KR20080052865A - Photosensitive resin composition - Google Patents
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- KR20080052865A KR20080052865A KR1020060124591A KR20060124591A KR20080052865A KR 20080052865 A KR20080052865 A KR 20080052865A KR 1020060124591 A KR1020060124591 A KR 1020060124591A KR 20060124591 A KR20060124591 A KR 20060124591A KR 20080052865 A KR20080052865 A KR 20080052865A
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- G02F1/133345—Insulating layers
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
본 발명은 감광성 수지 조성물에 관한 것으로, 특히 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물 및 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체, 다관능성 아크릴 단량체, 광중합 개시제 및 용매를 포함하는 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition, and in particular, to a photosensitive resin comprising an acrylic copolymer, a polyfunctional acrylic monomer, a photopolymerization initiator and a solvent obtained by copolymerizing an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof and an olefinically unsaturated compound. It relates to a resin composition.
본 발명에 따른 감광성 수지 조성물은 기계적 물성 및 고온에서의 내열성이 우수하여 LCD 제조공정의 패턴 스페이서 박막을 형성하기에 적합할 뿐만 아니라, 기재와의 접착성과 내샌드블라스트성이 우수하면서 동시에 높은 해상도를 가지고, 고감도로 기재의 미세 패턴 형성이 가능하다.The photosensitive resin composition according to the present invention has excellent mechanical properties and high heat resistance at high temperatures, and is not only suitable for forming a pattern spacer thin film in an LCD manufacturing process, but also excellent in adhesiveness and sandblast resistance to a substrate and at the same time high resolution. It is possible to form a fine pattern of the substrate with high sensitivity.
Description
본 발명은 감광성 수지 조성물에 관한 것으로, 기계적 물성 및 고온에서의 내열성이 우수하여 LCD 제조공정의 패턴 스페이서 박막을 형성하기에 적합할 뿐만 아니라, 기재와의 접착성과 내샌드블라스트성이 우수하면서 동시에 높은 해상도를 가지고, 고감도로 기재의 미세 패턴 형성이 가능한 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition, and excellent in mechanical properties and high heat resistance at high temperatures, not only suitable for forming a pattern spacer thin film of the LCD manufacturing process, but also excellent adhesion and sandblast resistance to the substrate and at the same time high It relates to a photosensitive resin composition having a resolution and capable of forming a fine pattern of a substrate with high sensitivity.
자외선을 이용하여 알칼리 수용액에서 현상이 가능한 미세 패턴을 형성하는 감광성 수지 조성물은 형성된 패턴의 기계적 물성, 내열성, 박막 제조시 막의 특성 등이 매우 중요하다. 이러한 감광성 수지 조성물은 인쇄 회로기판에 사용되는 드라이 필름 포토레지스트, 반도체 회로 제작용 포토레지스트 등으로 이용되어 왔으며, 이 외에도 EL(electroluminescence), LCD(liquid crystal display) 등의 디스플레이 분야에서도 널리 사용되고 있다.In the photosensitive resin composition for forming a fine pattern that can be developed in an aqueous alkali solution using ultraviolet rays, the mechanical properties, heat resistance, and film properties of the thin film are very important. The photosensitive resin composition has been used as a dry film photoresist for a printed circuit board, a photoresist for fabricating a semiconductor circuit, and the like, and is widely used in display fields such as EL (electroluminescence) and LCD (liquid crystal display).
특히, 최근의 LCD 분야에서는 액정 화면의 천연색을 구현하기 위하여 칼라 필터 포토레지스트 또는 액정 소자를 구동하는 TFT(thin film transister) 기판의 보호막 뿐만 아니라 광 시야각을 구현하는 돌출막으로도 그 용도가 확대되고 있으 며, 특히 안료가 포함되지 않은 투명한 감광성 수지 조성물은 칼라 필터의 보호막이나 TFT 기판의 보호막으로 매우 중요한 역할을 해오고 있다.In particular, in the recent LCD field, the use of the color filter photoresist or the TFT (thin film transister) substrate driving the liquid crystal device, as well as the protruding film to realize the wide viewing angle, to extend the color of the liquid crystal display, In particular, the transparent photosensitive resin composition containing no pigment plays a very important role as a protective film of a color filter or a protective film of a TFT substrate.
현재 개발되고 있는 패턴 스페이서용 감광성 수지 조성물은 LCD의 화소를 구성할 때 사용되는 블랙 매트릭스(black matrix)용 수지 조성물과 함께 매우 중요한 응용분야의 하나로 손꼽히고 있다. 이러한 감광성 수지 조성물들은 기존의 금속이나 무기물을 대체하는 의미를 가지고 있어서 더욱 그 용도가 확대되고 있다.The photosensitive resin composition for the pattern spacer, which is currently being developed, is considered as one of the very important application fields together with the resin composition for the black matrix used when configuring the pixels of the LCD. These photosensitive resin compositions have a meaning of replacing existing metals or inorganic materials, and their use is further expanded.
