KR100463309B1 - Resist Composition For Column Spacer of LCD - Google Patents
Resist Composition For Column Spacer of LCD Download PDFInfo
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- KR100463309B1 KR100463309B1 KR10-2001-0017151A KR20010017151A KR100463309B1 KR 100463309 B1 KR100463309 B1 KR 100463309B1 KR 20010017151 A KR20010017151 A KR 20010017151A KR 100463309 B1 KR100463309 B1 KR 100463309B1
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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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
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Abstract
본 발명은 액정표시소자 컬럼 스페이서용 레지스트 조성물에 관한 것으로서, 하기 일반식 1로 표시되는 바인더 수지, 하기 일반식 2로 표시되는 바인더 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 바인더 수지 10 내지 40중량부, 에틸렌 불포화 결합을 갖는 다관능성 모노머 1 내지 20중량부, 광개시제 1.25 내지 10중량부 및 에폭시기를 포함하는 실리콘계 화합물 0.001 내지 1.2중량부를 함유하는 것을 특징으로 한다. 본 발명에 따른 레지스트 조성물은 내열성이 우수할 뿐만 아니라, 액정표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 평탄성, 해상성, 잔막률 및 패턴 안정성이 양호하다.The present invention relates to a resist composition for a liquid crystal display device column spacer, comprising 10 to 40 parts by weight of a binder resin selected from the group consisting of a binder resin represented by the following general formula (1), a binder resin represented by the following general formula (2), and a mixture thereof: 1 to 20 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond, 1.25 to 10 parts by weight of a photoinitiator, and 0.001 to 1.2 parts by weight of a silicone compound containing an epoxy group. The resist composition according to the present invention is not only excellent in heat resistance, but also can be patterned to an appropriate thickness when forming column spacers of liquid crystal display devices, and has good flatness, resolution, residual film ratio, and pattern stability.
<일반식 1><Formula 1>
<일반식 2><Formula 2>
Description
본 발명은 액정표시소자의 컬럼 스페이서용 레지스트 조성물에 관한 것으로, 보다 상세하게는 액정표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 평탄성, 해상성, 잔막률 및 패턴 안정성이 우수한 레지스트 조성물에 관한 것이다.The present invention relates to a resist composition for a column spacer of a liquid crystal display device, and more particularly to a resist composition capable of forming a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device and having excellent flatness, resolution, residual film ratio, and pattern stability. It is about.
통상적으로 액정표시소자(LCD)는 2장의 마주보는 상하 패널과, 패널 사이에 삽입되는 스페이서 및 액정으로 구성되는데, 스페이서는 액정층의 두께, 즉 패널 사이의 간격인 셀갭을 유지시키는 기능을 한다. 셀갭이 일정하게 유지되어야만 고속 응답성, 높은 콘트라스트성, 광시야 각도성 등의 액정표시소자 성능이 구현될 수 있다.Typically, a liquid crystal display (LCD) is composed of two opposing top and bottom panels, a spacer inserted between the panels and a liquid crystal, and the spacer functions to maintain a cell gap, that is, the thickness of the liquid crystal layer, that is, the gap between the panels. Only when the cell gap is kept constant can the performance of liquid crystal display devices such as high-speed response, high contrast, and wide viewing angle be implemented.
