KR20110011996A - Cleaning composition and process of cleaning panel using the composition - Google Patents
Cleaning composition and process of cleaning panel using the composition Download PDFInfo
- Publication number
- KR20110011996A KR20110011996A KR1020090069506A KR20090069506A KR20110011996A KR 20110011996 A KR20110011996 A KR 20110011996A KR 1020090069506 A KR1020090069506 A KR 1020090069506A KR 20090069506 A KR20090069506 A KR 20090069506A KR 20110011996 A KR20110011996 A KR 20110011996A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- cleaning
- cleaning liquid
- formula
- flat panel
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
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- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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Abstract
Description
본 발명은 액정 디스플레이, 플라즈마 디스플레이, 플렉서블 디스플레이 등의 플랫 패널 디스플레이(이하‘FPD’라 한다)용 기판의 세정액 및 이것을 이용한 세정 방법에 관한 것이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid for a substrate for flat panel displays (hereinafter referred to as "FPD"), such as a liquid crystal display, a plasma display, and a flexible display, and a cleaning method using the same.
액정 디스플레이로 대표되는 FPD는, 반도체 디바이스와 같이, 성막, 노광, 배선 에칭 등의 공정을 거쳐 제품이 제조된다. 하지만, 이러한 공정에 의해서, 기판 표면에 각종의 유기물이나 무기물 등의 크기가 1㎛ 이하의 매우 작은 파티클(Particle)의 부착 오염이 발생한다. 이러한 오염물이 부착한 채로, 다음의 공정 처리를 실시했을 경우, 막의 핀홀이나 피트, 배선의 단선이나 브릿지(Bridge)가 발생하여, 제품의 제조수율이 저하된다.FPD represented by a liquid crystal display is manufactured like a semiconductor device through processes, such as film-forming, exposure, wiring etching, and the like. However, by such a process, adhesion contamination of very small particles having a size of 1 μm or less of various organic materials or inorganic materials occurs on the surface of the substrate. When the following process treatment is carried out with these contaminants attached, pinholes, pits, disconnection of wires or bridges are generated, and the yield of the product is reduced.
따라서 오염물을 제거하기 위한 세정이 각 공정간에 행해지고 있고, 이를 위한 세정액에 대해서도 많은 제안이 나와 있다. 예를 들면, 일본공개특허 2005-154558호 공보에는, H3PO4, HF, 암모니아, 및/또는 아민을 함유하는 세정액이 제안 되고 있다. 그렇지만, 이 특허는 반도체 디바이스용 세정액일뿐만 아니라, 가장 대표적인 FPD 기판인 유리기판과, 가장 대표적인 배선재료인 Al을 격렬하게 에칭(Etching)하는 HF를 포함하고 있기 때문에, FPD용 기판의 세정에는 사용할 수 없다. Therefore, cleaning to remove contaminants is performed between the steps, and many proposals have been made for the cleaning liquid for this purpose. For example, Japanese Laid-Open Patent Publication No. 2005-154558 proposes a cleaning liquid containing H 3 PO 4 , HF, ammonia, and / or an amine. However, this patent is not only a cleaning liquid for semiconductor devices, but also includes a glass substrate, which is the most representative FPD substrate, and HF, which intensively etches Al, which is the most representative wiring material, and thus can be used to clean the FPD substrate. Can't.
일본공개특허 2000-232063호 공보에는 인산과 인산 암모늄을 부식방지제로 이용하는 것이 제안되었으나, 적용 공정이 레지스트 잔사제거용일 뿐만 아니라 사용된 조성물의 pH도 산성범위에서 사용되고 있어, 세정 초기의 단계의 기본적 특성인 유기물이나 무기물 등의 크기가 1㎛이하의 매우 작은 파티클(Particle) 제거성과 알루미늄 배선의 부식 방지성과의 양립이 불충분하다.Japanese Unexamined Patent Application Publication No. 2000-232063 proposes to use phosphoric acid and ammonium phosphate as corrosion inhibitors, but the application process is not only for removing resist residues, but also the pH of the used composition is used in an acidic range. Phosphorus organic matter, inorganic matters, and the like have a very small particle removal of less than 1 μm and insufficient compatibility between corrosion resistance of aluminum wiring.
한편, 대한민국등록특허 10-0574607호 공보에는 산성의 pH 환경 하에 탈이온수, 유기화합물 및 암모늄화합물을 포함하는 세정액을 제안하였다. 그러나 상기의 특허와 마찬가지로 산성 범위의 용액이므로 세정 초기의 단계의 기본적 특성인 유기물이나 무기물 등의 크기가 1 ㎛이하의 매우 작은 파티클(Particle) 제거성이 불충분하다.On the other hand, Korean Patent Publication No. 10-0574607 proposed a cleaning solution containing deionized water, organic compounds and ammonium compounds in an acidic pH environment. However, as in the above patent, since the solution is in the acidic range, very small particles (particles) having a size of 1 μm or less, which is a basic characteristic of the initial stage of cleaning, is insufficient.
한편, 대한민국 등록특허 10-0599849호 공보에서 요소 및/또는 에틸렌요소, 제 4급 암모늄수산화물, 암모니아 등의 알칼리 성분, 시트르산(CITRIC ACID), 말산(MALIC ACID), 타르타르산(TARTARIC ACID) 등의 유기산 및/또는 그 염, 그리고 잔량이 탈이온 증류수를 포함하는 세정액을 제안하였으나, 장시간 사용 시 요소 또는 에틸렌 요소의 석출 문제가 발생할 수 있다. On the other hand, Korean Patent Publication No. 10-0599849 discloses an organic acid such as urea and / or ethylene urea, quaternary ammonium hydroxide, alkali components such as ammonia, citric acid (CITRIC ACID), malic acid (MALIC ACID), tartaric acid (TARTARIC ACID) And / or a salt thereof and a residual amount of the washing liquid containing deionized distilled water, but problems of precipitation of urea or ethylene urea may occur when used for a long time.
본 발명의 목적은 FPD 기판을 제작하는 공정에서 유리기판 상에 존재하는 유기오염물이나 파티클 제거에 적합한 세정액 조성물 및 세정 방법을 제공하는 것이다.It is an object of the present invention to provide a cleaning liquid composition and cleaning method suitable for removing organic contaminants or particles present on a glass substrate in a process of manufacturing an FPD substrate.
