KR100481667B1 - Developer for dye dispersing photoresist - Google Patents
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- KR100481667B1 KR100481667B1 KR10-2001-0047453A KR20010047453A KR100481667B1 KR 100481667 B1 KR100481667 B1 KR 100481667B1 KR 20010047453 A KR20010047453 A KR 20010047453A KR 100481667 B1 KR100481667 B1 KR 100481667B1
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/004—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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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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Abstract
본 발명은 포토레지스트 현상액에 관한 것으로서, 본 발명에 따른 현상액은 (a) 알칼리 화합물, (b) 폴리옥시에틸렌-폴리옥시프로필렌-폴리옥시에틸렌 트리블락 공중합체 또는 폴리옥시프로필렌-폴리옥시에틸렌-폴리옥시프로필렌 트리블락공중합체로부터 선택된 1종 이상의 제1 계면활성제 및 에테르화 폴리옥시에틸렌·폴리옥시프로필렌 블락공중합체로부터 선택된 1종 이상의 제2 계면활성제를 포함한다. 본 발명에 따른 현상액은 기포가 적을 뿐 아니라 현상 잔사가 적고 생산성이 우수하다. The present invention relates to a photoresist developer, wherein the developer according to the present invention comprises (a) an alkali compound, (b) a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer or a polyoxypropylene-polyoxyethylene-poly One or more first surfactants selected from oxypropylene triblock copolymers and one or more second surfactants selected from etherified polyoxyethylene-polyoxypropylene block copolymers. The developer according to the present invention not only has a small bubble but also has a low developing residue and excellent productivity.
Description
본 발명은 포토레지스트 현상액에 관한 것으로서, 보다 상세하게는 칼라액정디스플레이의 칼라필터 제조시에 사용되는 안료분산 포토레지스트용 현상액에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist developer, and more particularly, to a developer for pigment dispersion photoresists used in the production of color filters for color liquid crystal displays.
칼라액정디스플레이(LCD)의 제조방법에 대해서는 여러가지 방법이 제안되어 있지만 최근에는 유리등의 투명 기판위에 블랙매트릭스(black matrix)를 제조하고, 그 위에 적색, 녹색, 청색의 화소를 성형한 칼라 필터를 적층한 다음, 그 위에 인듐틴옥사이드(ITO)와 같은 투명전도막을 스퍼터링(sputtering)하여 투명전극을 만든 후, 그 위에 배향막을 성형하고 액정을 배향하는 방법이 일반적으로 사용된다.Various methods have been proposed for manufacturing a color liquid crystal display (LCD), but recently, a black matrix is manufactured on a transparent substrate such as glass, and a color filter in which red, green, and blue pixels are formed thereon is used. After lamination, a method of forming a transparent electrode by sputtering a transparent conductive film such as indium tin oxide (ITO) thereon and then forming an alignment film thereon and aligning the liquid crystal is generally used.
칼라 필터 제조방법에는 안료분산법, 염색법, 염료분산법, 인쇄법, 전착법 등의 방법이 알려져 있고 염료분산법, 염색법 등은 텔레비전용 액정디스플레이에 사용되지만 범용적으로 많이 사용되지는 않는다. Pigment dispersion method, dyeing method, dye dispersion method, printing method, electrodeposition method and the like are known as color filter manufacturing methods. Dye dispersion method and dyeing method are used for liquid crystal displays for televisions, but they are not widely used.
안료분산법은 칼라필터 화소의 위치, 막 두께의 정밀도가 높고 수명이 길며 핀홀 등의 문제가 적기 때문에 컴퓨터를 비롯한 일반적인 기기의 액정디스플레이용으로 주류를 이루고 있다. 안료분산법은 유기안료 혹은 무기안료를 분산시킨 칼라포토레지스트를 스핀코팅(spin coating)하여 특정한 화소의 패턴을 성형하는 방법으로 칼라 필터를 제조한다. 종래의 안료분산법에 의해 제조된 칼라필터의 착색층은 적색, 녹색 및 청색의 화소만 있었지만 요즘에는 카본블랙 등을 분산시킨 블랙매트릭스 층도 칼라포토레지스트를 이용하여 만들고 있다. Pigment dispersion method has become mainstream for the liquid crystal display of general devices such as computers because of the high position of the color filter pixel, the precision of the film thickness, the long life, and the small number of pinholes. In the pigment dispersion method, a color filter is manufactured by spin coating a color photoresist in which an organic pigment or an inorganic pigment is dispersed to form a pattern of a specific pixel. Although the colored layer of the color filter manufactured by the conventional pigment dispersion method had only the red, green, and blue pixel, the black matrix layer which disperse | distributed carbon black etc. is also made using the color photoresist nowadays.