현재 가장 많이 사용되고 있는 스페이서 형성 방법으로는 셀갭보다 직경이 조금 더 큰 투명한 구형 또는 실린더형의 폴리메틸메타크릴레이트나 실리카 입자를 분산, 도포하는 방법이 이용되고 있다. 이러한 방법은 액정을 주입할 때 구형이나 실린더형 입자가 부분적으로 응집하는 현상이 발생될 뿐만 아니라 액정 패널의 이동이나 진동, 충격 등에 의해 입자의 위치가 이동하여 균일한 분산이 이루어지지 않으므로 셀갭의 편차가 발생하여 일정한 셀갭이 유지되기 어렵다. 이에 따라, 액정층의 두께가 불균일하게 되어 액정표시소자의 색상이 변화하고 화상이 뒤틀리는 문제점이 발생한다. 또한, 배향막에 스크래치를 생성시켜 배향막을 손상시킬 수 있으며 상하 패널 기판을 압착 봉지할 때 전극이 손상 받을 가능성도 있다. 이러한 문제점들은 TFT LCD 등의 액정표시소자들의 대형화 추세에 따라, 또는 휴대전화, 호출기 등의 정보 단말기나 이동형 통신기, 차량용 운항 시스템 등에 대한 용도가 증대됨에 따라 더욱 심각해진다.The most widely used spacer formation method is a method of dispersing and applying transparent spherical or cylindrical polymethyl methacrylate or silica particles which are slightly larger in diameter than the cell gap. This method not only partially aggregates spherical or cylindrical particles when injecting liquid crystals, but also disperses cell gaps because the particles are not uniformly dispersed due to movement, vibration, or impact of the liquid crystal panel. Occurs, so that a constant cell gap is difficult to be maintained. Accordingly, the thickness of the liquid crystal layer is uneven, so that the color of the liquid crystal display element changes and the image is distorted. In addition, the alignment film may be scratched to damage the alignment film, and the electrode may be damaged when the upper and lower panel substrates are pressed and sealed. These problems become more serious as the size of liquid crystal display devices such as TFT LCDs increases, or as the use of information terminals such as mobile phones and pagers, mobile communication devices, and vehicle navigation systems increases.
이러한 문제점을 해결하기 위한 방법으로서 광경화성 조성물을 이용하여 고정형 컬럼 스페이서를 형성하는 방법이 제안되었다. 대한민국 공개공보 제1999-88297호에는 아크릴산과 아크릴레이트의 공중합체, 다가의 아크릴레이트 가교제 및 광개시제로 이루어진 조성물을 도포한 후 자외선을 조사하여 원하는 부분을 경화시키고 경화되지 않은 부분을 염기 수용액으로 세척하여 제거하는 방법으로 스페이서를 형성하는 방법이 개시되어 있다. 이러한 방법은 일정한 간격으로 일정한 두께를 갖는 고정된 스페이서를 형성할 수 있으므로, 외부 환경에 관계 없이 균일한 셀갭을 유지할 수 있는 장점이 있다.As a method for solving this problem, a method of forming a fixed column spacer using a photocurable composition has been proposed. Korean Laid-Open Publication No. 1999-88297 discloses a composition consisting of a copolymer of acrylic acid and acrylate, a polyvalent acrylate crosslinking agent and a photoinitiator, and then irradiates with UV rays to cure the desired portion, and to wash the uncured portion with an aqueous base solution. A method of forming a spacer as a method of removal is disclosed. This method can form a fixed spacer having a constant thickness at regular intervals, there is an advantage that can maintain a uniform cell gap regardless of the external environment.
그러나, 상기 공개특허에서 개시하고 있는 광경화성 조성물로는 액정표시장치에서 사용되는 셀갭인 3 내지 10㎛의 두께를 형성하는데 문제가 있다. 즉, 상기 조성물로는 스핀코팅 방법에 의해 3 내지 10㎛의 두께를 갖는 필름을 제조하기에 적당한 점도를 달성하기가 어려우므로, 상기 조성물을 스핀코팅하고 경화시켜 현상하는 작업을 수회 반복하여 적절한 두께를 갖는 스페이서를 형성해야 하는 번거러움이 있다. 또한, 상기 조성물은 아크릴계 수지를 주성분으로 사용하므로 경화 후 부피 수축이 발생하여 균일한 두께를 갖는 스페이서를 형성하기 어려우며, 내열성 및 패턴 안정성 또한 불량하다.However, the photocurable composition disclosed in the above-described patent has a problem in forming a thickness of 3 to 10 μm, which is a cell gap used in a liquid crystal display device. That is, since it is difficult to achieve a viscosity suitable for producing a film having a thickness of 3 to 10 μm by the spin coating method, the operation of spin coating, curing, and developing the composition is repeated several times to obtain an appropriate thickness. There is a hassle to form a spacer having a. In addition, since the composition uses an acrylic resin as a main component, volume shrinkage occurs after curing, making it difficult to form a spacer having a uniform thickness, and also having poor heat resistance and pattern stability.