본 발명의 또 다른 목적은 FPD 기판상에 형성되어 있는 구리, 알루미늄 혹은 구리 합금 배선, 알루미늄 합금 배선을 부식시키지 않는 세정액 조성물 및 세정 방법을 제공하는 것이다.Still another object of the present invention is to provide a cleaning liquid composition and a cleaning method which do not corrode copper, aluminum or copper alloy wiring, and aluminum alloy wiring formed on the FPD substrate.
본 발명은 하기 화학식 1 또는 화학식 2로 표시되는 고리형 아민 화합물; 아졸계 화합물, 알칸올 아민염 및 환원제로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함하는 첨가제; 및 물을 포함하는 것을 특징으로 하는 플랫 패널 디스플레이 기판용 세정액 조성물을 제공한다.The present invention is a cyclic amine compound represented by the formula (1) or formula (2); Additives comprising one or two or more selected from the group consisting of azole compounds, alkanol amine salts and reducing agents; And it provides a cleaning liquid composition for a flat panel display substrate comprising water.
<화학식 1><Formula 1>
<화학식 2><Formula 2>
상기 화학식 1 및 상기 화학식 2에서, R1, R2 및 R4는 각각 독립적으로 수소, C1~C10의 직쇄 또는 사슬형 알킬기, C6~C10의 아릴기C1~C10의 직쇄 또는 사슬형 알킬아미노기, C1~C10의 직쇄 또는 사슬형 히드록시알킬기, C1~C10의 직쇄 또는 사슬형 알킬벤젠기 또는 아미노기이고, R3 및 R5는 수소, C1~C10의 직쇄 또는 사슬형 알킬기, C6~C10의 아릴기, C1~C10의 직쇄 또는 사슬형 알킬아미노기 또는 아미노기이고, X1은 C, S, O 또는 N이고, n1은 1 또는 2의 정수이고, n2는 1 내지 4의 정수이다.In Formula 1 and Formula 2, R 1, R 2 and R 4 are each independently hydrogen, C 1 ~ C 10 straight-chain or a chain-like alkyl group, a straight-chain of C 6 ~ C 10 aryl group, C 1 ~ C 10 of Or a chain alkylamino group, C 1 to C 10 straight or chain hydroxyalkyl group, C 1 to C 10 linear or chain alkylbenzene group or amino group, R 3 and R 5 are hydrogen, C 1 to C 10 Is a linear or chain alkyl group of C 6 to C 10 aryl, C 1 to C 10 linear or chain alkylamino group or amino group, X 1 is C, S, O or N, n 1 is 1 or 2 It is an integer, n 2 is an integer of 1 to 4.
또한, 본 발명은 상기 세정액 조성물을 이용한 플랫 패널 디스플레이 기판의 세정방법을 제공한다.The present invention also provides a method for cleaning a flat panel display substrate using the cleaning liquid composition.
본 발명의 세정액 조성물은 플랫 패널 디스플레이 기판의 유리 표면에 대한 유기물오염 및 파티클 제거력이 우수하고, 기판상에 형성되어 있는 구리 및 구리 합금 배선의 부식방지 효과가 우수하고, 다량의 탈이온수를 포함하고 있어 취급이 용이하며 환경적으로 유리한 효과가 있다.The cleaning liquid composition of the present invention has excellent organic contamination and particle removal ability on the glass surface of the flat panel display substrate, excellent corrosion protection effect of copper and copper alloy wiring formed on the substrate, and contains a large amount of deionized water. It is easy to handle and has an environmentally beneficial effect.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 플랫 패널 디스플레이 기판용 세정액 조성물은 고리형 아민 화합물, 첨가제 및 물을 포함한다.The cleaning liquid composition for a flat panel display substrate of the present invention contains a cyclic amine compound, an additive, and water.
본 발명의 플랫 패널 디스플레이 기판용 세정액 조성물에 포함되는 고리형 아민 화합물은 하기 화학식 1 또는 화학식 2로 표시된다. The cyclic amine compound included in the cleaning liquid composition for a flat panel display substrate of the present invention is represented by the following general formula (1) or (2).
<화학식 1><Formula 1>
<화학식 2><Formula 2>
상기 화학식 1 및 상기 화학식 2에서, R1, R2 및 R4는 각각 독립적으로 수소, C1~C10의 직쇄 또는 사슬형 알킬기, C6~C10의 아릴기C1~C10의 직쇄 또는 사슬형 알 킬아미노기, C1~C10의 직쇄 또는 사슬형 히드록시알킬기, C1~C10의 직쇄 또는 사슬형 알킬벤젠기 또는 아미노기이고, R3 및 R5는 수소, C1~C10의 직쇄 또는 사슬형 알킬기, C6~C10의 아릴기, C1~C10의 직쇄 또는 사슬형 알킬아미노기 또는 아미노기이고, X1은 C, S, O 또는 N이고, n1은 1 또는 2의 정수이고, n2는 1 내지 4의 정수이다.In Formula 1 and Formula 2, R 1, R 2 and R 4 are each independently hydrogen, C 1 ~ C 10 straight-chain or a chain-like alkyl group, a straight-chain of C 6 ~ C 10 aryl group, C 1 ~ C 10 of or a chain-like Al skill group, C 1 ~ C 10 straight-chain or a chain hydroxyalkyl group, C 1 ~ linear or chain-like alkyl benzene group or an amino group of the C 10 of, R 3 and R 5 is hydrogen, C 1 ~ C 10 straight or chain alkyl group, C 6 to C 10 aryl group, C 1 to C 10 straight chain or chain alkylamino group or amino group, X 1 is C, S, O or N, n 1 is 1 or It is an integer of 2 , n <2> is an integer of 1-4.
상기 화학식 1 또는 화학식 2로 표시되는 고리형 아민 화합물은 조성물 총 중량에 대하여 0.05 내지 5중량%로 포함되는 것이 바람직하며, 0.1 내지 1중량%로 포함되는 것이 보다 바람직하다. 상술한 범위 미만으로 포함되면 충분한 세정효과를 구현할 수 없고, 상술한 범위를 초과하여 포함되면 세정액 내의 활동도를 저하시켜 파티클 제거 효과를 감소시키거나 구리, 구리합금, 알루미늄 또는 알루미늄 합금으로 이루어진 배선에 대한 부식이 증가한다. The cyclic amine compound represented by Formula 1 or Formula 2 is preferably included in 0.05 to 5% by weight, more preferably in 0.1 to 1% by weight based on the total weight of the composition. If it is included in the above-mentioned range, sufficient cleaning effect cannot be realized, and if it is included in the above-mentioned range, the activity in the cleaning liquid may be reduced to reduce particle removal effect or to the wiring made of copper, copper alloy, aluminum, or aluminum alloy. Corrosion increases.