일본특허 특개평 제11-249322호에는 알칼리화합물로 무기알칼리 외에 알카놀아민을 제2성분으로 사용하고 알킬(아릴, 알킬아릴)기에 폴리옥시에틸렌과 폴리옥시프로필렌을 부가한 비이온계면활성제를 사용하여 현상 잔사가 없는 현상방법을 개시하고 있으며, 특개평 제7-120935호에서는 알칼리 화합물과 폴리옥시에틸렌유도체를 사용한 방법으로 정밀한 패턴을 형성할 수 있다고 하였다. 또한, 특개평 제9-171261호에서는 수산화물과 탄산염을 병행 사용한 알칼리 용액과 폴리옥시에틸렌유도체를 사용한 방법으로 정밀한 패턴을 형성할 수 있다고 하였으며, 특개평 제8-101511호에는 지방산알카놀아마이드를 사용한 현상액을, 특개평 제11-305451호에서는 지방산아민에 에틴렌옥사이드 및 프로필렌옥사이드를 부가한 화합물을, 특개평 제11-242342호에서는 알킬페놀에 에틸렌옥사이드를 부가한 화합물을 안료 분산 칼라포토레지스트의 현상액으로 각각 제안하고 있다. In Japanese Patent Laid-Open No. 11-249322, an alkali compound is used, in addition to inorganic alkali, an alkanolamine as a second component, and a nonionic surfactant in which polyoxyethylene and polyoxypropylene are added to an alkyl (aryl, alkylaryl) group. Therefore, a developing method without developing residue is disclosed, and in Japanese Patent Laid-Open No. 7-120935, a precise pattern can be formed by a method using an alkali compound and a polyoxyethylene derivative. In addition, Japanese Patent Application Laid-Open No. 9-171261 discloses that a precise pattern can be formed by using an alkali solution and a polyoxyethylene derivative using a hydroxide and a carbonate in parallel, and Japanese Patent Laid-Open No. 8-101511 uses a fatty acid alkanolamide. A developer is disclosed in Japanese Patent Application Laid-Open No. 11-305451, and a compound in which ethylene oxide and propylene oxide are added to fatty acid amine. We propose each as developer.
그러나, 칼라필터 제조공정의 속도를 향상시키기 위해 현상액에 담그어 포토레지스트를 현상하는 방식에서 벗어나 현상액을 포토레지스트에 직접 뿌리는 방식으로 생산공정이 변하고 있기 때문에 기포가 적게 나는 현상액이 필요하게 되었다. 기존의 제안된 화합물의 구성으로 현상할 경우 스프레이 공정에서 다량의 기포가 발생해 생산속도를 빠르게 할 수 없다는 문제점이 있다.However, in order to improve the speed of the color filter manufacturing process, a developer having low bubbles is required because the production process is changed from a method of dipping in a developer to develop a photoresist and spraying the developer directly on the photoresist. When developing with the conventional composition of the proposed compound, there is a problem in that a large amount of bubbles are generated in the spraying process so that the production speed cannot be increased.
따라서, 본 발명이 이루고자 하는 기술적 과제는 스프레이 방식을 사용하는 포토레지스트 현상공정에서 기포 발생량이 적기 때문에 현상속도가 빠른 현상액을 제공하는 것이다. Therefore, the technical problem to be achieved by the present invention is to provide a developer having a high development speed because the amount of bubbles generated in the photoresist developing process using a spray method is small.