따라서, 본 발명이 이루고자 하는 기술적 과제는 액정표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 내열성, 패턴 안정성, 평탄성, 해상성, 및 잔막률이 우수한 레지스트 조성물을 제공하는데 있다.Accordingly, an aspect of the present invention is to provide a resist composition capable of forming a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device and having excellent heat resistance, pattern stability, flatness, resolution, and residual film ratio.
상기 기술적 과제를 달성하기 위하여 본 발명은 하기 일반식 1로 표시되는 바인더 수지, 하기 일반식 2로 표시되는 바인더 수지 및 이들의 혼합물로 이루어진 군으로부터 선택된 바인더 수지 10 내지 40중량부, 에틸렌 불포화 결합을 갖는 다관능성 모노머 1 내지 20중량부, 광개시제 1.25 내지 10중량부 및 에폭시기를 포함하는 실리콘계 화합물 0.001 내지 1.2중량부를 함유하는 것을 특징으로 하는 액정표시소자 컬럼 스페이서용 레지스트 조성물을 제공한다;In order to achieve the above technical problem, the present invention provides 10 to 40 parts by weight of a binder resin selected from the group consisting of a binder resin represented by the following general formula (1), a binder resin represented by the following general formula (2), and mixtures thereof, an ethylenically unsaturated bond It provides a resist composition for a liquid crystal display device column spacer comprising 1 to 20 parts by weight of a polyfunctional monomer having, 0.001 to 1.2 parts by weight of a silicon-based compound comprising a photoinitiator 1.25 to 10 parts by weight and an epoxy group;
<일반식 1><Formula 1>
상기 일반식 1에서, X는 수소원자 또는 메틸기이고, Y1은 탄소원자수가 2 내지 16인 알킬기 또는 하이드록시알킬기이고, Y2는 하기 화학식(Ⅰ) 내지 화학식(XX)로 표시되는 화합물로부터 선택된 어느 하나임;In Formula 1, X is a hydrogen atom or a methyl group, Y 1 is an alkyl group or hydroxyalkyl group having 2 to 16 carbon atoms, Y 2 is selected from compounds represented by the following formula (I) to formula (XX) Which one;
상기 화학식(Ⅰ) 내지 화학식(XX)에서, R1은 수소 또는 메틸기이고, R2는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, R3는 탄소원자수가 1 내지 10인 탄화수소의 잔류 그룹이고, R4는 수소 또는 메틸기이고, R5는 탄소원자수가 1 내지 10인 알킬렌 그룹이고, k는 0 내지 10의 정수임;In formulas (I) to (XX), R 1 is hydrogen or a methyl group, R 2 is an alkylene group having 1 to 10 carbon atoms, and R 3 is a residual group of hydrocarbon having 1 to 10 carbon atoms R 4 is hydrogen or a methyl group, R 5 is an alkylene group having 1 to 10 carbon atoms, and k is an integer of 0 to 10;
<일반식 2><Formula 2>
상기 일반식 2에서, 치환기 A는 벤질메타아크릴레이트(Benzyl Methacrylate), 스티렌(Styrene), 알파-메틸스티렌(α-methyl styrene), 이소보닐아크릴레이트(isobonyl acrylate) 및 이소보닐메타아크릴레이트(Isobonyl methacrylate)로 이루어진 군으로부터 선택된 어느 하나이고, B는 아크릴산 또는 메타아크릴산이고, C는 글리시딜 메타아크릴레이트(Glycidyl Methacrylate), 히드록시에틸 메타아크릴레이트(Hydroxymethyl Methacrylate), 디메틸아미노 메타아크릴레이트(Dimethylamino Methacrylate), 아크릴아미드(Acryl amide)로 이루어진 군으로부터 선택된 어느 하나임.In Formula 2, the substituent A is benzyl methacrylate (Benzyl Methacrylate), styrene (Styrene), alpha-methyl styrene (α-methyl styrene), isobonyl acrylate (isobonyl acrylate) and isobonyl methacrylate (Isobonyl) methacrylate, any one selected from the group consisting of B, acrylic acid or methacrylic acid, C is glycidyl methacrylate (Glycidyl Methacrylate), hydroxyethyl methacrylate (Hydroxymethyl Methacrylate), dimethylamino methacrylate (Dimethylamino Methacrylate), acrylamide (acryl amide) any one selected from the group consisting of.
