KR20130115926A - A composition for removing organic-inorganic hybrid alignment layer - Google Patents

A composition for removing organic-inorganic hybrid alignment layer Download PDF

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KR20130115926A
KR20130115926A KR1020120038728A KR20120038728A KR20130115926A KR 20130115926 A KR20130115926 A KR 20130115926A KR 1020120038728 A KR1020120038728 A KR 1020120038728A KR 20120038728 A KR20120038728 A KR 20120038728A KR 20130115926 A KR20130115926 A KR 20130115926A
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organic
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inorganic hybrid
methyl
composition
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KR101888696B1 (en
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이은상
방순홍
홍헌표
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동우 화인켐 주식회사
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0042Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/423Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/425Stripping 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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/426Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

Abstract

PURPOSE: A composition for eliminating an organic-inorganic hybrid alignment layer is provided to have a powerful removal strength to an organic alignment layer, to be able to effectively remove an alignment layer existing on the surface of a liquid crystal display panel, and to have the anti-corrosion property to the aluminum wiring. CONSTITUTION: A composition for eliminating an organic-inorganic hybrid alignment layer is characterized in comprising (A) an inorganic alkali compound; (B) more than one kind or two kinds of organic solvents; (C) an aliphatic polyhydric alcohol; (D) an anti-corrosive agent; and the residual amount of water. The composition for eliminating an organic-inorganic hybrid alignment layer is characterized in further comprising an organic alkali compound. The composition for eliminating an organic-inorganic hybrid alignment layer is characterized in comprising (A) 0.1-5 weight% of an inorganic alkali compound; (B) 30-80 weight% of more than one kind or two kinds of organic solvents; (C) 10-50 weight% of an aliphatic polyhydric alcohol; (D) 0.0001-1.0 weight% of an anti-corrosive agent; and the residual amount of water.

Description

유-무기 하이브리드형 배향막 제거 조성물{A COMPOSITION FOR REMOVING ORGANIC-INORGANIC HYBRID ALIGNMENT LAYER}Organic-inorganic hybrid alignment film removal composition {A COMPOSITION FOR REMOVING ORGANIC-INORGANIC HYBRID ALIGNMENT LAYER}

본 발명은 유-무기 하이브리드형 배향막 제거 조성물 및 상기 조성물을 사용하여 기판을 세정하는 공정을 포함하는 액정표시 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an organic-inorganic hybrid type alignment film removing composition and a method for manufacturing an array substrate for a liquid crystal display device comprising the step of cleaning the substrate using the composition.

일반적으로, 액정표시장치는 TFT 기판, 상기 TFT 기판에 대향하는 컬러필터 기판, 그리고 양 기판 사이에 개재되어 전기적인 신호가 인가됨에 따라 광의 투과 여부를 결정하는 액정을 포함하는 액정표시패널을 구비한다.In general, a liquid crystal display device includes a liquid crystal display panel including a TFT substrate, a color filter substrate facing the TFT substrate, and a liquid crystal interposed between both substrates to determine whether light is transmitted as an electric signal is applied. .

상기 TFT 기판과 컬러필터 기판 사이에 액정을 단순히 양 기판 사이에 끼우는 것 만으로는 같은 분자배열상태를 얻기가 어렵기 때문에 기판 내벽에 처리를 하여 배향막을 형성한다.It is difficult to obtain the same molecular alignment state simply by sandwiching the liquid crystal between the TFT substrate and the color filter substrate between the two substrates, so that an alignment film is formed by treating the inner wall of the substrate.

상기 배향막은 200℃ 이하에서 Film 형성이 가능하고, ITO 기판에 좋은 접착 특성이 있어야 한다. 배향막 도포 공정에 있어서 가장 중요한 점은 넓은 면적에 일정하고 균일하게 배향막을 도포하는 것이다. 보통 배향막의 두께는 500~1,000Å정도이며, 동일 기판에서는 100Å정도의 두께 차이에 의해 얼룩과 같은 불량이 발생할 수 있기 때문에 배향막의 두께 관리는 중요한 공정 관리 항목이 된다.The alignment layer should be able to form a film at 200 ° C. or lower, and have good adhesion properties to an ITO substrate. The most important point in the alignment film application process is to apply the alignment film uniformly and uniformly over a large area. Usually, the thickness of the alignment film is about 500 to 1,000 mm 3, and defects such as spots may occur due to a thickness difference of about 100 mm 3 on the same substrate, so the thickness management of the alignment film is an important process control item.