상기 화학식 1 또는 화학식 2로 표시되는 고리형 아민 화합물은 N-(2-히드록시에틸)피페리딘, N-(2-히드록시프로필)피페리딘, N-(2-히드록시 부틸)피페리딘, 1-(2-히드록시에틸)-2-피롤리돈, 1-(2-히드록시프로필)-2-피롤리돈 및 1-(2-히드록시부틸)-2-피롤리돈으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 이 중에서 N-(2-히드록시에틸)피페리딘, N-(2-히드록시프로필)피페리딘, 1-(2-히드록시에틸)-2-피롤리돈 등이 보다 바람직하다. The cyclic amine compound represented by Formula 1 or Formula 2 is N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N- (2-hydroxybutyl) pi Ferridine, 1- (2-hydroxyethyl) -2-pyrrolidone, 1- (2-hydroxypropyl) -2-pyrrolidone and 1- (2-hydroxybutyl) -2-pyrrolidone It is preferably one or two or more selected from the group consisting of. Among these, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, 1- (2-hydroxyethyl) -2-pyrrolidone, and the like are more preferable.
본 발명의 플랫 패널 디스플레이 기판용 세정액 조성물에 포함되는 첨가제 는 아졸계 화합물, 알칸올 아민염 및 환원제로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함한다. 상기 첨가제는 알루미늄, 구리, 또는 구리 합금, 알루미늄 합금 등의 금속막의 부식을 최소화한다.The additive contained in the cleaning liquid composition for a flat panel display substrate of the present invention includes one or two or more selected from the group consisting of an azole compound, an alkanol amine salt, and a reducing agent. The additive minimizes corrosion of metal films such as aluminum, copper, or copper alloys and aluminum alloys.
상기 첨가제는 조성물 총 중량에 대하여, 0.01 내지 10중량%로 포함되는 것이 바람직하고, 0.1 내지 3 중량%로 포함되는 것이 보다 바람직하다. 상술한 범위를 만족하면, 알루미늄, 구리, 또는 알루미늄 합금, 구리 합금 등의 금속막의 손상을 최소화하고, 경제적이다.The additive is preferably included in an amount of 0.01 to 10% by weight, and more preferably 0.1 to 3% by weight based on the total weight of the composition. When the above range is satisfied, damage to metal films such as aluminum, copper, or an aluminum alloy, a copper alloy is minimized and economical.
상기 아졸계 화합물은 트리아졸 고리를 포함하는 것이 바람직하다. 상기 트리아졸 고리에 존재하는 질소 원자의 비공유전자쌍이 구리와 전자적으로 결합하여 금속 부식을 제어한다. 상기 아졸계 화합물은 톨리트리아졸, 1,2,3-벤조트리아졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 3-아미노-1,2,4-트리아졸, 4-아미노-4H-1,2,4-트리아졸, 1-히드록시벤조트리아졸, 1-메틸벤조트리아졸, 2-메틸벤조트리아졸, 5-메틸벤조트리아졸, 벤조트리아졸-5-카르본산, 니트로벤조트리아졸 및 2-(2H-벤조트리아졸-2-일)-4,6-디-t-부틸페놀, 2,2’-[[[에틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다.It is preferable that the said azole type compound contains a triazole ring. Non-covalent electron pairs of nitrogen atoms present in the triazole ring electronically bond with copper to control metal corrosion. The azole compound is tolytriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole , 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5 -Carboxylic acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazole It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of -1-yl] methyl] imino] bisethanol.
상기 알칸올 아민염은 금속 패턴 및 산화막이 존재하는 기판의 세정 공정시 금속의 부식 및 산화막의 과식각을 방지하며 세정액의 pH변화를 억제하는 pH완충 효과를 갖는다. 상기 알칸올 아민염의 제조시 염 생성 반응의 온도는 90℃ 이하에서 유지되는 것이 바람직하다. The alkanol amine salt has a pH buffering effect that prevents corrosion of the metal and overetching of the oxide film during the cleaning process of the substrate having the metal pattern and the oxide film and suppresses the pH change of the cleaning solution. In the preparation of the alkanol amine salt, the temperature of the salt formation reaction is preferably maintained at 90 ° C or less.
상기 알칸올 아민염은 알킬 부분이 통상 저급 알킬 즉, C1 내지 C5 알킬인 알칸올아민으로부터 선택되는 것이 바람직하다. 또한, 1개 이상의 히드록시기가 남아있다면 다른 치환체가 아민기 중에 존재할 수 있으므로, 디메틸 메탄올아민염과 같은 다른 저급 알칸올 아민염을 사용하는 것도 바람직하다. 상기 알칸올 아민염의 구체적인 예로는 모노에탄올아민염, 디에탄올아민염, 트리에탄올아민염, 모노이소프로판올아민염, 디이소프로판올아민염 및 트리이소프로판올아민염 등을 들 수 있다. 상기 알칸올 아민염으로서, 시판된 제품을 사용해도 무방하다. 시판된 제품의 예로는 AB RUST CM(LABEMA Co. 제품), AB RUST A4(LABEMA Co. 제품), EMADOX-NA(LABEMA Co. 제품), EMADOX-NB(LABEMA Co. 제품), EMADOX-NCAL(LABEMA Co. 제품), EMADOX-102(LABEMA Co. 제품), EMADOX-103(LABEMA Co. 제품), EMADOX-D520(LABEMA Co. 제품) 및 AB Rust at(LABEMA Co. 제품) 등을 들 수 있다.The alkanol amine salt is preferably selected from alkanolamines wherein the alkyl moiety is usually lower alkyl, ie C1 to C5 alkyl. It is also preferable to use other lower alkanol amine salts, such as dimethyl methanolamine salt, since other substituents may be present in the amine group if one or more hydroxy groups remain. Specific examples of the alkanol amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts and triisopropanolamine salts. As the alkanol amine salt, a commercially available product may be used. Examples of commercially available products include AB RUST CM (product of LABEMA Co.), AB RUST A4 (product of LABEMA Co.), EMADOX-NA (product of LABEMA Co.), EMADOX-NB (product of LABEMA Co.), EMADOX-NCAL ( LABEMA Co.), EMADOX-102 (manufactured by LABEMA Co.), EMADOX-103 (manufactured by LABEMA Co.), EMADOX-D520 (manufactured by LABEMA Co.), and AB Rust at (manufactured by LABEMA Co.). .