상기 일반식 1로 표시되는 바인더 수지는 카르복시산이 포함된 모노머와 이중결합을 갖는 모노머의 공중합체로서, 이러한 공중합체를 포함하는 본 발명의 조성물로 도포 후 패턴 형성시, 현상 후 잔사 등의 결함이 없고 평탄화율이 매우 우수하다. 즉, 상기 일반식 1의 Y1는 2개 내지 16개의 탄소원자를 갖는 알킬기 또는 하이드록시알킬기로서 접착력의 향상에 도움을 주고, Y2에는 방향족기를 포함하는 아크릴 공중합 수지로 된 종래의 바인더 수지와는 달리 벌키(bulky)한 지환족 구조를 포함하여 잔막율을 높일 뿐만 아니라 유리전이온도가 높아 내열성도 우수하다.The binder resin represented by Formula 1 is a copolymer of a monomer containing a carboxylic acid and a monomer having a double bond, and when the pattern is formed after coating with the composition of the present invention containing such a copolymer, defects such as residue after development are developed. And the flattening rate is very good. That is, Y 1 of Formula 1 helps to improve adhesion as an alkyl group or a hydroxyalkyl group having 2 to 16 carbon atoms, and Y 2 is different from a conventional binder resin made of an acrylic copolymer resin containing an aromatic group. Unlike the bulky alicyclic structure, it not only increases the residual film ratio, but also has high glass transition temperature, which is excellent in heat resistance.
상기 일반식 1로 표시되는 바인더 수지의 평균 분자량은 2,000 내지 50,000, 분산도는 1.0 내지 5.0, 산도는 30 내지 400KOHmg/g인 것을 사용하는 것이 바람직하며, 평균 분자량 5,000 내지 40,000이고, 분산도는 1.6 내지 3.0이고, 산도는 50 내지 150KOHmg/g인 것을 사용하는 것이 더욱 바람직하다.The average molecular weight of the binder resin represented by the general formula 1 is preferably 2,000 to 50,000, the dispersion degree is 1.0 to 5.0, the acidity is 30 to 400KOHmg / g, the average molecular weight is 5,000 to 40,000, the dispersion degree is 1.6 It is more preferable to use what is -3.0 and acidity is 50-150KOHmg / g.
또한, 상기 일반식 2로 표시되는 바인더 수지를 사용할 때도 동일한 효과를 나타낸다. 특히, 상기 일반식 1로 표시되는 바인더 수지와 일반식 2로 표시되는 바인더 수지를 혼합하여 사용하는 경우, 조성물 중의 다관능성 모노머와 바인더 수지의 상용성이 증가하여 유리 표면과의 부착성이 개선되고 패턴의 내깨짐성을 향상시킬 뿐만 아니라 백화현상(whitening)도 사라지게 된다. 이러한 일반식 1로 표시되는 바인더 수지의 평균 분자량은 2,000 내지 100,000, 분산도는 1.0 내지 5.0, 산도는 30 내지 400 KOHmg/g인 것을 사용하는 것이 바람직하며, 평균 분자량은 5,000 내지 60,000, 분산도는 1.6 내지 3.0, 산도는 50 내지150 KOHmg/g인 것을 사용하는 것이 더욱 바람직하다.Moreover, the same effect is exhibited when using the binder resin represented by the said General formula (2). In particular, when the binder resin represented by the general formula (1) and the binder resin represented by the general formula (2) are used in combination, the compatibility of the polyfunctional monomer and the binder resin in the composition is increased to improve adhesion to the glass surface Not only does it improve the fracture resistance of the pattern, it also eliminates whitening. The average molecular weight of the binder resin represented by the general formula 1 is preferably 2,000 to 100,000, the dispersity is 1.0 to 5.0, the acidity is 30 to 400 KOHmg / g, the average molecular weight is 5,000 to 60,000, the dispersity is As for 1.6-3.0 and acidity, it is more preferable to use 50-150 KOHmg / g.