상기 배향막으로는 일반적으로 유기 배향막과 무기배향막으로 구분되며, 유기배향막으로는 폴리이미드계 고분자 화합물을 유기용매에 용해시킨 것을 ITO 기판위에 일정한 막두께로 도포후, 도포된 배향막을 균일하게 하기 위하여 건조과정을 거친다. 또한 무기배향막으로는 일반적으로 SiO2 산화막을 진공증착등의 방법을 통해 ITO 기판위에 도포후 사용하고 있다. 그러나 앞서 설명한 폴리이미드계등의 유기배향막은 ITO 기판위에 도포후 건조하는 과정에서 용매의 증발속도 등의 차이에 의해 균일 건조가 쉽지않고, 건조시 도포된 두께의 차이에 의해 얼룩등이 발생하기도 한다. 또한 건조 후 러빙이라는 공정을 통하여 폴리이미드계막에 러빙을 하면, 액정이 배향하게 되는데, 이러한 러빙공정 중 많은 불량을 일으키는 원인이 되기도 한다. 또한 SiO2 산화막계인 무기배향막은 러빙공정을 통하지 않고 이용이 가능하기 때문에 러빙에 따른 불량을 감소시키는 것이 가능하지만, 액정의 배향효과등 다른 문제점을 수반하고 있다. 이러한 이유로 인하여 폴리디메틸실록산이라는 유무기계가 혼합된 물질을 이용한 유-무기 하이브리드형 배향막의 개발이 진행되고 있다. 상기의 폴리디메틸실록산은 SiOxRy(0<x≤1, 0<y≤1, R은 탄소원자가 1에서 10까지의 구조를 가지는 알킬기 또는 알릴기 등임)의 구조를 가지는 물질로 폴리디메틸실록산계 유무기하이브리드형 물질을 ITO기판에 도포후 일정한 온도에서 일정시간 열처리하는 경우 ITO 기판과 접촉하는 부분에서는 실리콘(Si) 성분이 결합력을 가지며 ITO-Si간 결합력을 가지는 한편 ITO기판과 접촉하지 않는 상부층은 폴리디메틸실록산에 있는 알킬 또는 알릴기 등의 유기그룹이 존재하게 된다. 이와 같이 ITO와 접촉하는 부분에서는 무기배향막의 일종인 SiOx물질이, ITO와 접촉하지 않는 상부부분은 유기배향막의 일종인 유기물질(폴리디메틸실록산의 R 그룹에 해당)이 존재하는 유무기하이브리형 배향막이 형성되게 된다. 이러한 유-무기 하이브리드형 배향막의 경우, 유기배향막의 제거액이 무기배향막의 성질을 가지는 SiOx계 성분까지 제거해야 하므로 만족스러운 제거효과를 기대하기 어려우며, 또한 무기배향막만을 대상으로 하는 제거액으로는 유기계 성분의 제거하는 것에 어려운 점이 있다. The alignment layer is generally classified into an organic alignment layer and an inorganic alignment layer, and the organic alignment layer is dried by dissolving a polyimide polymer compound in an organic solvent at a constant film thickness on an ITO substrate and then uniformly applying the applied alignment layer. Go through the process. In addition, as an inorganic alignment film, a SiO 2 oxide film is generally applied to an ITO substrate by vacuum deposition or the like. However, the organic alignment film such as polyimide described above is not easy to uniformly dry due to the difference in the evaporation rate of the solvent in the process of drying after coating on the ITO substrate, and stains may occur due to the difference in thickness applied during drying. . In addition, when rubbing the polyimide-based film through a process called rubbing after drying, the liquid crystal is aligned, which may cause many defects during the rubbing process. In addition, since the inorganic alignment film, which is an SiO 2 oxide film system, can be used without going through a rubbing process, it is possible to reduce defects due to rubbing, but it has other problems such as an alignment effect of liquid crystals. For this reason, the development of an organic-inorganic hybrid alignment layer using a mixture of organic and inorganic machines, such as polydimethylsiloxane, is in progress. The polydimethylsiloxane is a material having a structure of SiO x R y (0 <x≤1, 0 <y≤1, R is an alkyl group or an allyl group having a structure of 1 to 10 carbon atoms) and polydimethylsiloxane When acid-based organic-inorganic hybrid materials are applied to an ITO substrate and heat-treated at a constant temperature for a predetermined time, the silicon (Si) component has a bonding force in the part in contact with the ITO substrate and has a bonding force between the ITO and Si, but does not contact the ITO substrate. The upper layer is provided with organic groups such as alkyl or allyl groups in the polydimethylsiloxane. In this way, in contact with ITO, the SiO x material, which is a kind of inorganic alignment film, and the upper part, which is not in contact with ITO, is an organic-inorganic hybrid type in which an organic material (corresponding to R group of polydimethylsiloxane) exists as a kind of organic alignment film. An alignment film is formed. In the case of such an organic-inorganic hybrid type alignment film, since the organic liquid alignment film removal liquid must remove even the SiO x component having the property of the inorganic alignment film, it is difficult to expect a satisfactory removal effect. There is a difficulty in getting rid of.

상기와 같은 액정 배향막 제거를 위한 발명으로서, 한국특허등록 제10-0733554호에서는 액정 배향막 제거액 및 이를 이용한 액정표시패널의 세정방법에 관하여 기재하고 있으나, 유-무기 하이브리드 배향막에 대해서는 제거성이 없다는 문제점이 있을 뿐만 아니라 아민을 필수적으로 필요로 한다는 한계가 있으며, 한국특허등록 제 10-0361481호 역시 유-무기 하이브리드 배향막에 대한 제거성이 없다. 따라서, 유-무기 하이브리드 배향막에 대해서도 제거성을 갖고, 알루미늄 배선에 대한 부식 방지성을 갖는 유-무기 하이브리드형 배향막 제거 조성물에 대한 개발의 필요성이 점점 커지고 있다.As the invention for removing the liquid crystal alignment layer as described above, Korean Patent Registration No. 10-0733554 describes a liquid crystal alignment layer removal liquid and a method of cleaning the liquid crystal display panel using the same, but there is no problem in removing the organic-inorganic hybrid alignment layer. In addition to this, there is a limitation in that an amine is necessary. Korean Patent Registration No. 10-0361481 also has no removal property for an organic-inorganic hybrid alignment layer. Therefore, there is an increasing need for development of an organic-inorganic hybrid type alignment film removing composition which has removability to an organic-inorganic hybrid alignment film and has corrosion resistance to aluminum wiring.

KRKR 10-073355410-0733554 BB KRKR 10-036148110-0361481 BB

본 발명은 상기한 종래기술의 문제점을 해결하기 위한 것으로서, 액정 표시 패널의 액정 배향막에 대하여 우수한 제거성을 확보하기 위하여, 유기 배향막 뿐만 아니라 유-무기 하이브리드 배향막에 대해서도 제거성을 갖고, 구리 배선 및 알루미늄 배선에 대한 부식 방지성을 갖는 유-무기 하이브리드형 배향막 제거 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems of the prior art, in order to ensure excellent removability with respect to the liquid crystal alignment film of the liquid crystal display panel, it has a removability not only for the organic alignment film but also organic-inorganic hybrid alignment film, copper wiring and It is an object of the present invention to provide an organic-inorganic hybrid type alignment film removing composition having corrosion protection against aluminum wiring.

