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and manufactured the photocurable resin composition.
상기와 같은 광경화성 수지 조성물을 스핀코터를 이용하여 유리기판 위에 막두께가 4㎛ 되도록 도포하고, 80℃에서 2분간 건조시킨 후, 소정 형태의 마스크를 얻어진 도막 위에 놓은 상태에서 365nm의 자외선을 150mJ/㎠로 조사하고, 알칼리 수용액을 현상액으로 이용하여 불필요한 부분을 용해, 제거하여 노광된 부위만을 잔존시켜 패턴을 형성시킨 후, 이를 클린 오븐에서 220℃로 30분 동안 소성하여 유리기판 위에 보호막을 형성하였다. The photocurable resin composition was coated on the glass substrate by using a spin coater so as to have a film thickness of 4 μm, dried at 80 ° C. for 2 minutes, and 150 mJ of 365 nm UV light was placed on the obtained coating film. Irradiated at / cm 2, using an aqueous alkaline solution as a developer, to dissolve and remove unnecessary portions, leaving only the exposed portions to form a pattern, and then baking the same at a clean oven at 220 ° C. for 30 minutes to form a protective film on the glass substrate. It was.
보호막을 형성한 다음, 다음과 같은 방법으로 밀착성, 패턴모양, 평탄도, 내열성, 내용제성을 측정하여 그 결과를 다음 표 2에 나타내었다.After the protective film was formed, the adhesion, pattern shape, flatness, heat resistance, and solvent resistance were measured by the following method, and the results are shown in Table 2 below.
1)밀착성: 바둑판 무늬 테이프법에 따라 보호막에 100개의 바둑판 무늬를 커 터 나이프로 형성하고 밀착성 시험을 행하여 박리된 바둑판 무늬의 수를 측정하고 다음 기준에 의하여 보호막의 밀착성을 평가하였다. 1) Adhesiveness: According to the checkered tape method, 100 checkered patterns were formed on the protective film with a cutter knife, and the adhesion test was performed to measure the number of peeled checkered patterns, and the adhesiveness of the protective film was evaluated according to the following criteria.
○ - 박리된 바둑판 무늬의 수 5개 이하, ○-5 or less peeled checkerboard patterns,
△ - 박리된 바둑판 무늬의 수 6∼49개△-6 to 49 stripped checkerboard patterns
× - 박리된 바둑판 무늬의 수 50개 이상×-50 or more peeled checkered patterns
2)패턴모양: ITO가 스파트된 유리기판에 상기의 조성물을 이용항 패턴을 형성한 후 라이 패턴의 수직 방향으로 절단하고, 패턴의 단면 방향을 전자현미경으로 관찰하여 바닥과 탑의 길이비가 85% 이상이면 양호, 85% 이하이면 불량으로 표시.2) Pattern shape: After forming the pattern using the composition on the glass substrate on which ITO was spattered, cut it in the vertical direction of the lie pattern, and observe the cross-sectional direction of the pattern with an electron microscope, and the length ratio of the bottom and the tower was 85%. If it is above, it is good. If it is 85% or less, it is marked as bad.
3)평탄도3) Flatness
ITO가 스파트된 유리 기판에 상기의 조성물을 패턴을 형성한 후 각각 다른 25곳의 코팅막의 표면 요철을 α 스텝을 이용하여 최대 두께와 최소 두께의 차를 구하였다. After the pattern of the composition was formed on the glass substrate on which ITO was spattered, the difference between the maximum thickness and the minimum thickness was determined by using α step for the surface irregularities of the 25 coating layers, respectively.
4)내열성4) heat resistance
보호막을 클린 오븐 240℃, 60분 동안 가열하고, 가열 전후에 투과 스펙트럼을 측정하고 다음 기준에 의하여 보호막의 내열성을 평가하였다. The protective film was heated in a clean oven at 240 ° C. for 60 minutes, and the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.