상기 목적을 해결하기 위해, 본 발명에 따른 안료분산 포토레지스트용 현상액은 (a) 알칼리 화합물; (b) 하기 화학식 1의 폴리옥시에틸렌-폴리옥시프로필렌-폴리옥시에틸렌 트리블락공중합체 또는 화학식 2의 폴리옥시프로필렌-폴리옥시에틸렌-폴리옥시프로필렌 트리블락공중합체로부터 선택되는 1종 이상의 제1 계면활성제; 및
(상기 식에서 R은 알킬기, 아릴기, 알킬아릴기 모두 가능하며 알킬기의 경우 탄소수가 1-20개, 아릴기의 탄소수는 6-30개, 알킬아릴기의 탄소수는 7-30개이고 a는 5-20이며 b는 1-10임)(Wherein R is an alkyl group, an aryl group, or an alkylaryl group, and in the case of an alkyl group, 1-20 carbon atoms, 6-30 carbon atoms in an aryl group, 7-30 carbon atoms in an alkylaryl group, and a is 5- 20 and b is 1-10)
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상기 식에서 폴리프로필렌옥사이드는 친유기로 작용하며 폴리에틸렌옥사이드는 친수기로 작용한다. 상기 식에 표시된 에틸렌 옥사이드-프로필렌옥사이드 트리블락공중합체에서 양쪽에 붙은 에틸렌 옥사이드 또는 프로필렌옥사이드의 반복단위 수는 같다. 또한 상기 식에서 제 1계면활성제의 전체 분자량은 1,000∼30,000이고 폴리프로필렌옥사이드의 분자량은 950∼4,000 사이가 바람직하다. 현상액으로 사용될 때 기포 발생량은 분자전체에서 폴리프로필렌옥사이드가 차지하는 분율이 클수록 적게 발생한다. 상기 고분자는 바스프(BASF), 아이씨아이(ICI) 등에서 플루로닉 (Pluronic), 폴록사머(Poloxamer)라는 상품명으로 상업화되어 있다. 구체적인 제품명으로는 바스프사의 에틸렌옥사이드-프로필렌옥사이드-에틸렌옥사이드 형으로는 L10, L31, L35, F38, L42, L43, L44, L61, L62, L63, L64, P65, F68, L72, P75, F77, L81, P84, P85, F87, F88, L92, F98, L101, P103, P104, P105, F018, L121, L122, P123, F127 등이 있으며 프로필렌옥사이드-에틸렌옥사이드-프로필렌옥사이드 형으로는 10R5, 10R8, 12R3, 17R1, 17R2, 17R4,17R8, 25R1, 25R2, 25R4, 25R5, 31R1, 31R2, 31R4 등이 있다.상기 화학식 3 및 4에서, R은 알킬기, 아릴기, 알킬아릴기 모두 가능하며 알킬기의 경우 탄소수가 1∼20개, 아릴기의 탄소수는 6∼30개, 알킬아릴기의 탄소수는 7∼30개인 것이 일반적이며 더 바람직하게는 알킬기의 경우 탄소수 6∼16개, 아릴기의 경우 탄소수가 12∼27개, 알킬아릴기의 경우 탄소수가 12∼27개이다. 에틸렌옥사이드 반복단위 a는 5∼20가 일반적이며 더 바람직하게는 7∼15고, 프로필렌옥사이드 반복단위 b는 1∼10이 일반적이며 더 바람직하게는 1∼5정도이다. a가 5 이하가 되면 물에 잘 녹지 않고 20 이상이 되면 침투력이 나빠져 현상시간이 증가하게 된다. b가 10 이상이 되면 물에 잘 녹지 않게 된다.Wherein polypropylene oxide acts as a lipophilic group and polyethylene oxide acts as a hydrophilic group. In the ethylene oxide-propylene oxide triblock copolymer represented by the above formula, the number of repeating units of ethylene oxide or propylene oxide attached to both sides is the same. In the above formula, the total molecular weight of the first surfactant is preferably 1,000 to 30,000 and the molecular weight of the polypropylene oxide is preferably 950 to 4,000. When used as a developer, the amount of bubble generation occurs as the fraction of polypropylene oxide in the whole molecule increases. The polymer is commercialized under the trade names Pluronic, Poloxamer, etc. from BASF, ICI, and the like. As a specific product name, BASF's ethylene oxide-propylene oxide-ethylene oxide type is L10, L31, L35, F38, L42, L43, L44, L61, L62, L63, L64, P65, F68, L72, P75, F77, L81 , P84, P85, F87, F88, L92, F98, L101, P103, P104, P105, F018, L121, L122, P123, F127, etc.As a propylene oxide-ethylene oxide-propylene oxide type, 10R5, 10R8, 12R3, 17R1, 17R2, 17R4, 17R8, 25R1, 25R2, 25R4, 25R5, 31R1, 31R2, 31R4 and the like. In Chemical Formulas 3 and 4, R is both an alkyl group, an aryl group, an alkylaryl group, and in the case of an alkyl group, It is generally 1 to 20 carbon atoms, 6 to 30 carbon atoms for the aryl group, 7 to 30 carbon atoms for the alkylaryl group, more preferably 6 to 16 carbon atoms for the alkyl group, 12 to 27 carbon atoms for the aryl group In the case of a dog and an alkylaryl group, it is 12-27 carbon atoms. As for ethylene oxide repeating unit a, 5-20 are common, More preferably, it is 7-15, and propylene oxide repeating unit b is 1-10 normally, More preferably, it is about 1-5. If a is less than 5, it is difficult to dissolve in water, but if it is more than 20, the penetration force worsens and the development time is increased. When b is more than 10, it is difficult to dissolve in water.