상기 목적을 달성하기 위하여,In order to achieve the above object,

본 발명은 (A) 무기 알칼리 화합물; (B) 1종 또는 2종 이상의 유기 용제; (C) 지방족 다가 알코올; (D) 부식방지제; 및 잔량의 물을 포함하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물을 제공한다.The present invention (A) an inorganic alkali compound; (B) one or two or more organic solvents; (C) aliphatic polyhydric alcohols; (D) corrosion inhibitors; And it provides an organic-inorganic hybrid type alignment film removal composition comprising a residual amount of water.

또한, 본 발명은 상기 유-무기 하이브리드형 배향막 제거 조성물을 사용하여 기판을 세정하는 공정을 포함하는 액정 표시 장치용 어레이 기판의 제조방법을 제공한다.In addition, the present invention provides a method of manufacturing an array substrate for a liquid crystal display device comprising the step of cleaning the substrate using the organic-inorganic hybrid type alignment film removal composition.

본 발명에 따른 유-무기 하이브리드형 배향막 제거 조성물은 유기 배향막에 대한 제거력이 강할 뿐만 아니라, 유-무기 하이브리드 배향막의 제거력도 갖고 있어, 액정 표시 패널의 표면에 존재하는 배향막을 효과적으로 제거할 수 있으며, 구리 배선 및 알루미늄 배선에 대한 부식 방지성을 갖게 된다. 또한 본 발명의 유-무기 하이브리드형 배향막 제거 조성물을 사용하는 경우, 액정 표시 장치의 불량률을 감소시켜 전체적인 제조 공정에 소요되는 비용을 절감할 수 있다.The organic-inorganic hybrid alignment layer removing composition according to the present invention not only has a strong removal force with respect to the organic alignment layer, but also has a removal force with the organic-inorganic hybrid alignment layer, and can effectively remove the alignment layer present on the surface of the liquid crystal display panel. It has corrosion protection against copper wiring and aluminum wiring. In addition, when using the organic-inorganic hybrid type alignment film removal composition of the present invention, it is possible to reduce the defect rate of the liquid crystal display device to reduce the cost of the entire manufacturing process.

도 1은 본 발명의 유-무기 하이브리드형 배향막 제거 조성물을 사용하여 세정하기 전의 기판의 사진이다.
도 2는 본 발명의 유-무기 하이브리드형 배향막 제거 조성물을 사용하여 세정한 후의 기판의 사진이다.
1 is a photograph of a substrate before cleaning using the organic-inorganic hybrid type alignment film removal composition of the present invention.
2 is a photograph of a substrate after cleaning using the organic-inorganic hybrid type alignment film removal composition of the present invention.

이하 본 발명에 따른 유-무기 하이브리드형 배향막 제거 조성물을 상세히 설명한다.Hereinafter, the organic-inorganic hybrid type alignment film removing composition according to the present invention will be described in detail.

본 발명에 따른 유-무기 하이브리드형 배향막 제거 조성물은 (A) 무기 알칼리 화합물; (B) 1종 또는 2종 이상의 유기 용제; (C) 지방족 다가 알코올; (D) 부식방지제; 및 잔량의 물을 포함한다.
The organic-inorganic hybrid type alignment film removing composition according to the present invention comprises (A) an inorganic alkali compound; (B) one or two or more organic solvents; (C) aliphatic polyhydric alcohols; (D) corrosion inhibitors; And residual water.

본 발명에 있어서, 상기 무기 알칼리 화합물로서는 수산화칼륨(potassium hydroxide), 수산화나트륨(sodium hydroxide), 탄산나트륨(sodium carbonate), 탐산 칼륨(potassium carbonate)로 이루어진 군에서 선택된 어느 하나 또는 2종 이상을 조합하여 사용할 수 있으며, 조성물 총 중량에 대하여 0.1 내지 5.0 중량%로 포함되는 것이 바람직하며, 0.3 내지 3.0 중량%로 포함되는 것이 보다 바람직하다. 상기 알칼리 화합물이 0.1 중량% 미만으로 포함되는 경우에는 배향막 제거 속도가 늦거나 제거가 되지 않으며, 5중량%를 초과하여 포함되는 경우에는 배선재료의 부식을 방지할 수가 없다.
In the present invention, the inorganic alkali compound is any one or two or more selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and a combination thereof. It may be used, it is preferably included in 0.1 to 5.0% by weight, more preferably 0.3 to 3.0% by weight relative to the total weight of the composition. When the alkali compound is included in less than 0.1% by weight, the alignment film removal rate is slow or not removed. When the alkali compound is included in an amount of more than 5% by weight, corrosion of the wiring material cannot be prevented.

본 발명에 있어서, 상기 유기 용제로서는 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노부틸에테르, 트리에틸렌글리콜 모노메틸에테르, 디메틸포름아마이드 (DMF), N-메틸포름아마이드, 디메틸아세트아마이드(DMAc), N-메틸아세트아마이드, 디에틸아세트아마이드(DEAc), N-메틸 피롤리돈(NMP), N-에틸 피롤리돈(NEP), N-프로틸 피롤리돈(NPP), N-하이드록시메틸 피롤리돈 및 N-하이드록시에틸 피롤리돈 등으로 이루어진 군에서 1종 또는 2종 이상을 혼합하여 사용할 수 있다. In the present invention, the organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dimethyl Formamide (DMF), N-methylformamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone ( NEP), N-propyl pyrrolidone (NPP), N-hydroxymethyl pyrrolidone, N-hydroxyethyl pyrrolidone, etc. can be used 1 type or in mixture of 2 or more types.