본 발명에 따른 액정표시소자 컬럼 스페이서용 레지스트 조성물에 함유되는 에틸렌 불포화 결합을 갖는 다관능성 모노머는 통상적인 감광성 조성물에 사용하는 에틸렌성 불포화 결합을 갖는 중합성 화합물을 사용할 수 있는데, 예를 들어, 에틸렌글리콜디(메타)아크릴레이트, 에틸렌옥사이드기의 수가 2 내지 14인 폴리에틸렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트 등의 다가 알콜과 α,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물; 트리메틸올프로판트리글리시딜에테르아크릴산 부가물, 비스페놀 A 디글리시딜에테르아크릴산 부가물 등의 글리시딜기 함유 화합물에 (메타)아크릴산을 부가하여 얻어지는 화합물; β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트부가물 등의 수산기 및 에틸렌성 불포화 결합을 갖는 화합물과 다가 카르복시산과의 에스테르 화합물 또는 폴리이소시아네이트와의 부가물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 (메타)아크릴산알킬에스테르 등을 단독으로 또는 이들 중 둘 이상을 혼합하여 사용하는 것이 효과적이다.As the multifunctional monomer having an ethylenically unsaturated bond contained in the resist composition for a liquid crystal display device column spacer according to the present invention, a polymerizable compound having an ethylenically unsaturated bond used in a conventional photosensitive composition may be used. Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having the number of ethylene oxide groups 2 to 14, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tree ( Meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic Esterified polyhydric alcohols such as late and α, β-unsaturated carboxylic acids Eojineun compound; Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as trimethylolpropanetriglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group and an ethylenically unsaturated bond, such as a phthalic acid diester of β-hydroxyethyl (meth) acrylate, a toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, or a polyhydric carboxylic acid, or Adducts with polyisocyanates; (Meth) acrylic acid alkyl esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, or the like, alone or in combination of two or more thereof It is effective to use.
이러한 에틸렌 불포화 결합을 갖는 중합성 화합물인 다관능성 모노머와 바인더 수지의 조성을 본 발명에 따라 적절히 조절함으로써 고내열성, 고투명성, 고평탄화율 및 패턴안정성을 유지할 수 있는 컬럼 스페이서용 레지스트 조성물을 제조할 수 있다.By appropriately adjusting the composition of the polyfunctional monomer and the binder resin, which are polymerizable compounds having an ethylenically unsaturated bond, according to the present invention, a resist composition for column spacers capable of maintaining high heat resistance, high transparency, high flattening rate and pattern stability can be prepared. have.
또한, 본 발명의 레지스트 조성물에 함유되는 광개시제로는 투명성을 높이며 dose량을 최소화하기 위해서 아세토페논계나 벤조페논계를 광개시제를 단독으로 또는 이들을 혼합하여 사용하는 것이 바람직하다. 광개시제 자체가 색을 가지면 투명성을 저하시키는 작용을 하므로 노광 시 사용하는 파장대에서 적절한 감도를 갖고 광개시제 자체에 색을 갖지 않는 이러한 광개시제를 사용하면 고투명성을 실현할 수 있다. 일반적으로 아크릴계 다기능 모노머를 사용하는 가교 반응에서 광개시제는 사용하는 자외선의 파장에 맞추어서 사용되는데, 가장 널리 사용되는 자외선 파장인 수은 램프는 310∼420nm 영역의 파장을 가지므로 이 파장 영역에서 라디칼을 발생하는 광개시제를 사용하는 것이 바람직하다.In addition, as the photoinitiator contained in the resist composition of the present invention, it is preferable to use acetophenone series or benzophenone series alone or in combination thereof in order to increase transparency and minimize dose. If the photoinitiator itself has a color, the transparency is lowered. Therefore, high transparency can be achieved by using such a photoinitiator having appropriate sensitivity in the wavelength band used during exposure and having no color in the photoinitiator itself. In general, in the crosslinking reaction using an acrylic multifunctional monomer, a photoinitiator is used according to the wavelength of ultraviolet rays used. The mercury lamp, which is the most widely used ultraviolet ray, has a wavelength in the range of 310 to 420 nm, and generates radicals in this wavelength range. Preference is given to using photoinitiators.