상기 알칼리 화합물로는 무기 알칼리 화합물 및 유기 알칼리 화합물 모두 사용 가능하며, 구체적으로 수산화리튬, 수산화나트륨, 수산화칼륨, 탄산리튬, 탄산칼륨 및 탄산나트륨로 이루어진 군으로부터 선택되는 무기 알칼리 화합물 또는 암모니아수, 모노에탄올아민, 디에탄올아민, 트리에탄올아민, 모노에틸아민, 디에틸아민, 트리에틸아민 및 테트라메틸암모늄하이드록사이드로 이루어진 군으로부터 선택되는 유기 알칼리 화합물을 사용할 수 있다. 알칼리 화합물은 앞에서 언급된 화합물 1종이상의 혼합물을 사용해 pH가 9∼13정도 되도록 조절하여 사용하는 것이 일반적이다. 더 바람직하게는 pH 10∼12.5이며 pH가 9이하가 되면 현상잔류물이 생기는 경우가 있고 pH 13이상이 되면 화소의 부분 혹은 전체가 박리될 수 있다.As the alkali compound, both an inorganic alkali compound and an organic alkali compound can be used, and specifically, an inorganic alkali compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, potassium carbonate and sodium carbonate or ammonia water, monoethanolamine , An organic alkali compound selected from the group consisting of diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine and tetramethylammonium hydroxide can be used. The alkali compound is generally used to adjust the pH to about 9-13 using a mixture of at least one compound mentioned above. More preferably, when the pH is 10 to 12.5 and the pH is 9 or less, developing residues may occur. When the pH is 13 or more, a part or the whole of the pixel may be peeled off.
또한, 상기 제1 계면활성제의 농도는 0.03∼0.5중량%이며, 바람직하게는 0.05 ∼0.3중량%이다. 계면활성제의 농도가 0.03중량%이하이면 현상 잔류물이 생기고 0.5중량% 이상이 되면 기포가 발생하여 현상속도가 떨어지게 된다. Moreover, the density | concentration of the said 1st surfactant is 0.03-0.5 weight%, Preferably it is 0.05-0.3 weight%. If the concentration of the surfactant is less than 0.03% by weight, developing residues are formed. When the concentration of the surfactant is more than 0.5% by weight, bubbles are generated to decrease the developing speed.
본 발명에 따른 현상액에 있어, 제1 계면활성제를 단독으로 사용해도 충분히 기포가 적은 칼라포토레지스트의 현상이 가능하지만 제2 계면활성제와 병행 사용할 경우, 현상 잔사가 적어 화소의 패턴이 정밀해진다. 상기 제2 계면활성제를 병용한 현상액에서 계면활성제의 전체농도는 0.03∼0.5%이고 전체 계면활성제 중 제2 계면활성제의 비율은 90% 이하이며 더 바람직하게는 70% 이하이다. 제2 계면활성제의 비율이 90% 이상이 되면 기포가 발생하여 작업속도가 떨어지게 된다. In the developer according to the present invention, even when the first surfactant is used alone, development of a sufficiently small color photoresist is possible, but when used in combination with the second surfactant, there is less development residue and the pattern of the pixel is precise. In the developer using the second surfactant in combination, the total concentration of the surfactant is 0.03 to 0.5%, and the ratio of the second surfactant in the total surfactant is 90% or less, more preferably 70% or less. When the ratio of the second surfactant is 90% or more, bubbles are generated to decrease the working speed.