본 발명에 있어서, 상기 유기 용제는 조성물 총 중량에 대하여 30 내지 80 중량%로 포함되는 것이 바람직하며, 40 내지 60 중량%로 포함되는 것이 보다 바람직하다. 상기 유기 용제가 30 중량% 미만으로 포함되는 경우에는 배향막 박리 속도가 늦거나 제거가 되지 않으며, 80 중량%를 초과하여 포함되는 경우에는 다른 성분의 함량이 부족해져, 배선재료의 부식이 증가한다.
In the present invention, the organic solvent is preferably included in 30 to 80% by weight, more preferably in 40 to 60% by weight relative to the total weight of the composition. When the organic solvent is included in less than 30% by weight, the alignment film peeling rate is not slowed or removed. When the organic solvent is included in an amount of more than 80% by weight, the content of other components is insufficient, which increases corrosion of the wiring material.

본 발명에 있어서, 상기 지방족 다가 알코올로서는 글리세롤, 글루코오스, 만노오스, 갈릭토오스, 솔비통, 만니톨, 폴리에틸렌글리콜로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물을 사용할 수 있으며, 조성물 총 중량에 대하여 10 내지 50 중량%로 포함되는 것이 바람직하며, 20 내지 40 중량%로 포함되는 것이 보다 바람직하다. 상기 지방족 다가 알코올이 10 중량% 미만으로 포함되는 경우에는 배선재료의 부식이 증가하게 되고, 50 중량%를 초과하여 포함되는 경우에는 배향막 제거성이 떨어지게 된다.
In the present invention, as the aliphatic polyhydric alcohol, any one or a mixture of two or more selected from the group consisting of glycerol, glucose, mannose, galactose, sorbitan, mannitol, and polyethylene glycol can be used, and the total weight of the composition is 10 It is preferably included in the 50 to 50% by weight, more preferably included in 20 to 40% by weight. When the aliphatic polyhydric alcohol is included in less than 10% by weight, the corrosion of the wiring material is increased, and when included in excess of 50% by weight, the alignment film removal property is inferior.

본 발명에 있어서, 상기 부식방지제로서는 2,2’-[[[벤조트리아졸]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스메탄올, 2,2’-[[[에틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스카르복시산, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스메틸아민 및 2,2’-[[[아민-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올로 이루어진 군에서 선택되는 어느 하나 또는 2종 이상의 혼합물을 사용할 수 있다. In the present invention, as the corrosion inhibitor, 2,2 '-[[[benzotriazole] methyl] imino] bisethanol and 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] Methyl] imino] bismethanol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen- Benzotriazol-1-yl] methyl] imino] bisethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] biscarboxylic acid, 2,2'- [[[Methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine and 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino ] Any one or a mixture of two or more selected from the group consisting of bisethanol can be used.

또한, 상기 부식방지제로서는 하기 화학식 1로 표시되는 벤조트리아졸 유도체를 사용할 수 있다.In addition, a benzotriazole derivative represented by the following general formula (1) may be used as the corrosion inhibitor.

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

(상기 화학식 1에서, R13 내지 R15는 서로 독립적으로 수소, 할로겐, 알킬기, 시클로알킬기, 알릴기, 아릴기, 아미노기, 알킬아미노기, 니트로기, 시아노기, 메르캅토기, 알킬메르캅토기, 히드록실기, 히드록시알킬기, 카르복실기, 카르복시알킬기, 아실기, 알콕시기 또는 헤테로고리아미노산을 치환기로 갖는 1가의 기이다.)(In Formula 1, R 13 to R 15 are each independently hydrogen, halogen, alkyl group, cycloalkyl group, allyl group, aryl group, amino group, alkylamino group, nitro group, cyano group, mercapto group, alkyl mercapto group, It is a monovalent group having a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group or a heterocyclic amino acid as a substituent.)

상기 부식방지제는 세정액 조성물 총 중량에 대하여 0.0001 내지 1.0중량%로 포함하는 것이 바람직하며, 보다 바람직하게는 0.01 내지 0.5중량%인 것이 좋다. 이때, 상기 부식방지제의 함량이 0.0001중량% 미만일 경우, 금속배선에 대한 부식이 발생하는 문제점이 있고, 1.0중량%를 초과할 경우, 경제성이 떨어지는 문제점이 있다.
The corrosion inhibitor is preferably included in 0.0001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight relative to the total weight of the cleaning liquid composition. At this time, when the content of the corrosion inhibitor is less than 0.0001% by weight, there is a problem that the corrosion on the metal wiring occurs, when the content exceeds 1.0% by weight, there is a problem of low economic efficiency.

본 발명에 있어서, 상기 물은 특별히 한정되는 것은 아니나, 반도체 공정용의 물로서, 비저항값이 18MΩ/cm 이상인 탈이온수를 사용하는 것이 바람직하다. 상기 물은 전체 조성물의 총 중량이 100 중량%가 되도록 하는 잔량으로 포함되므로, 다른 구성성분의 함량에 따라 조정될 수 있다.
In the present invention, the water is not particularly limited, but as the water for the semiconductor process, it is preferable to use deionized water having a specific resistance value of 18 MPa / cm or more. The water is included in the remaining amount such that the total weight of the entire composition is 100% by weight, so that it can be adjusted according to the contents of other components.

본 발명에 따른 유-무기 하이브리드형 배향막 제거 조성물은 유기 알칼리성 화합물을 추가로 포함할 수 있다. 유기 알칼리 화합물로서는 테트라메틸암모늄하이드록 사이드(tetramethyl ammonium hydroxide, (CH3)4NOH), 테트라에틸암모늄하이드록사이드(tetraethyl ammonium hydroxide, (C2H5)4NOH), 테트라프로필암모늄하이드록사이드(tetrapropyl ammonium hydroxide, (C3H7)4NOH), 테트라부틸암모늄하이드록사이드(tetrabutyl ammonium hydroxide, (C4H9)4NOH), 탄산염, 인산염, 암모니아 및 알킬아민, 알릴아민, 알칸올아민, 알콕시아민 및 고리형아민으로 이루어진 군에서 선택된 아민류로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물을 사용할 수 있다.The organic-inorganic hybrid alignment layer removing composition according to the present invention may further include an organic alkaline compound. Examples of the organic alkali compound include tetramethyl ammonium hydroxide (CH 3 ) 4 NOH, tetraethyl ammonium hydroxide (C 2 H 5 ) 4 NOH, and tetrapropyl ammonium hydroxide. (tetrapropyl ammonium hydroxide, (C 3 H 7 ) 4 NOH), tetrabutyl ammonium hydroxide, (C 4 H 9 ) 4 NOH), carbonates, phosphates, ammonia and alkylamines, allylamines, alkanols Any one or a mixture of two or more selected from the group consisting of amines selected from the group consisting of amines, alkoxyamines and cyclic amines can be used.