종래 감광성 수지 조성물은 일반적으로 알칼리 수용액에 의하여 용해 또는 팽윤되는 매트릭스 수지; 2개 이상의 에틸렌성 불포화 결합을 갖는 다기능성 아크릴 모노머; 광중합 개시제; 및 용매를 포함하며, 여기에 필요에 따라 제막성능을 향상시키거나 기판과의 접착력을 향상시키는 여러 가지 첨가제들로 이루어져 있다.Conventional photosensitive resin compositions generally include matrix resins dissolved or swelled by aqueous alkali solution; Multifunctional acrylic monomers having two or more ethylenically unsaturated bonds; Photopolymerization initiator; And it contains a solvent, and it is made of various additives to improve the film forming performance or the adhesion to the substrate as necessary.
상기와 같은 성분으로 구성된 종래의 감광성 수지 조성물은 에틸렌성 불포화기를 함유하는 다기능성 모노머들이 매트릭스 수지 속에 균일하게 분포되어 있다가 자외선이 조사되면 광개시제에 의해 생성된 라디칼에 의해 가교가 일어나 그물구조를 형성하게 된다. 상기 그물구조가 형성된 부분은 알칼리 현상액에 용해되지 않으므로 패턴을 이루게 된다. 그러나 이러한 방식으로는 가교의 밀도가 충분히 크지 못한 이유로 미세 패턴의 형성이 어렵고, 기계적 물성이 우수하지 못하며, 고온에서 내열성이 좋지 않아 원하는 패턴 형태를 계속 유지하지 못한다는 문제점이 있었다.In the conventional photosensitive resin composition composed of the above components, multifunctional monomers containing ethylenically unsaturated groups are uniformly distributed in the matrix resin, and when ultraviolet rays are irradiated, crosslinking occurs by radicals generated by the photoinitiator to form a net structure. Done. The portion where the net structure is formed is not dissolved in the alkaline developer, thereby forming a pattern. However, in such a method, it is difficult to form a fine pattern because the density of the crosslinking is not large enough, and there is a problem in that the mechanical properties are not excellent and the desired pattern shape cannot be maintained continuously due to poor heat resistance at high temperature.
이와 같은 형상을 개선하기 위하여 에폭시기를 메트릭스에 함유하는 감광성 수지 조성물들이 제조되었으나, 매트릭스의 안정성이 저하되어 조성물이 보관 중에 임의로 가교반응을 일으켜 패턴 형성이 불가능하고, 점도가 높아지는 등의 문제점이 있었다. In order to improve such a shape, photosensitive resin compositions containing an epoxy group in a matrix were prepared, but the stability of the matrix was deteriorated, so that the composition randomly crosslinked during storage, thus preventing the formation of a pattern and increasing the viscosity.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 투과율, 절연성, 내화학성, 내열성, 감도 등의 성능이 우수하고, 평탄성, 코팅성, 및 고내열성을 현저히 향상시켜 LCD 제조공정의 패턴 스페이서 박막을 형성하기에 적합할 뿐만 아니라, 기재와의 접착성과 내샌드블라스트성이 우수하면서 동시에 높은 해상도를 가지고, 고감도로 기재의 미세 패턴 형성이 가능한 감광성 수지 조성물을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention is excellent in the performance of transmittance, insulation, chemical resistance, heat resistance, sensitivity, etc., and significantly improve the flatness, coating properties, and high heat resistance pattern spacer thin film of the LCD manufacturing process It is an object of the present invention to provide a photosensitive resin composition which is not only suitable for forming a film, but also excellent in adhesiveness and sandblast resistance to a substrate and at the same time having a high resolution and capable of forming a fine pattern of the substrate with high sensitivity.
본 발명의 다른 목적은 우수한 평탄성, 코팅성, 및 고내열성을 가져 LCD 제조공정에 적용되는 패턴 스페이서 박막을 형성하기에 적합한 감광성 수지 조성물, 및 감광성 패턴 스페이서 박막을 제공하는 것이다.It is another object of the present invention to provide a photosensitive resin composition suitable for forming a pattern spacer thin film having excellent flatness, coating property, and high heat resistance, which is applied to an LCD manufacturing process, and a photosensitive pattern spacer thin film.
상기 목적을 달성하기 위하여, 본 발명은 감광성 수지 조성물에 있어서,In order to achieve the above object, the present invention provides a photosensitive resin composition,
a)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물; 및 ⅱ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체;a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof; And ii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound;
b) 하기 화학식 1 또는 화학식 2로 표시되는 다관능성 아크릴 단량체;b) a polyfunctional acrylic monomer represented by Formula 1 or Formula 2 below;
c) 광중합 개시제; 및c) photopolymerization initiator; And
d) 용매;d) solvents;
를 포함하는 것을 특징으로 하는 감광성 수지 조성물을 제공한다:It provides a photosensitive resin composition comprising:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 화학식 2의 식에서,In the formula of Formula 1 and Formula 2,
A는 
또한 본 발명은 상기 감광성 수지 조성물을 이용하여 제조되는 것을 특징으로 하는 감광성 패턴 스페이서 박막을 제공한다.In another aspect, the present invention provides a photosensitive pattern spacer thin film which is prepared using the photosensitive resin composition.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명의 감광성 수지 조성물은 a)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물 및 ⅱ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체; b) 상기 화학식 1 또는 화학식 2로 표시되는 다관능성 아크릴 단량체; c) 광중합 개시제; 및 d) 용매를 포함하는 것을 특징으로 한다.The photosensitive resin composition of this invention is a acrylic copolymer obtained by copolymerizing a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and ii) an olefinic unsaturated compound; b) a polyfunctional acrylic monomer represented by Formula 1 or Formula 2; c) photopolymerization initiator; And d) a solvent.