상기 환원제는 금속 배선의 부식 진행 단계라 할 수 있는 산화막 형성을 억제함으로써 금속 배선의 부식을 방지하는 역할을 한다. 상기 환원제는 엘리소르빈산, 비타민 C 및 알파 토코페롤으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. The reducing agent serves to prevent corrosion of the metal wiring by inhibiting the formation of an oxide film, which may be referred to as the progress of corrosion of the metal wiring. The reducing agent is preferably one or two or more selected from the group consisting of elisorbic acid, vitamin C and alpha tocopherol.
본 발명의 플랫 패널 디스플레이 기판용 세정액 조성물에 포함되는 물은 잔량 포함된다. 상기 물은 탈이온수인 것이 바람직하고, 탈이온 증류수인 것이 보다 바람직하다. 상기 물이 포함되면, 경제적이고 환경친화적인 세정액 조성물을 제공할 수 있다.The residual amount of water contained in the cleaning liquid composition for flat panel display substrates of this invention is contained. It is preferable that it is deionized water, and, as for the said water, it is more preferable that it is deionized distilled water. When the water is included, it is possible to provide an economical and environmentally friendly cleaning liquid composition.
본 발명의 플랫 패널 디스플레이 기판용 세정액 조성물은 폴리카르복실산 공중합체, 양자성 알킬렌글리콜 모노알킬에테르 화합물 및 계면활성제로 이루어진 군에서 선택되는 1종 또는 2종 이상을 더 포함하는 것이 바람직하다.It is preferable that the cleaning liquid composition for flat panel display substrates of this invention further contains 1 type (s) or 2 or more types selected from the group which consists of a polycarboxylic acid copolymer, a proton alkylene glycol monoalkyl ether compound, and surfactant.
본 발명의 세정액 조성물에 추가로 포함된 폴리카르복실산계 공중합체는 금속부식방지 및 pH조절제 역할을 한다. The polycarboxylic acid copolymer further included in the cleaning liquid composition of the present invention serves as a metal corrosion prevention and pH adjusting agent.
상기 폴리카르복실산 공중합체는 금속의 표면에 보호막층을 형성하여 알칼리 이온과의 과도한 반응을 억제하여 금속의 부식방지을 방지할 수 있고, pH조절제 역할을 한다. 상기 폴리카르복실산 공중합체는 하기 화학식 3으로 표시되는 구조단위를 포함하는 것이 바람직하다.The polycarboxylic acid copolymer may form a protective layer on the surface of the metal to inhibit excessive reaction with alkali ions, thereby preventing corrosion of the metal, and serves as a pH adjusting agent. The polycarboxylic acid copolymer preferably includes a structural unit represented by the following formula (3).
<화학식 3><Formula 3>
상기 화학식 3에서,In Chemical Formula 3,
R7 내지 R9 는 각각 독립적으로, 수소, 메틸기, 에틸기 또는 (CH2)m2COOM2이고, M1 및 M2는 각각 독립적으로 수소, 알칼리 금속, 알칼리 토금속, 암모늄기, C1~C10의 알킬암모늄기 또는 C1~C10의 치환알킬암모늄기이고, m1 및 m2 는 각각 독립적으로 0 내지 2의 정수이다.R 7 to R 9 are each independently hydrogen, methyl group, ethyl group or (CH 2 ) m 2 COOM 2 , and M 1 and M 2 are each independently hydrogen, alkali metal, alkaline earth metal, ammonium group, C 1 to C 10 It is an alkylammonium group of or C 1 ~ C 10 substituted alkylammonium group, m 1 and m 2 are each independently an integer of 0 to 2.
상기 폴리카르복실산 공중합체는 상기 화학식 3으로 표시되는 구조단위를 갖는 단량체를 포함하는 것이 바람직하다. 상기 화학식 3으로 표시되는 구조단위를 갖는 단량체는 아크릴산, 메틸(메타)아크릴산, 에틸(메타)아크릴산, 트리메틸아크릴산, 말레산, 푸마르산, 이타콘산, 크로톤산, 시트라콘산, 비닐초산, 4-펜텐산 및 이들의 염으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 이 중에서 금속을 고속으로 연마한다는 관점에서 아크릴산, 메틸(메타)아크릴산 및 말레산이 보다 바람직하다. The polycarboxylic acid copolymer preferably includes a monomer having a structural unit represented by Chemical Formula 3. Monomers having a structural unit represented by the formula (3) are acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, vinyl acetate, 4-pen It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of tennic acids and their salts. Among them, acrylic acid, methyl (meth) acrylic acid and maleic acid are more preferable from the viewpoint of polishing the metal at high speed.
또한, 상기 폴리카르복실산계 공중합체는 상기 화학식 3으로 표시되는 구조단위를 가지는 단량체와 공중합 가능한 다른 단량체를 1종 또는 2종 이상 사용하여도 된다. 이들의 구체적인 예로는, 폴리아크릴산 중합체(PAA), 폴리메틸(메타)아크릴산 공중합체(PMAA), 폴리아크릴산말레산 공중합체(PAMA), 폴리아크릴산메틸(메타)아크릴산 공중합체(PAMAA), 폴리말레산 공중합체(PMA), 폴리메틸(메타)아크릴산말레산 공중합체(PMAMA) 및 이들의 염 등을 들 수 있다. In addition, the polycarboxylic acid copolymer may use one kind or two or more kinds of other monomers copolymerizable with the monomer having the structural unit represented by the formula (3). Specific examples thereof include polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polyacrylic acid maleic acid copolymer (PAMA), polymethyl acrylate (meth) acrylic acid copolymer (PAMAA), polymale Acid copolymer (PMA), polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), these salts, etc. are mentioned.
상기 폴리카르복시산 공중합체는 조성물 총 중량에 대하여, 0.01중량% 내지 10중량%로 포함되는 것이 바람직하며, 0.05중량% 내지 5중량%으로 포함되는 것이 보다 바람직하며, 0.1중량% 내지 1중량%으로 포함되는 것이 가장 바람직하다.The polycarboxylic acid copolymer is preferably included in an amount of 0.01% to 10% by weight, more preferably 0.05% to 5% by weight, and 0.1% to 1% by weight, based on the total weight of the composition. Most preferably.