상기 아민류에는 메틸아민, 에틸아민, 모노이소프로필아민, n-부틸아민, sec-부틸아민, 이소부틸아민, t-부틸아민, 펜틸아민 등의 1차 아민; 디메틸아민, 디에틸아민, 디프로필아민, 디이소프로필아민, 디부틸아민, 디이소부틸아민, 메틸에틸아민, 메틸프로필아민, 메틸이소프로필아민, 메틸부틸아민, 메틸이소부틸아민 등의 2차 아민; 디에틸 히드록시아민, 트리메틸아민, 트리에틸아민, 트리프로필아민, 트리부틸아민, 트리펜틸아민, 디메틸에틸아민, 메틸디에틸아민 및 메틸디프로필아민 등의 3차 아민; 콜린, 모노에탄올아민, 디에탄올아민, 트리에탄올아민, 모노프로판올아민, 2-아미노에탄올, 2-(에틸아미노)에탄올, 2-(메틸아미노)에탄올, N-메틸 디에탄올아민, N,N-디메틸에탄올아민, N,N-디에틸아미노에탄올, 2-(2-아미노에틸아미노)-1-에탄올, 1-아미노-2-프로판올, 2-아미노-1-프로판올, 3-아미노-1-프로판올, 4-아미노-1-부탄올, 디부탄올아민 등의 알칸올아민; (부톡시메틸)디에틸아민, (메톡시메틸)디에틸아민, (메톡시메틸)디메틸아민, (부톡시메틸)디메틸아민, (이소부톡시메틸)디메틸아민, (메톡시메틸)디에탄올아민, (히드록시에틸옥시메틸)디에틸아민, 메틸(메톡시메틸)아미노에탄, 메틸(메톡시메틸)아미노에탄올, 메틸(부톡시메틸)아미노에탄올, 2-(2-아미노에톡시)에탄올 등의 알콕시아민; 1-(2-히드록시에틸)피페라진, 1-(2-아미노에틸)피페라진, 1-(2-히드록시에틸)메틸피페라진, N-(3-아미노프로필)모폴린, 2-메틸피페라진, 1-메틸피페라진, 1-아미노-4-메틸피페라진, 1-벤질 피페라진, 1-페닐 피페라진, N-메틸모폴린, 4-에틸모폴린, N-포름일모폴린, N-(2-히드록시에틸)모폴린, N-(3-히드록시프로필)모폴린 등의 환을 형성한 고리형아민 등이 있다.Examples of the amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Secondary such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, etc. Amines; Tertiary amines such as diethyl hydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; Choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyl diethanolamine, N, N-dimethyl Ethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine , (Hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol Alkoxyamines; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methyl Piperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenyl piperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N And cyclic amines having a ring such as-(2-hydroxyethyl) morpholine or N- (3-hydroxypropyl) morpholine.

상기 유기 알칼리 화합물은 조성물 총 중량에 대하여 0.1 내지 5.0 중량%로 포함되는 것이 바람직하며, 0.3 내지 3.0 중량%로 포함되는 것이 보다 바람직하다. 상기 유기 알칼리 화합물이 0.1 중량% 미만으로 포함되는 경우에는 배향막 제거 속도가 늦거나 제거가 되지 않을 뿐만 아니라, 방식효과가 없어지면, 5중량%를 초과하여 포함되는 경우에는 배선재료의 부식을 방지할 수가 없다.
The organic alkali compound is preferably included in 0.1 to 5.0% by weight, more preferably 0.3 to 3.0% by weight relative to the total weight of the composition. When the organic alkali compound is included in less than 0.1% by weight, not only the removal rate of the alignment film is slow or not removed, and when the anticorrosive effect is eliminated, when the organic alkali compound is contained in an amount of more than 5% by weight, corrosion of the wiring material may be prevented. none.

본 발명에 따른 유-무기 하이브리드형 배향막 제거 조성물은 이 분야에서 통상적으로 사용되는 계면활성제 등의 첨가제를 추가로 포함할 수 있다. 상기 첨가제로는 일반적으로 사용되고 있는 비이온성 계면활성제, 양이온성 계면활성제, 음이온성 계면활성제를 들 수 있으며, 이들은 각각 단독으로 또는 혼합하여 사용할 수 있다.
The organic-inorganic hybrid alignment layer removing composition according to the present invention may further include additives such as surfactants commonly used in the art. The additives include nonionic surfactants, cationic surfactants and anionic surfactants which are generally used, and these may be used alone or in combination.

본 발명의 유-무기 하이브리드형 배향막 제거 조성물을 사용하여 유-무기 하이브리드형 배향막을 제거하는 방법으로는 침지법이 일반적이지만 기타의 방법, 예를 들면 분무법에 의한 방법을 사용할 수도 있다. 본 발명에 의한 조성물로 처리한 후의 세정제로는 알코올과 같은 유기용매를 사용할 필요가 없고 물로 세정하는 것만으로도 충분하다.As a method for removing the organic-inorganic hybrid alignment film using the organic-inorganic hybrid alignment film removal composition of the present invention, the dipping method is generally used, but other methods such as a spraying method may also be used. As a cleaning agent after treatment with the composition according to the present invention, it is not necessary to use an organic solvent such as alcohol, and only washing with water is sufficient.