본 발명에 사용되는 상기 a)의 아크릴계 공중합체는 현상할 때에 스컴이 발생하지 않는 소정의 패턴을 용이하게 형성할 수 있도록 하는 작용을 한다.The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which scum does not occur when developing.
상기 a)의 아크릴계 공중합체는 ⅰ) 불포화 카르본산, 불포화 카르본산무수물, 또는 이들의 혼합물 및 ⅱ) 올레핀계 불포화 화합물을 단량체로 하여 용매 및 광중합 개시제의 존재하에서 라디칼 반응하여 제조할 수 있다.The acrylic copolymer of a) may be prepared by radical reaction in the presence of a solvent and a photopolymerization initiator using i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof and ii) an olefinic unsaturated compound as monomers.
본 발명에 사용되는 상기 a)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물은 아크릴산, 메타크릴산 등의 불포화 모노카르본 산; 말레인산, 푸마르산, 시트라콘산, 메타콘산, 이타콘산 등의 불포화 디카르본산; 또는 이들의 불포화 디카르본산의 무수물 등을 단독 또는 2 종 이상 혼합하여 사용할 수 있으며, 특히 아크릴산, 메타크릴산, 또는 무수말레인산을 사용하는 것이 공중합 반응성과 현상액인 알칼리 수용액에 대한 용해성에 있어 더욱 바람직하다.A) i) Unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof used in the present invention include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid and itaconic acid; Or anhydrides of these unsaturated dicarboxylic acids, or the like, may be used alone or in combination of two or more thereof. Particularly, acrylic acid, methacrylic acid, or maleic anhydride may be used in terms of copolymerization reactivity and solubility in aqueous alkali solution. Do.
상기 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물은 전체 총 단량체에 대하여 10 내지 90 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 10 내지 70 중량%로 포함되는 것이다. 그 함량이 10 중량% 미만일 경우에는 알칼리 수용액에 용해되기 어려운 문제점이 있으며, 90 중량%를 초과할 경우에는 알칼리 수용액에 대한 용해성이 너무 커지는 문제점이 있다.The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably included in 10 to 90% by weight, more preferably 10 to 70% by weight relative to the total total monomers. If the content is less than 10% by weight, there is a problem that is difficult to dissolve in the aqueous alkali solution, when it exceeds 90% by weight there is a problem that the solubility in the aqueous alkali solution is too large.
본 발명에 사용되는 상기 a) ⅱ)의 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, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이 트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트, 스티렌, α-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐톨루엔, p-메톡시 스티렌, 1,3-부타디엔, 이소프렌, 또는 2,3-디메틸 1,3-부타디엔 등을 사용할 수 있으며, 상기 화합물을 단독 또는 2 종 이상 혼합하여 사용할 수 있다.The olefinically unsaturated compound of a) ii) used in the present invention is 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, dicy Clofentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, Phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p- Methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3-butadiene may be used, and the compound may be used alone or in combination of two or more thereof. .
특히, 상기 올레핀계 불포화 화합물은 스티렌, 디시클로펜타닐 메타크릴레이트, 또는 p-메톡시 스티렌을 사용하는 것이 공중합 반응성 및 현상액인 알칼리 수용액에 대한 용해성 측면에서 더욱 바람직하다.In particular, the olefinically unsaturated compound is more preferable in terms of solubility in an aqueous alkali solution which is copolymerization reactivity and developer using styrene, dicyclopentanyl methacrylate, or p-methoxy styrene.
상기 올레핀계 불포화 화합물은 전체 총 단량체에 대하여 10 내지 90 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 20 내지 70 중량%로 포함되는 것이다. 그 함량이 10 중량% 미만일 경우에는 공중합체의 보존 안정성이 저하되는 문제점이 있으며, 90 중량%를 초과할 경우에는 공중합체가 알칼리 수용액에 용해되기 어려운 문제점이 있다.The olefinically unsaturated compound is preferably included in 10 to 90% by weight, more preferably 20 to 70% by weight relative to the total total monomers. If the content is less than 10% by weight, there is a problem that the storage stability of the copolymer is lowered, and when the content exceeds 90% by weight, the copolymer is difficult to be dissolved in an aqueous alkali solution.
또한, 상기 아크릴계 공중합체는 5 내지 40 중량부 포함되는 것이 바람직한데, 상기 아크릴계 공중합체가 5 중량부 미만일 경우 빛에 의한 패턴 형성이 충분하게 이루어지지 않을 가능성이 있으며, 40 중량부를 초과할 경우 전체 혼합물의 산가가 낮아져 빛을 받지 않은 부위도 현상액에 깨끗하게 용해되기 어려워 패턴 분리가 어려워지기 때문이다. In addition, the acrylic copolymer is preferably included 5 to 40 parts by weight, when the acrylic copolymer is less than 5 parts by weight there is a possibility that the pattern formation by light is not sufficient, if the total weight exceeds 40 parts by weight This is because the acid value of the mixture is lowered, so that even the unlighted portion is difficult to dissolve in the developer solution, making it difficult to separate the pattern.