이러한 광개시제로는 Irgacure 369, Irgacure 907, EPD/BMS 혼합계 등의 벤조페논계와 트리아진계 광개시제가 있는데, 예를 들면 벤조페논, 페닐비페닐케톤, 1-히드록시-1-벤조일시클로헥산, 벤질, 벤질디메틸케탈, 1-벤질-1-디메틸아미노-1-(4-모폴리노-벤조일)프로판, 2-모폴릴-2-(4-메틸머캅토)벤조일프로판, 치오잔톤(thSuch photoinitiators include benzophenone-based and triazine-based photoinitiators such as Irgacure 369, Irgacure 907, and EPD / BMS mixed system. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl , Benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, thioxanthone (th
ioxanthone), 1-클로로-4-프록시치오잔톤, 이소프로필치오잔톤, 디에틸치오잔톤,에틸안트라퀴논, 4-벤조일-4-메틸디페닐설파이드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 벤조일포름산메틸, 1,7-비스(9-아크리디닐)헵탄, 9-n-부틸-3,6-비스(2-모폴리노-이소부틸로일)카바졸, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스(트리클로로메틸)-s-트리아진 등이 있다.ioxanthone), 1-chloro-4- hydroxy thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl-4-methyl diphenyl sulfide, benzoin butyl ether, 2-hydroxy-2- Benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoyl formate, 1,7-bis (9-acridinyl ) Heptane, 9-n-butyl-3,6-bis (2-morpholino-isobutyloyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2 -Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine and the like.
본 발명의 레지스트 조성물에 함유되는 에폭시기를 갖는 실리콘계 첨가물은 ITO 전극과 조성물과의 접착력을 향상시키고 경화 후 내열 특성을 향상시킨다. 이러한 실리콘계 화합물로는 (3-글리시드옥시프로필)트리메톡시(에톡시)실레인 (3-글리시드옥시프로필)메틸디메톡시(에톡시)실레인, (3-글리시드옥시프로필) 디메틸메톡시(에톡시)실레인, 3, 4-에폭시부틸트리메톡시(에톡시)실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시(에톡시)실레인 등이 있으며, 이들을 각각 단독으로 또는 이들을 혼합하여 사용할 수 있다.The silicone-based additive having an epoxy group contained in the resist composition of the present invention improves adhesion between the ITO electrode and the composition and improves heat resistance properties after curing. Such silicone compounds include (3-glycidoxypropyl) trimethoxy (ethoxy) silane (3-glycidoxypropyl) methyldimethoxy (ethoxy) silane, (3-glycidoxypropyl) dimethyldimethyl Oxy (ethoxy) silane, 3,4-epoxybutyltrimethoxy (ethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy (ethoxy) silane, and the like. Each can be used individually or in mixture of these.
또한, 본 발명의 컬럼 스페이서용 레지스트 조성물에는 필요에 따라 광증감제, 열중합 금지제, 소포제, 레벨링제 등의 상용성이 있는 첨가제를 첨가할 수 있다.In addition, additives having compatibility such as photosensitizers, thermal polymerization inhibitors, antifoaming agents and leveling agents can be added to the resist composition for column spacers of the present invention.