상기 양자성 알킬렌글리콜 모노알킬에테르 화합물은 유기 오염물을 용해시키는 용매 역할을 한다. 또한 상기 양자성 알킬렌글리콜 모노알킬에테르 화합물은 용매로서의 기능 외에도 세정액의 표면장력을 저하시켜 유리기판에 대한 습윤성을 증가시키므로 세정력을 향상시켜 준다. The protic alkylene glycol monoalkyl ether compound serves as a solvent for dissolving organic contaminants. In addition to the function as a solvent, the proton alkylene glycol monoalkyl ether compound lowers the surface tension of the cleaning solution to increase the wettability on the glass substrate, thereby improving the cleaning power.
상기 양자성 알킬렌글리콜 모노알킬에테르 화합물은 에틸렌글리콜모노부틸 에테르(BG), 디에틸렌글리콜 모노메틸에테르(MDG), 디에틸렌글리콜 모노에틸에테르(carbitol), 디에틸렌글리콜 모노부틸에테르(BDG), 디프로필렌글리콜 모노메틸에테르(DPM), 디프로필렌글리콜 모노에틸에테르(MFDG), 트리에틸렌글리콜 모노부틸에테르(BTG), 트리에틸렌글리콜 모노에틸에테르(MTG) 및 프로필렌글리콜 모노메틸에테르(MFG)로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것이 바람직하다.The protic alkylene glycol monoalkyl ether compound is ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), Dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG) and propylene glycol monomethyl ether (MFG) It is preferable that it is 1 type, or 2 or more types selected from a group.
상기 양자성 알킬렌글리콜 모노알킬에테르 화합물은 조성물 총 중량에 대하여 0.05 내지 20중량%로 포함되는 것이 바람직하고, 0.5 내지 10중량%로 포함되는 것이 보다 바람직하다. 상술한 범위 미만으로 포함되면 양자성 알킬렌글리콜 모노알킬에테르 화합물의 추가에 기인한 세정액 조성물의 유기 오염물에 대한 용해력 증가를 기대할 수 없다. 상술한 범위를 초과하여 포함되면 습윤성 증가에 대한 더 이상의 효과를 기대할 수 없다.The protic alkylene glycol monoalkyl ether compound is preferably contained in 0.05 to 20% by weight, more preferably in 0.5 to 10% by weight based on the total weight of the composition. When included below the above range, it is not possible to expect an increase in the solubility of the cleaning liquid composition to organic contaminants due to the addition of the protic alkylene glycol monoalkyl ether compound. If included beyond the above range, no further effect on the increase in wettability can be expected.
상기 계면활성제는 기판에 대한 습윤성을 증가시켜 균일한 세정이 이루어지도록 하며 금속 패턴 및 산화막이 존재하는 기판의 세정 공정시 금속의 부식 및 산화막의 과식각을 방지하는 효과를 갖는다. 상기 계면활성제는 음성 계면활성제, 양성 계면활성제 및 비이온성의 계면활성제으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 특히 이들 가운데 습윤성이 우수하고 기포 발생이 보다 적은 비이온성 계면활성제를 이용하는 것이 바람직하다.The surfactant increases the wettability of the substrate so that uniform cleaning is performed, and has an effect of preventing corrosion of the metal and over-etching of the oxide film during the cleaning process of the substrate including the metal pattern and the oxide film. It is preferable that the said surfactant is 1 type (s) or 2 or more types chosen from the group which consists of a negative surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, it is preferable to use nonionic surfactant which is excellent in wettability and has less bubble generation.
상기 비이온성 계면활성제는 폴리옥시에틸렌/폴리옥시프로필렌 글리콜형, 폴리옥시에틸렌알킬에테르형, 폴리옥시에틸렌 알킬페닐에테르형, 폴리옥시에틸렌/폴리옥시프로필렌알킬에테르형, 폴리옥시에틸렌/폴리옥시부틸렌알킬에테르형, 폴리 옥시에틸렌알킬아미노에테르형, 폴리옥시에틸렌알킬아미드에테르형, 폴리에틸렌글리콜지방산에스테르형, 솔비탄지방산 에스테르형, 지방산 에스테르형, 글리세린 지방산 에스테르형, 폴리글리세롤 지방산 에스테르형, 글리세린에스테르형, 알키롤아미드형, 지방산 아미드형 및 옥시에틸렌 첨가 지방산 아미드형으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 이 중에서도, 계면활성제 분자의 구조 중에 친수기로서 옥시 에틸렌기(EO기)를 갖고, 소수기로서는 옥시프로필렌기(PO기) 및 또는 옥시 부틸렌기(BO기)을 가지는, 폴리옥시에틸렌/폴리옥시부틸렌알킬에테르형 공중합체인 것이 바람직하다. 여기서, EO기는 -CH2-CH2-O-로 표시되고, 옥시 프로필렌기는 -CH(CH3)-CH2-O- 또는 -CH2-CH(CH3)-O-, 옥시 부틸렌기는 -CH2-CH2-CH2-CH2-O-, -CH(CH3)-CH2-CH2-O-, -CH2-CH(CH3)-CH2-O-, 또는 -CH2-CH2-CH(CH3)2-O-로 표시된다. EO기와 PO기, BO기의 공중합 부분은, 블록 공중합체이어도, 랜덤한 공중합체이어도, 블록(block)성을 띤 랜덤(random) 다중합체이어도 좋다. 또한 그 공중합 분자는, EO기와 PO기에 의한 공중합체, EO기와 BO기에 의한 공중합체, 혹은 EO기와 PO기, BO기에 의한 공중합체이어도 좋다. 친수기의 EO기와, 소수기의 PO기 또는 BO기의, 계면활성제 분자 중에서의 존재 비율로서는, EO기의 총 몰수를 X, PO기 또는 BO기의 총 몰수를 Y라고 했을 경우, X/(X+Y)이 0.05 내지 0.7의 범위인 것이 바람직하다.The nonionic surfactants are polyoxyethylene / polyoxypropylene glycol type, polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxyethylene / polyoxypropylene alkyl ether type, polyoxyethylene / polyoxybutylene Alkyl ether type, polyoxyethylene alkyl amino ether type, polyoxyethylene alkylamide ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, fatty acid ester type, glycerin fatty acid ester type, polyglycerol fatty acid ester type, glycerin ester type It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of alkyramide type | mold, fatty acid amide type, and oxyethylene addition fatty acid amide type. Among these, polyoxyethylene / polyoxybutylene, which has an oxyethylene group (EO group) as a hydrophilic group in the structure of a surfactant molecule, and has an oxypropylene group (PO group) and or an oxy butylene group (BO group) as a hydrophobic group. It is preferable that it is an alkyl ether type copolymer. Here, the EO group is represented by -CH 2 -CH 2 -O-, the oxypropylene group is -CH (CH 3 ) -CH 2 -O- or -CH 2 -CH (CH 3 ) -O-, and the oxybutylene group -CH 2 -CH 2 -CH 2 -CH 2 -O-, -CH (CH 3 ) -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -CH 2 -O-, or- CH 2 -CH 2 -CH (CH 3 ) 2 -O-. The copolymerization portion of the EO group, the PO group, and the PO group may be a block copolymer, a random copolymer, or a random polypolymer having block properties. In addition, the copolymer molecule may be a copolymer of an EO group or a PO group, a copolymer of an EO group or a PO group, or a copolymer of the EO group or a PO group or a BA group. As an abundance ratio in the surfactant molecule of the EO group of the hydrophilic group and the PO group or the BOH group of the hydrophilic group, X / (X + It is preferable that Y) is in the range of 0.05 to 0.7.