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이하, 실시예 및 비교예를 통해 본발명을 보다 구체적으로 설명하지만 본발명이 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
실시예 1Example 1
유기안료로서는 적색의 경우 칼라인덱스명으로 피그먼트 레드 224, 177을 각각 40g을 사용하였다. 알칼리 가용성수지로서 아크릴산/메타크릴산/2-하이드록시 에틸메타크릴레이트/벤질메타크릴레이트 공중합체(공중합비 = 10/10/10/70, 수평균분자량 10,000) 40g, 다관능단량체로서 디펜타에리스톨 헥사아크릴레이트 20g, 광중합개시제로서 2,2-비스(2,4디클로로페닐)-4,4,5,5-테트라페닐-1,2-디이미다졸 5g과 4,4,-비스(디에틸아미노)벤조페논 5g과 2-벤질-2-디메틸아민노-1-(4-몰포리노페닐)부탄-1-온 20g, 또 촉매로서 감마-메타크릴록시프로필메틸디메톡시실란 10g을 유기용제, 에틸렌글리콜 에틸에테르 아세테이트와 섞어 1000g의 포토레지스트 액상 조성물을 제조하였다. 안료농도는 전고형분중 약 44%였다. 다음으로, 표면에 나트륨이온이 용출되는 것을 방지하기 위해, 포토레지스트 액상 조성물을 이산화규소막을 코팅한 소다글래스기판 위에 스핑코팅하여 도포했다. 코팅된 기판을 약 80℃에서 10분간 베이킹하여 2.0㎛의 막을 얻었다. 베이킹한 기판을 실온까지 냉각한 후 포토마스크(photomask)를 기판 사이에 두고 수은등을 사용하여 365nm, 405nm 및 436nm의 각 파장을 함유하는 자외선을 10mJ/cm2의 노광량으로 노광하였다. 한편, 알칼리 화합물로서 수산화칼륨, 제1 계면활성제로서 17R4(바스프사 제조) 0.1g을 포함하며 pH가 12.0인 현상액을 제조하였다. 노광된 기판을 상기 현상액 600g을 스프레이하여 현상한 후, 증류수로 세정하여 화소를 형성하였다. 현상할 때 기포가 넘치지 않도록 조절하여 현상속도를 조절하였으며 화소가 형성된 후 전자현미경으로 화소를 관찰하여 현상의 선명도를 관찰하였다.As an organic pigment, 40g of pigment red 224 and 177 was used for the color index name in the case of red, respectively. 40 g of acrylic acid / methacrylic acid / 2-hydroxy ethyl methacrylate / benzyl methacrylate copolymer (copolymerization ratio = 10/10/10/70, number average molecular weight 10,000) as an alkali-soluble resin, dipenta as a polyfunctional monomer 20 g of erythol hexaacrylate, 5 g of 2,2-bis (2,4 dichlorophenyl) -4,4,5,5-tetraphenyl-1,2-diimidazole and 4,4, -bis (as photopolymerization initiator) 5 g of diethylamino) benzophenone, 20 g of 2-benzyl-2-dimethylamineno-1- (4-morpholinophenyl) butan-1-one, and 10 g of gamma-methacryloxypropylmethyldimethoxysilane as catalysts 1000 g of a photoresist liquid composition was prepared by mixing with a solvent and ethylene glycol ethyl ether acetate. The pigment concentration was about 44% of the total solids. Next, in order to prevent elution of sodium ions on the surface, the photoresist liquid composition was spun-coated and applied on a soda glass substrate coated with a silicon dioxide film. The coated substrate was baked at about 80 ° C. for 10 minutes to obtain a 2.0 μm film. After baking the board | substrate to room temperature, the ultraviolet-ray containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed by the exposure amount of 10 mJ / cm <2> using a mercury lamp, using a photomask between substrates. On the other hand, a developer was prepared containing 0.1 g of potassium hydroxide as the alkali compound and 0.1 g of 17R4 (manufactured by BASF Corporation) as the first surfactant and having a pH of 12.0. The exposed substrate was developed by spraying 600 g of the developer, and then washed with distilled water to form a pixel. The development speed was controlled by adjusting the bubble so that it did not overflow, and the sharpness of the phenomenon was observed by observing the pixel with an electron microscope after the pixel was formed.