본 발명의 유-무기 하이브리드형 배향막 제거 조성물은 반도체 또는 전자제품, 특히 액정패널의 유-무기 하이브리드형 배향막의 제거 공정에서 유용하게 사용될 수 있다.
The organic-inorganic hybrid alignment layer removing composition of the present invention can be usefully used in the process of removing the organic-inorganic hybrid alignment layer of a semiconductor or electronic product, especially a liquid crystal panel.

이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

실시예Example

실시예 1~7 및 비교예 1~8: 유-무기 하이브리드형 배향막 제거 조성물의 제조Examples 1-7 and Comparative Examples 1-8: Preparation of Organic-Inorganic Hybrid Alignment Film-Removing Composition

하기 표 1에 기재된 성분을 해당 조성비로 혼합하여 실시예 1~7 및 비교예 1~8의 유-무기 하이브리드형 배향막 제거용 세정제 조성물을 제조하였다.The components shown in Table 1 were mixed at the corresponding composition ratios to prepare cleaning compositions for removing the organic-inorganic hybrid type alignment films of Examples 1 to 7 and Comparative Examples 1 to 8.

알칼리alkali 용제solvent 다가 알코올Polyhydric alcohol 부식방지제Corrosion inhibitor water 종류Kinds amount 종류Kinds amount 종류Kinds amount 종류Kinds amount 실시예1Example 1 KOHKOH 0.10.1 MTGMTG 3030 GlycerinGlycerin 5050 d-1d-1 0.050.05 잔량Balance 실시예2Example 2 KOHKOH 33 BDGBDG 6060 GlycerinGlycerin 3030 d-1d-1 0.050.05 잔량Balance 실시예3Example 3 KOHKOH 55 MTGMTG 8080 GlycerinGlycerin 1010 d-1d-1 0.050.05 잔량Balance 실시예4Example 4 NaOHNaOH 33 MTGMTG 6060 GlycerinGlycerin 3030 d-1d-1 0.050.05 잔량Balance 실시예5Example 5 KOHKOH 33 BDGBDG 6060 PEGPEG 3030 d-1d-1 0.10.1 잔량Balance 실시예6Example 6 KOH/TMAHKOH / TMAH 1.5/1.51.5 / 1.5 BDGBDG 6060 GlycerinGlycerin 3030 d-1d-1 0.050.05 잔량Balance 실시예7Example 7 KOHKOH 33 BDGBDG 6060 GlycerinGlycerin 3030 d-2d-2 0.050.05 잔량Balance 비교예1Comparative Example 1 -- -- MTGMTG 3030 GlycerinGlycerin 5050 d-1d-1 0.050.05 잔량Balance 비교예2Comparative Example 2 KOHKOH 1010 MTGMTG 3030 GlycerinGlycerin 5050 d-1d-1 0.050.05 잔량Balance 비교예3Comparative Example 3 KOHKOH 55 -- -- GlycerinGlycerin 3030 d-1d-1 0.050.05 잔량Balance 비교예4Comparative Example 4 KOHKOH 0.10.1 MTGMTG 6060 -- -- d-1d-1 0.050.05 잔량Balance 비교예5Comparative Example 5 KOHKOH 33 MTGMTG 9090 GlycerinGlycerin 55 d-1d-1 0.050.05 잔량Balance 비교예6Comparative Example 6 KOHKOH 33 MTGMTG 2020 GlycerinGlycerin 6060 d-1d-1 0.050.05 잔량Balance 비교예7Comparative Example 7 KOHKOH 33 MTGMTG 6060 GlycerinGlycerin 3030 d-1d-1 -- 잔량Balance 비교예8Comparative Example 8 KOHKOH 33 BDGBDG 2020 GlycerinGlycerin 3030 d-1d-1 0.050.05 잔량Balance

KOH: 수산화 칼륨KOH: Potassium Hydroxide

NaOH: 수산화 나트륨NaOH: Sodium Hydroxide

BDG: 디에틸렌글리콜 모노부틸에테르BDG: diethylene glycol monobutyl ether

MTG: 트리에틸렌글리콜 모노메틸에테르MTG: triethylene glycol monomethyl ether

PEG: 폴리에틸렌글리콜PEG: Polyethylene glycol

TMAH: 테트라메틸암모늄하이드록 사이드(tetramethyl ammonium hydroxide)TMAH: tetramethyl ammonium hydroxide

d-1: 2,2’-[[[에틸-1H -벤조트리아졸-1-일]메틸]이미노]비스에탄올d-1: 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol

d-2: 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스카르복시산
d-2: 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] biscarboxylic acid

실험예: 유-무기 하이브리드형 배향막 제거 조성물의 특성 평가Experimental Example: Evaluation of Properties of Organic-Inorganic Hybrid Alignment Film-Removing Composition

1) 유-무기 하이브리드형 배향막의 제거력 평가1) Evaluation of Removal Force of Organic-Inorganic Hybrid Alignment Layer

유-무기 하이브리드형 배향막 제거력 평가를 위해, 유-무기 하이브리드형 배향막 (Butyl-Si-(O-Me)3)이 코팅된 유리기판을 1.5cm × 6cm 크기로 준비하였다. 준비된 기판을 실시예1~7 및 비교예1~8의 조성물에 1분간 및 3분간 실온에서 침지하여 세정하였다. 세정 후 초순수로 30초 동안 세척하고 질소로 건조하여, 평가 결과를 하기 표 2에 나타내었다.
In order to evaluate the organic-inorganic hybrid alignment layer removal ability, a glass substrate coated with an organic-inorganic hybrid alignment layer (Butyl-Si- (O-Me) 3) was prepared in a size of 1.5 cm × 6 cm. The prepared substrates were immersed in the compositions of Examples 1-7 and Comparative Examples 1-8 for 1 minute and 3 minutes at room temperature and washed. After washing for 30 seconds with ultrapure water and dried with nitrogen, the evaluation results are shown in Table 2 below.