또한, 상기 비이온성 계면활성제의 말단은, 단지 수소, 수산기, 알킬기 및 알케닐기로 이루어진 군에서 선택되는 1종 또는 2종 이상이어도 무방하다. 또한, 에틸렌 디아민이나 글리세린을 부가시킨 구조이어도 무방하다. 이러한 비이온성 계면활성제의 예로는, 폴리옥시에틸렌/폴리옥시프로필렌 축합물, 폴리옥시에틸렌/폴리옥시부틸렌 축합물, 폴리옥시에틸렌/폴리옥시프로필렌 디카닐에테르축합물, 폴리옥시에틸렌/폴리옥시프로필렌 데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시프로필렌 운데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시프로필렌 도데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시프로필렌 테트라데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시부틸렌 데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시부틸렌 운데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시부틸렌 도데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시부틸렌 테트라데카닐에테르축합물, 폴리옥시에틸렌/폴리옥시프로필렌2-에틸헥실에테르, 폴리옥시에틸렌/폴리옥시프로필렌 라우릴에테르, 폴리옥시에틸렌/폴리옥시프로필렌 스테아릴에테르, 글리세린부가형 폴리옥시에틸렌/폴리옥시프로필렌 축합물, 글리세린부가형 폴리옥시에틸렌/폴리옥시부틸렌 축합물 에틸렌디아민부가형 폴리옥시에틸렌/폴리옥시프로필렌 축합물, 에틸렌디아민부가형 폴리옥시에틸렌/폴리옥시부틸렌 축합물 폴리옥시에틸렌/폴리옥시부틸렌2-에틸헥실에테르, 폴리옥시에틸렌/폴리옥시부틸렌 라우릴에테르, 폴리옥시에틸렌/폴리옥시부틸렌 스테아릴에테르 등을 들 수 있다. 바람직하게는 폴리옥시에틸렌/폴리옥시프로필렌 축합물, 폴리옥시에틸렌 폴리옥시부틸렌 축합물, 글리세린부가형 폴리옥시에틸렌 폴리옥시프로필렌 축합물 및 에틸렌디아민부가형 폴리옥시에틸렌 폴리옥시프로필렌 축합물이고, 보다 바람직하게는 폴리옥시에틸렌 폴리옥시프로필렌 축합물 또는 에틸렌디아 민부가형 폴리옥시에틸렌 폴리옥시프로필렌 축합물이다. In addition, the terminal of the said nonionic surfactant may be 1 type, or 2 or more types chosen from the group which consists only of a hydrogen, a hydroxyl group, an alkyl group, and an alkenyl group. Moreover, the structure which added ethylene diamine and glycerol may be sufficient. Examples of such nonionic surfactants include polyoxyethylene / polyoxypropylene condensates, polyoxyethylene / polyoxybutylene condensates, polyoxyethylene / polyoxypropylene dicanylether condensates, polyoxyethylene / polyoxypropylene Decanyl ether condensates, polyoxyethylene / polyoxypropylene undecanyl ether condensates, polyoxyethylene / polyoxypropylene dodecanyl ether condensates, polyoxyethylene / polyoxypropylene tetradecanyl ether condensates, polyoxyethylene / Polyoxybutylene decanyl ether condensate, polyoxyethylene / polyoxybutylene undecanyl ether condensate, polyoxyethylene / polyoxybutylene dodecanyl ether condensate, polyoxyethylene / polyoxybutylene tetradecanyl ether Condensate, polyoxyethylene / polyoxypropylene 2-ethylhexyl ether, polyoxyethylene / polyoxypropylene lauryl Le, polyoxyethylene / polyoxypropylene stearyl ether, glycerin addition polyoxyethylene / polyoxypropylene condensate, glycerin addition polyoxyethylene / polyoxybutylene condensate ethylenediamine addition polyoxyethylene / polyoxypropylene condensate, Ethylenediamine addition type polyoxyethylene / polyoxybutylene condensate polyoxyethylene / polyoxybutylene 2-ethylhexyl ether, polyoxyethylene / polyoxybutylene lauryl ether, polyoxyethylene / polyoxybutylene stearyl ether Etc. can be mentioned. Preferred are polyoxyethylene / polyoxypropylene condensates, polyoxyethylene polyoxybutylene condensates, glycerin added polyoxyethylene polyoxypropylene condensates and ethylenediamine added polyoxyethylene polyoxypropylene condensates, more preferably Is a polyoxyethylene polyoxypropylene condensate or an ethylene diamine-added polyoxyethylene polyoxypropylene condensate.
상기 계면활성제는 조성물 총 중량에 대하여, 0.001 내지 1.0중량%로 포함되는 것이 바람직하고, 0.01 내지 0.5중량%로 포함되는 것이 보다 바람직하다. 상술한 범위 미만으로 포함되면 유리기판의 세정 균일도 증가 효과가 미미하며, 상술한 범위를 초과하여 포함되면 세정 균일도는 일정하나 그 이상 증가하지 않고 일정 범위 내에서 수렴한다.The surfactant is preferably included in 0.001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight based on the total weight of the composition. If it is included in the above-described range, the cleaning uniformity increase effect of the glass substrate is insignificant. If it is included in the above-mentioned range, the cleaning uniformity is constant but converges within a certain range without increasing more.
본 발명의 세정액 조성물의 pH는 바람직하게는 pH7 내지 pH13, 보다 바람직하게는 pH 8 내지 pH 11의 범위이다.The pH of the cleaning liquid composition of the present invention is preferably in the range of pH 7 to pH 13, more preferably pH 8 to pH 11.