상기와 같은 단량체를 아크릴계 공중합체로 중합하기 위해 사용되는 용매는 메탄올, 테트라히드로퓨란, 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 디메틸에테르, 에틸렌글리콜 디에틸에테르, 에틸렌글리콜 메틸에틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 프로필에테르, 프로필렌글리콜 부틸에테르, 프로필렌글리콜 메틸에테르아세테이트, 프로필렌글리콜 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-메틸 프로피온산메틸, 2-히드록시 2-메틸 프로피온산에틸, 히드록시 초산메틸, 히드록시 초산에틸, 히드록시 초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시 프로피온산메틸, 3-히드록시 프로피온산에틸, 3-히드록시 프로피온산프로필, 3-히드록시 프로피온산부틸, 2-히드록시 3-메틸 부탄산메틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산프로필, 메톡시초산부틸, 에톡시초산메틸, 에톡시초산에틸, 에톡시초산프로필, 에톡시초산부틸, 프로폭시초산메틸, 프로폭시초산에틸, 프로폭시초산프로필, 프로폭시초산부틸, 부톡시초산메틸, 부톡시초산에틸, 부톡시초산프로필, 부톡시초산부틸, 2-메톡시프로피온산메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산프로필, 2-메톡시프로피온산부 틸, 2-에톡시프로피온산메틸, 2-에톡시프로피온산에틸, 2-에톡시프로피온산프로필, 2-에톡시프로피온산부틸, 2-부톡시프로피온산메틸, 2-부톡시프로피온산에틸, 2-부톡시프로피온산프로필, 2-부톡시프로피온산부틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-메톡시프로피온산프로필, 3-메톡시프로피온산부틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산프로필, 3-에톡시프로피온산부틸, 3-프로폭시프로피온산메틸, 3-프로폭시프로피온산에틸, 3-프로폭시프로피온산프로필, 3-프로폭시프로피온산부틸, 3-부톡시프로피온산메틸, 3-부톡시프로피온산에틸, 3-부톡시프로피온산프로필, 또는 3-부톡시프로피온산부틸 등과 같은 에테르류 등을 사용할 수 있으며, 상기 화합물을 단독 또는 2 종 이상 혼합하여 사용할 수 있다.Solvents used to polymerize such monomers into acrylic copolymers include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol mono. Methyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene Glycol Methyl Ether Acetate, Propylene Glycol Ethyl Acetate, Propylene Glycol Propyl Ether Acetate, Propylene Glycol Butyl Ether Acetate, Propylene Glycol Methyl Ethyl Propionate, Propylene Glycol Ethyl Propionate Nitrate, 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, propyl acetate , Butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, lactic acid Ethyl, propyl lactate, butyl lactate, methyl 3-hydroxy propionate, ethyl 3-hydroxy propionate, propyl 3-hydroxy propionate, butyl 3-hydroxy propionate, methyl 2-hydroxybutyrate, methoxyacetic acid To methyl, ethyl methoxy acetate, methoxy methoxy acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, propoxy acetate Propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate,Ethers such as methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, etc. may be used, and the compounds may be used alone or in combination of two or more thereof. have.
상기와 같은 단량체를 아크릴계 공중합체로 중합하기 위해 사용되는 광중합 개시제는 라디칼 광중합 개시제를 사용할 수 있으며, 구체적으로 2,2-아조비스이소부티로니트릴, 2,2-아조비스(2,4-디메틸발레로니트릴), 2,2-아조비스(4-메톡시 2,4-디메틸발 레로니트릴), 1,1-아조비스(시클로헥산-1-카르보니트릴), 또는 디메틸 2,2-아조비스이소부틸레이트 등을 사용할 수 있다. The photopolymerization initiator used to polymerize such monomers into an acrylic copolymer may use a radical photopolymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethyl Valeronitrile), 2,2-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2-azobis Isobutylate and the like can be used.
상기와 같은 단량체를 용매와 광중합 개시제 존재하에서 라디칼 반응시켜 제조되는 a)의 아크릴계 공중합체는 폴리스티렌 환산중량평균분자량(Mw)이 5,000 내지 30,000인 것이 바람직하며, 더욱 바람직하게는 5,000 내지 20,000인 것이다. 상기 폴리스티렌 환산중량평균분자량이 5,000 미만인 경우에는 현상성, 잔막율 등이 저하되거나, 패턴 형상, 내열성 등이 뒤떨어진다는 문제점이 있으며, 30,000을 초과하는 경우에는 감도가 저하되거나 패턴 현상이 뒤떨어진다는 문제점이 있다.The acrylic copolymer of a) prepared by radical reaction of such a monomer in the presence of a solvent and a photopolymerization initiator preferably has a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 30,000, more preferably 5,000 to 20,000. If the polystyrene reduced weight average molecular weight is less than 5,000, there is a problem that developability, residual film ratio, etc. are lowered, or the pattern shape, heat resistance, etc. are inferior. If the polystyrene conversion weight average molecular weight is more than 30,000, the sensitivity is lowered or the pattern is poor. There is a problem.
본 발명에 사용되는 상기 b)의 화학식 1 또는 화학식 2로 표시되는 다관능성 아크릴 단량체는 광중합 개시제에 의해 작동하는 가교제의 작용을 한다.The polyfunctional acrylic monomer represented by Chemical Formula 1 or Chemical Formula 2 of b) used in the present invention functions as a crosslinking agent operated by a photopolymerization initiator.