<평가 기준><Evaluation Criteria>

○: 유-무기 하이브리드형 배향막이 제거되었을 때, ○: when the organic-inorganic hybrid type alignment film is removed,

△: 50%정도 제거되었을 때,?: When about 50% was removed,

×: 제거가 되지 않았을 때X: When no removal was made

또한, 실시예1의 세정액 조성물로 유-무기 하이브리드형 배향막을 제거한 전후의 결과를 도 1 및 도 2에 나타내었다.
In addition, the results before and after removing the organic-inorganic hybrid alignment layer with the cleaning liquid composition of Example 1 are shown in Figs.

2) 구리 및 알루미늄 에칭 속도 측정2) copper and aluminum etching rate measurement

먼저, 알루미늄이 2000Å 두께로 도포된 유리 기판과 구리가 2500Å 두께로 도포된 유리 기판을 상기 실시예 1 내지 7 및 비교예 1 내지 8에서 제조한 세정액에 각각 30분간 디핑(dipping)시켰다. 이때, 상기 세정액의 온도는 40℃이고, 상기 유리 기판에 도포된 알루미늄 및 구리 막의 두께를 디핑 전후로 측정하고, 각각의 용해속도를 두께 변화로부터 에칭속도를 계산하여 측정하고, 그에 대한 평가를 하기 표 2에 나타내었다.First, a glass substrate coated with 2000 mm thick and a glass substrate coated with 2500 mm thick were dipped into the cleaning liquids prepared in Examples 1 to 7 and Comparative Examples 1 to 8 for 30 minutes, respectively. At this time, the temperature of the cleaning solution is 40 ℃, the thickness of the aluminum and copper film applied to the glass substrate was measured before and after dipping, and each dissolution rate was measured by calculating the etching rate from the change in thickness, the evaluation for the following table 2 is shown.

Cu 에칭속도Cu etching rate Al 에칭속도 (A/분)Al etching rate (A / min) 유-무기 하이브리드형 배향막 제거력Organic-inorganic hybrid type alignment film removal force 1 분1 minute 3 분3 minutes 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 실시예7Example 7 비교예1Comparative Example 1 ΧΧ ΧΧ 비교예2Comparative Example 2 ΧΧ 비교예3Comparative Example 3 ΧΧ 비교예4Comparative Example 4 비교예5Comparative Example 5 비교예6Comparative Example 6 ΧΧ ΧΧ 비교예7Comparative Example 7 ΧΧ 비교예8Comparative Example 8 ΧΧ ΧΧ

알루미늄 및 구리 부식Aluminum and copper corrosion

◎: 우수(2A/분 미만)◎: excellent (less than 2A / min)

○: 양호(5A/분 미만)○: good (less than 5A / min)

△: 미흡(10A/분 미만)(Triangle | delta): Inadequate (less than 10 A / min)

X: 불량(10A/분 이상)
X: Poor (10 A / min or more)

상기 표 2의 시험 결과로부터, 본 발명의 세정제 조성물인 실시예 1~7의 조성물은 비교예 1~8의 조성물과 비교하여, 실온에서 유-무기 하이브리드형 배향막 제거력이 우수하며, 알루미늄에 대한 방식성도 대체적으로 우수하다는 것을 확인할 수 있었다.From the test results of Table 2, the composition of Examples 1 to 7 of the cleaning composition of the present invention is superior to the composition of Comparative Examples 1 to 8, the organic-inorganic hybrid type alignment film removal force at room temperature, the method for aluminum It was confirmed that the castle is generally excellent.

Claims (12)