본 발명의 세정액 조성물을 이용한 세정방법은 당 업계에 통상적으로 알려진 방법에 의하여 수행할 수 있다. 상기 세정방법은 스프레이(spray) 방식, 스핀(spin) 방식, 딥핑(dipping) 방식 및 초음파를 이용한 딥핑방식으로 이루어진 군에서 선택되는 1종 또는 2종 이상으로 수행되는 것이 바람직하다. 본 발명의 세정방법이 가장 우수한 세정 효과를 나타낼 수 있는 온도는 20내지 80℃이며, 바람직하게는 20내지 50℃이다. 또한 본 발명의 세정방법은 30초 내지 10분 동안 수행되는 것이 바람직하다.The cleaning method using the cleaning liquid composition of the present invention can be carried out by methods commonly known in the art. The cleaning method is preferably performed by one or two or more selected from the group consisting of a spray method, a spin method, a dipping method, and a dipping method using ultrasonic waves. The temperature at which the cleaning method of the present invention can exhibit the most excellent cleaning effect is 20 to 80 ° C, preferably 20 to 50 ° C. In addition, the cleaning method of the present invention is preferably carried out for 30 seconds to 10 minutes.
이하, 실시예를 들어 본 발명을 상세히 설명하지만, 본 발명은 하기 실시예로만 한정되는 것은 아니다. 하기 실시예는 본 발명의 바람직한 조성뿐만 아니라 본 발명의 조성물을 이용하기 위한 바람직한 세정방법을 제시한다.Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. The following examples set forth preferred compositions for the present invention as well as preferred methods for using the compositions of the present invention.
실시예1 내지 실시예19 및 비교예1 내지 비교예3: 세정액 조성물의 제조Examples 1 to 19 and Comparative Examples 1 to 3: Preparation of Cleaning Liquid Composition
표 1에 기재된 구성성분 및 조성으로 혼합하고 교반하여 세정액 조성물을 제조하였다.Washing liquid compositions were prepared by mixing and stirring with the ingredients and compositions shown in Table 1.
공중합쳬Polycarboxylic acid
Copolymerization
주) NHEP: N-(2-히드록시에틸)피페리딘NHEP: N- (2-hydroxyethyl) piperidine
NHPP: N-(2-히드록시프로필)피페리딘 NHPP: N- (2-hydroxypropyl) piperidine
HEP: 1-(2-히드록시에틸)-2-피롤리돈HEP: 1- (2-hydroxyethyl) -2-pyrrolidone
TMAH: 테트라메틸암모늄 히드록시드TMAH: Tetramethylammonium Hydroxide
NH4OH: 암모늄 히드록시드NH 4 OH: ammonium hydroxide
MEA: 모노 에탄올 아민MEA: Monoethanol Amine
*1): 2,2’-[[[에틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올* 1): 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol
*2): EMADOX-NA* 2): EMADOX-NA
*3): 아스코르빅산* 3): Ascorbic acid
*GE: 양자성 알킬렌글리콜 모노알킬에테르* GE: protic alkylene glycol monoalkyl ether
*4): 디에틸렌글리콜 모노메틸에테르* 4) diethylene glycol monomethyl ether
*5): 디에틸렌글리콜 모노부틸에테르* 5) diethylene glycol monobutyl ether
*6): 트리에틸렌글리콜 모노에틸에테르* 6): triethylene glycol monoethyl ether
*7): 폴리아크릴산중합체(PAA)* 7): polyacrylic acid polymer (PAA)
*8): 폴리메틸아크릴산공중합체(PMAA)* 8): polymethylacrylic acid copolymer (PMAA)
*9): 폴리옥시에틸렌/폴리옥시프로필렌 글리콜* 9): polyoxyethylene / polyoxypropylene glycol
*10): 폴리옥시에틸렌/폴리옥시프로필렌 에틸렌디아민 축합물* 10): polyoxyethylene / polyoxypropylene ethylenediamine condensate
시험예: 세정액 조성물의 특성 평가Test Example: Evaluation of Characteristics of Cleaning Liquid Composition
1) 구리 에칭 속도 평가1) copper etch rate evaluation
먼저 구리가 2500Å두께로 형성된 유리기판을 실시예1 내지 실시예12 및 비교예1 내지 비교예3의 세정액 조성물에 30분간 디핑시킨다. 이때 세정액의 온도는 40℃이며 구리 막의 두께를 디핑 이전 및 이후에 측정하고, 구리막의 용해속도를 구리막의 두께 변화로부터 계산하여 측정한다. 그 결과를 표 2에 기재하였다.First, a glass substrate having a copper thickness of 2500 kPa was dipped into the cleaning liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 3 for 30 minutes. At this time, the temperature of the cleaning liquid is 40 ℃ and the thickness of the copper film is measured before and after dipping, the dissolution rate of the copper film is calculated by calculating from the change in the thickness of the copper film. The results are shown in Table 2.
2) 유기 오염물 제거력 평가-12) Evaluation of Organic Pollutant Removal Capacity-1
유기 오염물의 제거력 평가를 위해 5㎝ x 5㎝ 크기로 형성된 유리기판 위에 사람의 지문 자국 또는 유기성분 사인펜으로 오염시키고, 오염된 기판을 스프레이식 유리 기판 세정장치를 이용하여 2분 동안 40℃에서 실시예4, 실시예8, 실시예12 내지 실시예19의 세정액 조성물로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. In order to evaluate the removal power of organic contaminants, the human body is stained with fingerprints or organic component pens on a glass substrate formed 5 cm x 5 cm, and the contaminated substrate is carried out at 40 ° C. for 2 minutes using a spray glass substrate cleaner. It wash | cleaned with the cleaning liquid composition of Example 4, Example 8, and Example 12-19. After washing for 30 seconds in ultrapure water and dried with nitrogen.