상기 화학식 1 또는 화학식 2로 표시되는 다관능성 아크릴 단량체는 하기 화학식 3 또는 화학식 4로 표시되는 화합물을 출발물질로 하여 제조할 수 있다.The polyfunctional acrylic monomer represented by Formula 1 or Formula 2 may be prepared by using a compound represented by Formula 3 or Formula 4 as a starting material.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 화학식 1 또는 화학식 2로 표시되는 다관능성 아크릴 단량체는 5 내지 40 중량부로 포함되는 것이 바람직하며, 더욱 바람직하게는 20 내지 30 중량부로 포함되는 것이다. 그 함량이 5 중량부 미만일 경우에는 얻어지는 스페이서 박막의 강도가 저하될 수 있는 문제점이 있으며, 40 중량부를 초과할 경우에는 얻어지는 스페이서의 밀착성이 저하되는 문제점이 있다.The polyfunctional acrylic monomer represented by Formula 1 or Formula 2 is preferably included in 5 to 40 parts by weight, more preferably 20 to 30 parts by weight. If the content is less than 5 parts by weight, there is a problem that the strength of the spacer thin film obtained may be lowered, and if it exceeds 40 parts by weight, there is a problem that the adhesion of the spacer obtained is lowered.
본 발명에 사용되는 상기 c)의 광중합 개시제는 통상의 감광성 수지 조성물에 사용되는 트라이진계, 벤조인, 아세토페논계, 이미다졸계, 포스핀 옥사이드계, 또는 트산톤계 등의 화합물을 1 종 이상 혼합하여 사용할 수 있으며, 구체적으로 2,4-비스트리클로로메틸-6-p-메톡시스틸-s-트라이진, 2-p-메톡시스틸-4,6-비스트리클로로메틸-s-트리아진, 2,4-트리클로로메틸-6-트리아진, 2,4-트리클로로메틸-4-메틸나프틸-6-트리아진, 벤조페논, p-(디에틸아미노)벤조페논, 2,2-디클로로-4-페녹시아세토페논, 2,2'-디에톡시아세토페논, 2,2'-디부톡시아세토페논, 2-히드록시-2-메틸프로리오페논, p-t-부틸트리클로로아세토페논, 디페닐 (2,4,6-트리메틸벤조일) 포스핀 옥사이드, 비스(2,4,6-트리메틸벤조일) 페닐 포스핀 옥사이드, 2-메틸티오크산톤, 2-이소부틸티오크산톤, 2-도데실티오크산톤, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 또는 2,2'-비스-2-클로로페닐-4,5,4'5'-테트라페닐-2'1,2'-비이미다졸 화합물 등을 단독 또는 2 종 이상 혼합하여 사용할 수 있다.The photopolymerization initiator of c) used in the present invention is a mixture of one or more compounds such as triazine, benzoin, acetophenone, imidazole, phosphine oxide, or thanthone used in a conventional photosensitive resin composition. 2,4-bistrichloromethyl-6-p-methoxysteel-s-triazine, 2-p-methoxysteel-4,6-bistrichloromethyl-s-triazine , 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2- Dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, di Phenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl Thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, or 2,2'-bis-2-chlorophenyl-4,5,4'5'-tetraphenyl-2 ' The 1,2'-biimidazole compound etc. can be used individually or in mixture of 2 or more types.
상기 광중합 개시제는 1 내지 50 중량부로 포함되는 것이 바람직하며, 더욱 바람직하게는 5 내지 30 중량부로 포함되는 것이다. 그 함량이 1 중량부 미만일 경우에는 얻어지는 스페이서 박막의 강도가 저하될 수 있는 문제점이 있으며, 50 중량부를 초과할 경우에는 액정중의 용출물이 증가하고 전압 유지율이 저하되는 문제점이 있다.The photopolymerization initiator is preferably included 1 to 50 parts by weight, more preferably 5 to 30 parts by weight. If the content is less than 1 part by weight, there is a problem that the strength of the obtained spacer thin film may be lowered. If the content is more than 50 parts by weight, the eluate in the liquid crystal increases and the voltage retention decreases.