(A) 무기 알칼리 화합물;
(B) 1종 또는 2종 이상의 유기 용제;
(C) 지방족 다가 알코올;
(D) 부식방지제;
및 잔량의 물을 포함하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
(A) an inorganic alkali compound;
(B) one or two or more organic solvents;
(C) aliphatic polyhydric alcohols;
(D) corrosion inhibitors;
And remaining amount of water, characterized in that the organic-inorganic hybrid type alignment film removal composition.
제 1항에 있어서,
유기 알칼리 화합물을 추가로 더 포함하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
The method of claim 1,
An organic-inorganic hybrid type alignment film removal composition, further comprising an organic alkali compound.
제 1항에 있어서,
(A) 무기 알칼리 화합물 0.1 ~ 5 중량%;
(B) 1종 또는 2종 이상의 유기 용제 30 ~ 80 중량%;
(C) 지방족 다가 알코올 10 ~ 50 중량%;
(D) 부식방지제 0.0001 ~ 1.0 중량 %;
및 잔량의 물을 포함하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
The method of claim 1,
(A) 0.1 to 5% by weight of an inorganic alkali compound;
(B) 30 to 80% by weight of one or two or more organic solvents;
(C) 10 to 50% by weight aliphatic polyhydric alcohol;
(D) 0.0001 to 1.0 weight percent corrosion inhibitor;
And remaining amount of water, characterized in that the organic-inorganic hybrid type alignment film removal composition.
제1항 또는 제2항에 있어서,
상기 무기 알칼리 화합물은 수산화칼륨(potassium hydroxide), 수산화나트륨(sodium hydroxide), 탄산나트륨(sodium carbonate), 탐산 칼륨(potassium carbonate)로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method according to claim 1 or 2,
The inorganic alkali compound is any one or a mixture of two or more selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate. Inorganic hybrid type alignment film removal composition.
제2항에 있어서,
상기 유기 알칼리 화합물은 테트라메틸암모늄하이드록 사이드(tetramethyl ammonium hydroxide, (CH3)4NOH), 테트라에틸암모늄하이드록사이드(tetraethyl ammonium hydroxide, (C2H5)4NOH), 테트라프로필암모늄하이드록사이드(tetrapropyl ammonium hydroxide, (C3H7)4NOH), 테트라부틸암모늄하이드록사이드(tetrabutyl ammonium hydroxide, (C4H9)4NOH), 탄산염, 인산염, 암모니아 및 알킬아민, 알릴아민, 알칸올아민, 알콕시아민 및 고리형아민으로 이루어진 군에서 선택된 아민류로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method of claim 2,
The organic alkali compound is tetramethyl ammonium hydroxide (CH 3 ) 4 NOH, tetraethyl ammonium hydroxide (C 2 H 5 ) 4 NOH, tetrapropylammonium hydroxide Tetrapropyl ammonium hydroxide, (C 3 H 7 ) 4 NOH, tetrabutyl ammonium hydroxide, (C 4 H 9 ) 4 NOH, carbonate, phosphate, ammonia and alkylamine, allylamine, alkanes An organic-inorganic hybrid alignment layer removing composition, characterized in that any one or a mixture of two or more selected from the group consisting of amines selected from the group consisting of olamines, alkoxyamines and cyclic amines.
제2항 또는 제 5항에 있어서
상기 유기 알칼리 화합물은 0.1중량% ~ 5중량%를 함유하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
The method according to claim 2 or 5
The organic-alkali compound contains 0.1 wt% to 5 wt% of an organic-inorganic hybrid alignment layer removing composition.
제1항 또는 제 2항에 있어서,
상기 유기 용제는 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노부틸에테르, 트리에틸렌글리콜 모노메틸에테르, 디메틸포름아마이드 (DMF), N-메틸포름아마이드, 디메틸아세트아마이드(DMAc), N-메틸아세트아마이드, 디에틸아세트아마이드(DEAc), N-메틸 피롤리돈(NMP), N-에틸 피롤리돈(NEP), N-프로틸 피롤리돈(NPP), N-하이드록시메틸 피롤리돈 및 N-하이드록시에틸 피롤리돈 등으로 이루어진 군에서 선택된 어느 하나 또는 이들의 혼합물인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method according to claim 1 or 2,
The organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dimethylformamide (DMF) , N-methylformamide, dimethylacetamide (DMAc), N-methylacetamide, diethylacetamide (DEAc), N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N- Removal of organic-inorganic hybrid alignment layer, characterized in that any one or a mixture thereof selected from the group consisting of propyl pyrrolidone (NPP), N-hydroxymethyl pyrrolidone, N-hydroxyethyl pyrrolidone and the like Composition.
제1항 또는 제2항에 있어서,
상기 지방족 다가 알코올은 글리세롤, 글루코오스, 만노오스, 갈릭토오스, 솔비통, 만니톨 및 폴리에틸렌글리콜로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물 인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method according to claim 1 or 2,
The aliphatic polyhydric alcohol is any one or a mixture of two or more selected from the group consisting of glycerol, glucose, mannose, galactose, sorbitan, mannitol and polyethylene glycol.
제1항 또는 제2항에 있어서,
상기 부식방지제는 2,2’-[[[벤조트리아졸]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스메탄올, 2,2’-[[[에틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스카르복시산, 2,2’-[[[메틸-1수소-벤조트리아졸-1-일]메틸]이미노]비스메틸아민 및 2,2’-[[[아민-1수소-벤조트리아졸-1-일]메틸]이미노]비스에탄올로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method according to claim 1 or 2,
The corrosion inhibitor is 2,2 '-[[[benzotriazole] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] Bismethanol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazole-1 -Yl] methyl] imino] bisethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] biscarboxylic acid, 2,2'-[[[methyl- Monohydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine and 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol Organic-inorganic hybrid alignment film removal composition, characterized in that at least one selected from the group.
제1항 또는 제2항에 있어서,
상기 부식방지제는 하기 화학식 1로 표시되는 벤조트리아졸 유도체인 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
[화학식 1]
Figure pat00002

(상기 화학식 1에서, R13 내지 R15는 서로 독립적으로 수소, 할로겐, 알킬기, 시클로알킬기, 알릴기, 아릴기, 아미노기, 알킬아미노기, 니트로기, 시아노기, 메르캅토기, 알킬메르캅토기, 히드록실기, 히드록시알킬기, 카르복실기, 카르복시알킬기, 아실기, 알콕시기 또는 헤테로고리아미노산을 치환기로 갖는 1가의 기이다.)
3. The method according to claim 1 or 2,
The corrosion inhibitor is an organic-inorganic hybrid type alignment film removal composition, characterized in that the benzotriazole derivative represented by the following formula (1).
[Formula 1]
Figure pat00002

(In Formula 1, R 13 to R 15 are each independently hydrogen, halogen, alkyl group, cycloalkyl group, allyl group, aryl group, amino group, alkylamino group, nitro group, cyano group, mercapto group, alkyl mercapto group, It is a monovalent group having a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group or a heterocyclic amino acid as a substituent.)
제1항 또는 제 2항에 있어서,
비이온성 계면활성제, 양이온성 계면활성제, 음이온성 계면활성제로 이루어진 군에서 선택된 어느 하나 또는 2종 이상의 혼합물을 추가로 더 포함하는 것을 특징으로 하는 유-무기 하이브리드형 배향막 제거 조성물.
3. The method according to claim 1 or 2,
An organic-inorganic hybrid alignment layer removing composition further comprising any one or a mixture of two or more selected from the group consisting of nonionic surfactants, cationic surfactants and anionic surfactants.
제1항 또는 제 2항의 유-무기 하이브리드형 배향막 제거 조성물을 사용하여 기판을 세정하는 공정을 포함하는 액정 표시 장치용 어레이 기판의 제조방법.A method for manufacturing an array substrate for a liquid crystal display device comprising the step of cleaning the substrate using the organic-inorganic hybrid type alignment film removing composition of claim 1.
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