이때 하기 표 2에서 유기 오염물의 제거 유무는 제거가 되었을 때, ○, 제거가 되지 않았을 때 x로 표시하였다. 또한 실시예16에 의한 유기 오염물 제거 결과를 도 1 내지 도 4에 나타내었다. 여기서, 도 1은 유기 오염물 중 유기 사인펜 자국으로 오염된 유리기판을 나타낸 사진이다. 도 2는 본 발명의 실시예13에 따른 세정액 조성물을 이용하여 유기 오염물 중 유기 사인펜 자국이 제거되는 결과를 나타내는 사진이다. 도 3은 유기 오염물 중 사람의 지문으로 오염된 유리기판을 나타낸 사진이다. 도 4는 본 발명의 실시예13에 따른 세정액 조성물을 이용하여 유기 오염물 중 사람의 지문성분이 제거되는 결과를 나타내는 사진이다.At this time, the presence or absence of the organic contaminants in Table 2, when removed, was indicated by x, when not removed. In addition, the results of removing organic contaminants according to Example 16 are shown in FIGS. 1 to 4. 1 is a photograph showing a glass substrate contaminated with an organic sign pen mark among organic contaminants. Figure 2 is a photograph showing the result of removing the organic sign pen marks in the organic contaminants using the cleaning liquid composition according to Example 13 of the present invention. 3 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants. 4 is a photograph showing a result of removing a fingerprint component of a human from organic contaminants using the cleaning liquid composition according to Example 13 of the present invention.
3) 유기 오염물 제거력 평가-23) Evaluation of Organic Pollutant Removal Capacity-2
또한, 유리기판을 대기중에 24시간 방치하여 대기중의 각종 유기물, 무기물, 파티클 등에 오염시킨 후 스프레이식 유리 기판 세정장치를 이용하여 2분동안 40℃에서 실시예4, 실시예8, 실시예12 내지 실시예19의 세정액 조성물으로 세정하였다 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. 상기 유리기판 위에 0.5㎕의 초순수 방울을 떨어뜨려 세정후의 접촉각을 측정하였다. 그 결과를 표 2에 나타내었다.In addition, the glass substrate is left in the air for 24 hours to contaminate various organic substances, inorganic substances, particles, and the like in the atmosphere, and then, using the spray-type glass substrate cleaning apparatus at 40 ° C. for 4 minutes, Examples 4 and 8 and 12 To the cleaning liquid composition of Example 19 to 30 seconds after washing in ultrapure water and then dried with nitrogen. 0.5 μl of ultrapure water was dropped on the glass substrate to measure the contact angle after washing. The results are shown in Table 2.
4) 유기 오염물 제거력 평가-34) Evaluation of organic pollutant removal-3
실시예4, 실시예8, 실시예12, 실시예13, 실시예16 및 실시예18의 세정액 조성물을 가지고, 유기 파티클 솔루션으로 오염시킨 유리기판에 대한 세정을 실시하였다. 즉, 유리기판을 평균 입자 크기가 0.8㎛인 유기 파티클 솔루션으로 오염시키고 1분간 3000rpm으로 스핀(spin) 드라이한 후 스프레이식 유리 기판 세정장치를 이용하여 2분동안 40℃에서 각각의 세정액으로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. 세정 전후의 파티클 수는 표면입자측정기(Topcon WM-1500)로 0.1㎛ 이상의 파티클 수를 측정하였고, 표 2에 나타내었다.The glass substrates having the cleaning liquid compositions of Examples 4, 8, 12, 13, 16 and 18 were contaminated with an organic particle solution were washed. That is, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spin dried at 3000 rpm for 1 minute, and then washed with each cleaning liquid at 40 ° C. for 2 minutes using a spray-type glass substrate cleaning device. . After washing for 30 seconds in ultrapure water and dried with nitrogen. The number of particles before and after cleaning was measured by a particle size measuring instrument (Topcon WM-1500) of 0.1 μm or more, and is shown in Table 2.
(Å/분)Cu etching rate
(Å / min)
사인펜abandonment
Signature pen
표 2를 참조하면, 실시예1 내지 12의 세정액 조성물은 구리에 대한 부식방지 효과가 있었다. 그러나 고리형 아민 화합물이 아닌 알카리성 화합물이 포함되어 있는 비교예1 내지 3의 경우에는, 구리의 부식 현상이 관찰되었다.Referring to Table 2, the cleaning liquid compositions of Examples 1 to 12 had an anticorrosion effect on copper. However, in the case of Comparative Examples 1 to 3 in which an alkaline compound other than the cyclic amine compound was contained, corrosion phenomenon of copper was observed.
실시예8, 실시예 12, 실시예13, 실시예16 내지 실시예19의 세정액 조성물은 모두 유기 오염물의 제거력이 있음을 보였으며, 접촉각이 20°내지 40°를 갖게 되어 유기 오염물의 제거능력을 나타내었다.The cleaning solution compositions of Examples 8, 12, 13, and 16-19 all showed the ability to remove organic contaminants, and had a contact angle of 20 ° to 40 ° to remove the organic contaminants. Indicated.
실시예4, 실시예8, 실시예12, 실시예13, 실시예16 및 실시예18의 세정액 조성물로 유기 파티클 솔루션으로 오염시킨 유리기판에 대한 세정을 실시하였을 때 77 내지 86%에 가까운 파티클 제거력을 나타내었다.Particle removal force of 77-86% when cleaning the glass substrate contaminated with the organic particle solution with the cleaning liquid compositions of Examples 4, 8, 12, 13, 16 and 18 Indicated.
도 1은 유기 오염물 중 유기 사인펜 자국으로 오염된 유리기판을 나타낸 사진이다.1 is a photograph showing a glass substrate contaminated with organic sign pen marks among organic contaminants.
도 2는 본 발명의 실시예16에 따른 세정액 조성물을 이용하여 유기 오염물 중 유기 사인펜 자국이 제거되는 결과를 나타내는 사진이다. Figure 2 is a photograph showing the result of removing the organic sign pen marks in the organic contaminants using the cleaning liquid composition according to Example 16 of the present invention.
도 3은 유기 오염물 중 사람의 지문으로 오염된 유리기판을 나타낸 사진이다.3 is a photograph showing a glass substrate contaminated with human fingerprints among organic contaminants.
도 4는 본 발명의 실시예16에 따른 세정액 조성물을 이용하여 유기 오염물 중 사람의 지문성분이 제거되는 결과를 나타내는 사진이다.4 is a photograph showing a result of removing a fingerprint component of a human from organic contaminants using the cleaning liquid composition according to Example 16 of the present invention.
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PCT/KR2010/005002 WO2011014027A2 (en) | 2009-07-29 | 2010-07-29 | Cleaning fluid composition and a cleaning method for a panel using the same |
TW099125187A TWI481706B (en) | 2009-07-29 | 2010-07-29 | Cleaning composition and method of cleaning panel using the composition |
JP2012522766A JP5890306B2 (en) | 2009-07-29 | 2010-07-29 | Cleaning liquid composition and panel cleaning method using the same |
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