현상속도는 칼라필터 1장을 현상하기 위한 속도로 표시하였으며 수치가 작을수록 현상속도가 빠름을 알수 있다. The development speed is expressed as the speed for developing one color filter, and the smaller the value, the faster the development speed.
실시예 2Example 2
제1 계면활성제로서 10R8(바스프사 제조) 0.1g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developing solution was prepared in the same manner as in Example 1 except that 0.1 g of 10R8 (manufactured by BASF Corporation) was used as the first surfactant.
실시예 3Example 3
제1 계면활성제로서 31R2(바스프사 제조) 0.1g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1 except that 0.1 g of 31R2 (manufactured by BASF Corporation) was used as the first surfactant.
실시예 4Example 4
제1 계면활성제로서 L31(바스프사 제조) 0.1g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1, except that 0.1 g of L31 (manufactured by BASF Corporation) was used as the first surfactant.
실시예 5Example 5
제1 계면활성제로서 L44(바스프사 제조) 0.1g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1 except that 0.1 g of L44 (manufactured by BASF Corporation) was used as the first surfactant.
실시예 6Example 6
제1 계면활성제로서 P103(바스프사 제조) 0.1g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1 except that 0.1 g of P103 (manufactured by BASF Corporation) was used as the first surfactant.
실시예 7Example 7
실시예 1에서 사용한 제1 계면활성제인 17R4(바스프사 제조)의 양을 0.05g으로 사용하여 농도를 변화시킨것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1 except that the concentration of 17R4 (manufactured by BASF Corporation), which is the first surfactant used in Example 1, was changed to 0.05 g.
실시예 8Example 8
실시예 1에서 사용한 제1 계면활성제인 17R4(바스프사 제조)의 양을 0.2g으로 사용하여 농도를 변화시킨것 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1, except that the concentration of 17R4 (manufactured by BASF Corporation), which is the first surfactant used in Example 1, was changed to 0.2 g.
실시예 9Example 9
알칼리 화합물로서 수산화나트륨을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 1 except that sodium hydroxide was used as the alkali compound.
실시예 10Example 10
제1 계면활성제로서 17R4(바스프사 제조) 0.07g을 포함하며 제2 계면활성제로서 NP-E10(한국 폴리올 제조) 0.03g을 포함하는 것을 제외하고는 실시예 1과 동일한 방법으로 현상액을 제조하였다. A developer was prepared in the same manner as in Example 1 except that 0.07 g of 17R4 (manufactured by BASF Corporation) was included as the first surfactant and 0.03 g of NP-E10 (manufactured by Korean Polyol) was included as the second surfactant.
실시예 11Example 11
제1 계면활성제로서 17R4(바스프사 제조) 0.04g 및 제2 계면활성제로서 NP-E10 0.06g을 포함하는 것을 제외하고는 실시예 10과 동일한 방법으로 현상액을 제조하였다. A developer was prepared in the same manner as in Example 10, except that 0.04 g of 17R4 (manufactured by BASF Corporation) and 0.06 g of NP-E10 were included as the second surfactant.
실시예 12Example 12
제2 계면활성제로서 NP-E10P2(한국 폴리올 제조) 0.03g을 포함하는 것을 제외하고는 실시예 10과 동일한 방법으로 현상액을 제조하였다. A developer was prepared in the same manner as in Example 10, except that 0.03 g of NP-E10P2 (manufactured by Korean Polyol) was included as the second surfactant.
실시예 13Example 13
제2 계면활성제로서 OP-E10(한국 폴리올 제조) 0.03g을 포함하는 것을 제외하고는 실시예 10과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 10, except that 0.03 g of OP-E10 (manufactured by Korean Polyol) was included as the second surfactant.
실시예 14Example 14
제2 계면활성제로서 LA-E7(한국 폴리올 제조) 0.03g을 포함하는 것을 제외하고는 실시예 10과 동일한 방법으로 현상액을 제조하였다. A developer was prepared in the same manner as in Example 10 except that 0.03 g of LA-E7 (manufactured by Korean Polyol) was included as the second surfactant.
비교예 1Comparative Example 1
제1 계면활성제를 사용하지 않고, 제2 계면활성제인 NP-E10의 양을 0.1g으로 사용하여 농도를 변화시킨것을 제외하고는 실시예 10과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 10, except that the concentration was changed by using the amount of NP-E10, which is the second surfactant, as 0.1 g without using the first surfactant.