양호: 투과 스펙트럼의 변화가 1% 미만Good: less than 1% change in transmission spectrum
불량: 투과 스펙트럼의 변화가 1% 이상Poor: more than 1% change in transmission spectrum
5)내용제성5) solvent resistance
막이 형성된 유리 기판을 NMP, IPA, 아세톤 각각의 용액에 30℃, 60분간 침지한 후, 보호막의 외관 변화 및 두께 변화를 관찰하여 막의 내용제성을 평가하였 다. After the glass substrate on which the film was formed was immersed in a solution of NMP, IPA, and acetone for 30 ° C. for 60 minutes, the change in appearance and thickness of the protective film was observed to evaluate the solvent resistance of the film.
양호: 외관, 두께 변화없슴Good: Appearance, no change in thickness
불량: 외관, 두께 변화있음Poor: appearance, thickness change
상기 표 2의 결과로부터, 본 발명에 따른 광경화형 수지 조성물은 내용제성, 밀착력, 내열성, 평탄도, 패턴모양이 우수함을 알 수 있다.
From the results of Table 2, it can be seen that the photocurable resin composition according to the present invention is excellent in solvent resistance, adhesion, heat resistance, flatness, pattern shape.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 알칼리 가용성 수지, 중합성 화합물, 실리콘계 다관능성 모노머 및 광개시제를 포함하는 광경화형 수지 조성물은 내열성이 우수할 뿐만 아니라 액정 표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 평탄성, 해상성, 내용제성 및 패턴 모양이 양호하여 액정 디스플레이 소자의 컬럼 스페이서용으로서 매우 적합하다. As described in detail above, the photocurable resin composition comprising an alkali-soluble resin, a polymerizable compound, a silicone-based polyfunctional monomer, and a photoinitiator according to the present invention not only has excellent heat resistance but also has an appropriate thickness when forming a column spacer of a liquid crystal display device. It is possible to form a pattern, and has good flatness, resolution, solvent resistance, and pattern shape, which is very suitable for column spacers of liquid crystal display elements.
Claims (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20100087659A (en) * | 2009-01-28 | 2010-08-05 | 제이에스알 가부시끼가이샤 | Radiation sensitive resin composition, and spacer for liquid crystal display device and forming method thereof |
| KR101146182B1 (en) | 2009-05-11 | 2012-05-24 | 주식회사 이그잭스 | Photo sensitive resin composition used as spacer structure in liquid crystal display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100594396B1 (en) * | 2004-10-20 | 2006-06-30 | 일동화학 주식회사 | A photosensitive resin composition used as spacer structure between glass substrates of liquid crystal display panel |
| TWI385485B (en) * | 2004-11-17 | 2013-02-11 | Jsr Corp | A photosensitive resin composition, a display panel spacer, and a display panel |
| KR100832587B1 (en) * | 2007-02-05 | 2008-05-26 | 한국기계연구원 | Magnetic levitation train using linear synchronous reluctance motor |
| KR101146179B1 (en) * | 2009-04-03 | 2012-05-24 | 주식회사 이그잭스 | Photo sensitive resin composition used as spacer structure in liquid crystal display panel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20000048286A (en) * | 1998-12-21 | 2000-07-25 | 윌리암 로엘프 드 보에르 | Photo curable resin composition and optical parts |
| KR20000058201A (en) * | 1999-02-25 | 2000-09-25 | 기타지마 요시토시 | Photosensitive resin composition, color filter, and copolymer resin useful for them |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20000048286A (en) * | 1998-12-21 | 2000-07-25 | 윌리암 로엘프 드 보에르 | Photo curable resin composition and optical parts |
| KR20000058201A (en) * | 1999-02-25 | 2000-09-25 | 기타지마 요시토시 | Photosensitive resin composition, color filter, and copolymer resin useful for them |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100087659A (en) * | 2009-01-28 | 2010-08-05 | 제이에스알 가부시끼가이샤 | Radiation sensitive resin composition, and spacer for liquid crystal display device and forming method thereof |
| KR101665402B1 (en) | 2009-01-28 | 2016-10-12 | 제이에스알 가부시끼가이샤 | Radiation sensitive resin composition, and spacer for liquid crystal display device and forming method thereof |
| KR101146182B1 (en) | 2009-05-11 | 2012-05-24 | 주식회사 이그잭스 | Photo sensitive resin composition used as spacer structure in liquid crystal display panel |
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