본 발명에 사용되는 상기 d)의 용매는 메탄올, 에탄올, 벤질 알코올, 헥실 알코올 등의 알코올류; 테트라히드로퓨란 등의 에테르류; 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르 아세테이트류; 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 디에틸렌글리콜디에틸에테르 등의 디에틸렌글리콜류; 프로필렌글리콜 메틸에테르, 프로필렌글리콜 에틸에테르, 프로필렌글리콜 프로필에테르, 프로필렌글리콜 부틸에테르 등의 프로필렌글리콜 모노알킬에테르류; 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 프로필에테르아세테이트, 프로필렌글리콜 부틸에테르아세테이트 등의 프로필렌글리콜 알킬에테르아세테이트류; 프로필렌글리콜 메틸에테르프로피오네이트, 프로필렌글리콜 에틸에테르프로피오네이트, 프로필렌글리콜 프로필에테르프로피오네이트, 프로필렌글리콜 부틸에테르프로피오네이트 등의 프로필렌글리콜 알킬에테르아세테이트류; 디프로필렌글리콜디메틸에테르, 디프로필렌글리콜메틸에틸에테르, 디프로필렌글리콜디에틸에테르 등의 디프로필렌글리콜디에틸에테르류; 톨루엔, 크실렌 등의 방향족 탄화수소류, 메틸에틸케톤, 시클로헥사논, 4-히드록시 4-메틸 2-펜타논 등의 케톤류, 또는 초산메틸, 초산에틸, 초산프로필, 초산부틸, 2-히드록시 프로피온산 에틸, 2-히드록시 2-메틸프로피온산 메틸, 2-히드록시 2-메틸프로피온산 에틸, 히드록시초산메틸, 히드록시초산에틸, 히드록시초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시프로피온산메틸, 3-히드록시프로피온산에틸, 3-히드록시프로피온산프로필, 3-히드록시프로피온산부틸, 2-히드록시 3-메틸부탄산 메틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산프로필, 메톡시초산부틸, 에톡시초산메틸, 에톡시초산에틸, 에톡시초산프로필, 에톡시초산부틸, 프로폭시초산메틸, 프로폭시초산에틸, 프로폭시초산프로필, 프로폭시초산부틸, 부톡시초산메틸, 부톡시초산에틸, 부톡시초산프로필, 부톡시초산부틸, 2-메톡시프로 피온산메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산프로필, 2-메톡시프로피온산부틸, 2-에톡시프로피온산메틸, 2-에톡시플피온산에틸, 2-에톡시프로피온산프로필, 2-에톡시프로피온산부틸, 2-부톡시프로피온산메틸, 2-부톡시프로피온산에틸, 2-부톡시프로피오산프로필, 2-부톡시프로피온산부틸, 3-메톡시프로피온산메틸 3-메톡시프로피온산에틸, 3-메톡시프로피온산프로필, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산프로필, 3-에톡시프로피온산부틸, 3-프로폭시프로피온산메틸, 3-프로폭시프로피온산에틸, 3-프로폭시프로피온산프로필, 3-프로폭시프로피온산부틸, 3-부톡시프로피온산메틸, 3-부톡시프로피온산에틸, 3-부톡시프로피온산프로필, 3-부톡시프로피온산부틸 등의 에스테르류 등이 있다. 특히, 상기 혼합가능한 용매는 벤질 알코올, 헥실 알코올, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 디에틸렌글리콜디에틸에테르, 디프로필렌글리콜디메틸에테르, 디프로필렌글리콜메틸에틸에테르, 또는 디프로필렌글리콜디에틸에테르인 것이 바람직하다.The solvent of d) used in the present invention is alcohols such as methanol, ethanol, benzyl alcohol, hexyl alcohol; 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, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl 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; Dipropylene glycol diethyl ether such as dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; Aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy 4-methyl 2-pentanone, or methyl acetate, ethyl acetate, propyl acetate, butyl acetate and 2-hydroxy propionic acid Ethyl, 2-hydroxy methyl 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, butoxy Methyl acetate, part Ethyl oxyacetate, butyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxy fluoride, propyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxy Butyl propionate, methyl 3-methoxypropionate ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl ethoxypropionate , 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butoxypropionate, 3-butoxy ethyl propionate, 3-butoxypropionate, 3-butoxypro Esters such as butyl pionate; and the like. In particular, the mixed solvent is benzyl alcohol, hexyl alcohol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, or dipropylene glycol It is preferable that it is diethyl ether.
상기 용매는 전체 감광성 수지 조성물의 고형분 함량이 10 내지 50 중량%가 되도록 포함되는 것이 바람직하다.The solvent is preferably included so that the solid content of the entire photosensitive resin composition is 10 to 50% by weight.
상기와 같은 성분으로 이루어지는 본 발명의 감광성 수지 조성물은 필요에 따라 e) 에폭시수지, f) 접착제, g) 아크릴 화합물, 및 h) 계면활성제를 추가로 포함할 수 있다. The photosensitive resin composition of this invention which consists of such a component as needed may further contain e) epoxy resin, f) adhesive, g) acrylic compound, and h) surfactant.
상기 e)의 에폭시 수지는 감광성 수지 조성물로부터 얻어지는 패턴의 내열성, 감도 등을 향상시키는 작용을 한다.The epoxy resin of the said e) functions to improve the heat resistance, sensitivity, etc. of the pattern obtained from the photosensitive resin composition.
상기 에폭시 수지는 비스페놀 A 형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 환상지방족 에폭시 수지, 글리시딜 에스테르형 에폭시 수지, 글리시딜 아민형 에폭시 수지, 복소환식 에폭시 수지, 또는 a)의 아크릴계 공중합체와는 다른 글리시딜 메타아크리레트를 (공)중합한 수지 등을 사용할 수 있으며, 특히 비스페놀 A 형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 또는 글리시딜 에스테르형 에폭시 수지를 사용하는 것이 바람직하다.The epoxy resin is bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, heterocyclic epoxy resin, Or a resin obtained by co-polymerizing glycidyl methacrylate different from the acrylic copolymer of a), and in particular, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or glycidyl ester type Preference is given to using epoxy resins.
상기 f)의 접착제는 기판과의 접착성을 향상시키는 작용을 하며, 카르복실기, 메타크릴기, 이소시아네이트기, 또는 에폭시기 등과 같은 반응성 치환기를 갖는 실란 커플링제 등을 사용할 수 있다. 구체적으로 γ-메타아크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, 또는 β-(3,4-에폭시 시클로 헥실)에틸트리메톡시실란 등을 사용할 수 있다.The adhesive of f) serves to improve adhesion to the substrate, and a silane coupling agent having a reactive substituent such as carboxyl group, methacryl group, isocyanate group, or epoxy group can be used. Specifically, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3 , 4-epoxy cyclohexyl) ethyltrimethoxysilane and the like can be used.