비교예 2Comparative Example 2
제1 계면활성제를 사용하지 않고, 제2 계면활성제인 OP-E10의 양을 0.1g으로 사용하여 농도를 변화시킨것을 제외하고는 실시예 13과 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 13, except that the concentration of the OP-E10, which is the second surfactant, was changed to 0.1 g without using the first surfactant.
비교예 3Comparative Example 3
제1 계면활성제를 사용하지 않고, 제2 계면활성제인 LA-E7의 양을 0.1g으로 사용하여 농도를 변화시킨것을 제외하고는 실시예 14와 동일한 방법으로 현상액을 제조하였다.A developer was prepared in the same manner as in Example 14, except that the concentration was changed by using the amount of LA-E7, which is the second surfactant, in 0.1 g without using the first surfactant.
상기 현상액의 조성 및 평가에 대한 결과를 하기 표 1에 나타낸다.The results of the composition and evaluation of the developer are shown in Table 1 below.
상기에서, 17R4, 10R8, 31R2, L31, L44, P103는 바스프사에서 생산하는 에틸렌옥사이드 -프로필렌옥사이드 트리 블락 코폴리머이고, NP-E10은 노닐페놀에 에틸렌옥사이드를 10몰 부가한 제품이며 NP-E10P2는 에틸렌옥사이드를 10몰, 프로필렌옥사이드 2몰 부가한 제품이다. 한편, OP, LA는 옥틸페놀, 라우릴알콜을 지칭한다.In the above description, 17R4, 10R8, 31R2, L31, L44 and P103 are ethylene oxide-propylene oxide triblock copolymers produced by BASF Corporation, NP-E10 is a product obtained by adding 10 moles of ethylene oxide to nonylphenol, and NP-E10P2. Is a product in which 10 mol of ethylene oxide and 2 mol of propylene oxide are added. On the other hand, OP, LA refers to octylphenol, lauryl alcohol.
패턴 선명도는 5:매우좋음, 4:좋음, 3:보통, 2:불량, 1:매우나쁨을 나타낸다.The pattern clarity is 5: very good, 4: good, 3: normal, 2: poor, 1: very bad.
상기 설명한 바와 같이, 본 발명에 의한 포토레지스트 현상액은 칼라필터의 제조에 있어서 알칼리 침투속도가 빠르고 현상 잔사가 적을 뿐만 아니라, 패턴 선명도가 우수하다. 또한, 스프레이식 현상공정시 기포의 발생이 적기 때문에 현상속도가 빨라서 생산성을 향상시킬 수 있다. As described above, the photoresist developer according to the present invention not only has a high alkali penetration rate and a low development residue in the production of a color filter, but also has excellent pattern clarity. In addition, since the generation of bubbles in the spray developing process is less, the development speed is faster, it is possible to improve the productivity.
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WO1996034317A1 (en) * | 1995-04-28 | 1996-10-31 | Polaroid Corporation | On-press removable overcoat for lithographic printing plates |
JPH11160866A (en) * | 1997-11-26 | 1999-06-18 | Fuji Photo Film Co Ltd | Positive photoresist composition |
JP2001075283A (en) * | 1999-09-06 | 2001-03-23 | Fuji Photo Film Co Ltd | Positive type electron beam or x-ray resist composition |
KR20010030347A (en) * | 1999-09-27 | 2001-04-16 | 무네유키 가코우 | Positive photoresist composition |
KR20010040136A (en) * | 1999-10-20 | 2001-05-15 | 무네유키 가코우 | Positive photoresist composition for far ultraviolet rays exposure |
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WO1996034317A1 (en) * | 1995-04-28 | 1996-10-31 | Polaroid Corporation | On-press removable overcoat for lithographic printing plates |
JPH11160866A (en) * | 1997-11-26 | 1999-06-18 | Fuji Photo Film Co Ltd | Positive photoresist composition |
JP2001075283A (en) * | 1999-09-06 | 2001-03-23 | Fuji Photo Film Co Ltd | Positive type electron beam or x-ray resist composition |
KR20010030347A (en) * | 1999-09-27 | 2001-04-16 | 무네유키 가코우 | Positive photoresist composition |
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