상기 g)의 아크릴 화합물은 감광성 수지 조성물로부터 얻어지는 패턴의 투과율, 내열성, 감도 등을 향상시키는 작용을 한다.The acrylic compound of g) functions to improve the transmittance, heat resistance, sensitivity and the like of the pattern obtained from the photosensitive resin composition.
바람직하기로는 상기 아크릴 화합물의 대표적인 예는 하기 화학식 5와 같다.Preferably, a representative example of the acrylic compound is represented by the following formula (5).
[화학식 5][Formula 5]
상기 화학식 5의 식에서,In the formula (5),
R은 수소원자, 탄소수 1∼5의 알킬기, 탄소수 1∼5의 알콕시기, 또는 탄소수 1∼5의 알카노일기이고,R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or an alkanoyl group of 1 to 5 carbon atoms,
1 < a < 6이고, a + b = 6이다.1 <a <6 and a + b = 6.
상기 i)의 계면활성제는 감광성 조성물의 도포성이나 현상성을 향상시키는 작용을 한다.The surfactant of i) functions to improve the applicability and developability of the photosensitive composition.
상기 계면활성제는 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르, F171, F172, F173(상품명: 대일본잉크사), FC430, FC431(상품명: 수미또모트리엠사), 또는 KP341(상품명: 신월화학공업사) 등을 사용할 수 있다. The surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem, Inc.), or KP341 (trade name: Shinwol) Chemical industry) and the like.
상기와 같은 성분으로 이루어지는 본 발명의 감광성 수지 조성물의 고형분 농도는 20 내지 50 중량%인 것이 바람직하며, 상기 범위의 고형분을 가지는 조성물은 0.1∼1.0 ㎛의 밀리포아필터 등으로 여과한 뒤 사용하는 것이 좋다.It is preferable that solid content concentration of the photosensitive resin composition of this invention which consists of the above components is 20 to 50 weight%, and the composition which has a solid content of the said range is used after filtering with a 0.1-1.0 micrometer millipore filter etc. good.
또한 본 발명은 상기와 같은 감광성 수지를 이용한 감광성 패턴 스페이서 박막의 형성방법을 제공하는 바, 구체적으로 상기 감광성 수지 조성물을 이용하여 감광성 패턴 스페이서 박막을 형성하는 방법은 다음과 같다.In addition, the present invention provides a method of forming the photosensitive pattern spacer thin film using the photosensitive resin as described above, specifically, the method of forming the photosensitive pattern spacer thin film using the photosensitive resin composition is as follows.
먼저 본 발명의 감광성 수지 조성물을 스프레이법, 롤코터법, 회전도포법 등으로 기판표면에 도포하고, 프리베이크에 의해 용매를 제거하여 도포막을 형성한다. 이때, 상기 프리베이크는 70∼110 ℃의 온도에서 1∼15 분간 실시하는 것이 바람직하다.First, the photosensitive resin composition of this invention is apply | coated to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, etc., A solvent is removed by prebaking, and a coating film is formed. At this time, it is preferable to perform the said prebaking for 1 to 15 minutes at the temperature of 70-110 degreeC.
그 다음, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 엑 스선 등을 상기 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다. Then, a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, x-rays and the like to the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.
상기 현상액은 알칼리 수용액을 사용하는 것이 좋으며, 구체적으로 수산화나트륨, 수산화칼륨, 탄산나트륨 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; 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액 등을 사용할 수 있다. 이때, 상기 현상액은 알칼리성 화합물을 0.1∼10 중량%의 농도로 용해시켜 사용되며, 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가할 수도 있다.The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and 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; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.
또한, 상기와 같은 현상액으로 현상한 후 초순수로 30∼90 초간 세정하여 불필요한 부분을 제거하고 건조하여 패턴을 형성하고, 상기 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 150∼250 ℃의 온도에서 30∼90 분간 가열처리하여 최종 패턴을 얻을 수 있다.In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, the pattern is applied to a heating apparatus such as an oven. By heating at a temperature of 150 to 250 ° C. for 30 to 90 minutes to obtain a final pattern.
본 발명에 따른 감광성 수지 조성물은 투과율, 절연성, 내화학성, 내열성, 감도 등의 성능이 우수하고, 평탄성, 코팅성, 및 고내열성을 현저히 향상시켜 LCD 제조공정의 패턴 스페이서 박막을 형성하기에 적합할 뿐만 아니라, 기재와의 접착성과 내샌드블라스트성이 우수하면서 동시에 높은 해상도를 가지고, 고감도로 기재의 미세 패턴 형성이 가능한 장점이 있다.The photosensitive resin composition according to the present invention has excellent performance in transmittance, insulation, chemical resistance, heat resistance, sensitivity, and the like, and is particularly suitable for forming a pattern spacer thin film in an LCD manufacturing process by remarkably improving flatness, coating property, and high heat resistance. In addition, there is an advantage in that the fine pattern of the substrate can be formed with high sensitivity while having excellent adhesiveness with the substrate and sandblast resistance and high resolution.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
메타크릴산 13 중량부, 메틸 메타크릴레이트 7 중량부를 넣고 공중합시킨 아크릴계 공중합체 20 중량부와, 상기 화학식 1에서 R이 수소인 단량체 20 중량부, 광중합 개시제로 2,4-비스트리클로로메틸-6-p-메톡시스틸-s-트라이진 5 중량부 용매로 프로필렌글리콜메틸에틸에테르 175 중량부 및 접착력 강화제로 글리시독시프로필트리메톡시실래인 1 중량부를 가하여 호모지나이저로 교반한 후, 0.2㎛의 테프론 필터로 여과하여 스핀 코팅하였다.20 parts by weight of an acrylic copolymer copolymerized with 13 parts by weight of methacrylic acid and 7 parts by weight of methyl methacrylate, 20 parts by weight of a monomer in which R is hydrogen in Formula 1, and 2,4-bistrichloromethyl- as a photopolymerization initiator 5 parts by weight of 6-p-methoxysteel-s-triazine was added 175 parts by weight of propylene glycol methylethyl ether and 1 part by weight of glycidoxypropyltrimethoxysilane as an adhesion enhancer, followed by stirring with a homogenizer. Spin coating was performed by filtration with a 0.2 μm Teflon filter.
상기 코팅된 유리기판을 100 ℃에서 2분간 전처리하였고, 포토 마스크를 이용하여 패턴을 형성하였다. 이때 사용된 노광량은 400 mJ/㎠였고, 현상액으로 약 1 분 50 초 동안 현상한 후, 220 ℃의 오븐에서 30 분간 후처리한 결과, 박막의 두께가 4.5 ㎛이고, 분해능이 10 ㎛인 최종 박막을 수득하였다.The coated glass substrate was pretreated at 100 ° C. for 2 minutes to form a pattern using a photo mask. The exposure dose used was 400 mJ / cm 2, developed for about 1 minute and 50 seconds with a developer, and after 30 minutes in an oven at 220 ° C., the final thin film had a thickness of 4.5 μm and a resolution of 10 μm. Obtained.
[비교예][Comparative Example]
메타크릴산 13 중량부, 메틸 메타크릴레이트 7 중량부를 넣고 공중합시킨 아크릴계 공중합체 20중량부와, 다관능성 아크릴 단량체로 펜타에리스리톨 테트라메틸아크릴레이트 20 중량부, 광중합 개시제로 비스-4,4'-디에틸아미노 벤조페논 5 중량부, 용매로 프로필렌글리콜메틸에틸에테르 54 중량부, 및 접착력 강화제로 글리시독시프로필트리메톡시실래인 1 중량부를 가하여 호모지나이저로 교반한 후, 0.2 ㎛의 테프론 필터로 여과하여 스핀 코팅하였다. 20 parts by weight of an acrylic copolymer copolymerized with 13 parts by weight of methacrylic acid and 7 parts by weight of methyl methacrylate, 20 parts by weight of pentaerythritol tetramethyl acrylate as a polyfunctional acrylic monomer, and a bis-4,4'- as a photopolymerization initiator. 5 parts by weight of diethylamino benzophenone, 54 parts by weight of propylene glycol methylethyl ether as a solvent, and 1 part by weight of glycidoxypropyltrimethoxysilane as an adhesion enhancer, followed by stirring with a homogenizer, followed by a 0.2 μm Teflon filter. Filtered and spin coated.
상기 코팅된 유리기판을 100 ℃에서 2 분간 전처리하였고, 포토 마스크를 이용하여 패턴을 형성하였다. 이때 사용된 노광량은 400 mJ/㎠였고, 현상액으로 약 1 분 50 초 동안 현상한 후, 220 ℃의 오븐에서 30 분간 후처리한 결과, 패턴이 완벽하게 분해되지 않았다.The coated glass substrate was pretreated at 100 ° C. for 2 minutes to form a pattern using a photo mask. The exposure dose used was 400 mJ / cm 2, and after developing for about 1 minute and 50 seconds with a developer, and after 30 minutes in an oven at 220 ° C., the pattern was not completely decomposed.
본 발명에 따른 감광성 수지 조성물은 LCD 제조공정의 패턴 스페이서 박막을 형성하기에 적합할 뿐만 아니라, 기재와의 접착성과 내샌드블라스트성이 우수하면서 동시에 높은 해상도를 가지고, 고감도로 기재의 미세 패턴 형성이 가능한 효과가 있다.The photosensitive resin composition according to the present invention is not only suitable for forming the pattern spacer thin film of the LCD manufacturing process, but also has excellent resolution and sandblast resistance with the substrate and at the same time has a high resolution, and the fine pattern formation of the substrate with high sensitivity is achieved. There is a possible effect.
이상에서 본 발명의 기재된 구체예에 대해서만 상세히 설명되었지만, 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, it is natural that such variations and modifications belong to the appended claims. .
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| US9457110B2 (en) | 2011-11-22 | 2016-10-04 | Heraeus Medical Gmbh | Method and composition for sterilization of a polymerizable monomer |
| US10350327B2 (en) | 2011-11-22 | 2019-07-16 | Heraeus Medical Gmbh | Method and composition for sterilization of a polymerizable monomer |
| US9448476B2 (en) | 2014-01-24 | 2016-09-20 | Samsung Display Co., Ltd. | Photoresist composition and method of manufacturing a thin film transistor substrate |
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