본 발명의 컬럼 스페이서용 레지스트 조성물은 용매를 가하여 기판 위에 스핀코팅한 후 마스크를 이용하여 자외선을 조사하여 알칼리 현상액으로 현상하는 방법을 통하여 컬럼 스페이서를 형성하게 되는데, 점도를 10 내지 35 cps 범위가 되도록 용매를 첨가하는 것이 셀갭을 3 내지 10㎛의 두께로 유지할 수 있는 코팅층을제조하는데 바람직하다. 더욱 바람직하게는 점도를 15 내지 30 cps가 되도록 조절하는 것이 코팅 후 박막의 핀홀(pin-hole)이 없고 박막의 두께를 조절하는데 보다 유리하다. 이러한 용매로는 조성물의 코팅성 외에 얻어지는 박막의 투명성, 바인더 수지, 다기능 모노머 및 기타 화합물과의 상용성을 고려할 때 에틸아세테이트, 부틸아세테이트, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸(또는 에틸)아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포룸아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMIn the resist composition for a column spacer of the present invention, a column spacer is formed through spin coating on a substrate by adding a solvent and then developing with an alkaline developer by irradiating ultraviolet rays using a mask, so that the viscosity is in the range of 10 to 35 cps. It is preferable to add a solvent to prepare a coating layer capable of maintaining the cell gap at a thickness of 3 to 10 mu m. More preferably, adjusting the viscosity to be 15 to 30 cps is more advantageous for controlling the thickness of the thin film without the pin-hole of the thin film after coating. Such solvents include ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate (EEP) in consideration of the transparency of the thin film obtained in addition to the coating properties of the composition, compatibility with binder resins, multifunctional monomers and other compounds. ), Ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl (or ethyl) acetate, acetone, methyl Isobutyl ketone, cyclohexanone, dimethylformumamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NM
P), γ-부틸로락톤, 디에틸에테르, 에틸렌글리콜디메틸에테르, 디글림, 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸(또는 에틸)셀로솔브, 디에틸렌글리콜메틸(또는 에틸) 에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄, 옥탄 중에서 선택된 한 개 또는 두 개 이상을 혼합한 용매를 사용할 수 있다.P), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl (or ethyl) cellosolve, diethylene glycol methyl One or two or more solvents selected from (or ethyl) ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane may be used.
이하, 본 발명을 구체적으로 설명하기 위해 실시예 및 비교예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어져서는 안된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되어지는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
<실시예 1><Example 1>
자외선 차단막과 교반기가 설치되어 있는 반응혼합조에 하기에 기재된 조성 및 함량에 따라 바인더 수지, 다관능성 모노머, 광개시제, 실란계 에폭시 화합물과 소정의 광증감제, 열중합금지제, 소포제, 레벨링제를 순차적으로 첨가하여 컬럼 스페이서용 레지스트 조성물을 제조한 후 상온에서 교반하였다. 이어서, 조성물에 용매를 가하여 레지스트 조성물의 점도를 25 cps로 조절하였다.A binder resin, a polyfunctional monomer, a photoinitiator, a silane-based epoxy compound, a predetermined photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, and a leveling agent are sequentially added according to the composition and content described below in the reaction mixing tank equipped with the UV blocking film and the stirrer. After adding to prepare a resist composition for a column spacer and stirred at room temperature. Then, a solvent was added to the composition to adjust the viscosity of the resist composition to 25 cps.
실시예 중 바인더 수지는 전술한 일반식 1(일반식 1에서 X는 메틸기이고, Y1은 탄소원자수가 4인 알킬기)의 Y2가 각각 화학식(Ⅰ) 내지 화학식(XX)인 것을 화학식(1-Ⅰ) 내지 화학식(1-XX)로 표시하였다.In the examples, the binder resin may be represented by formula (1) in which the Y 2 of the general formula 1 (wherein X is a methyl group and Y 1 is an alkyl group having 4 carbon atoms) is represented by formulas (I) to (XX), respectively. -I) to the formula (1-XX).
<실시예 2~32><Examples 2 to 32>
상기 실시예 1의 조성물의 성분 및 함량을 하기에 기재된 조성에 따라서 변화시킨 것을 제외하고는 동일한 방법으로 컬럼 스페이서용 레지스트 조성물을 제조하였다.A resist composition for a column spacer was prepared in the same manner except that the components and contents of the composition of Example 1 were changed according to the compositions described below.
<비교예 1~8><Comparative Examples 1 to 8>
상기 실시예 1의 바인더 수지 대신 하기 일반식 3으로 표시되는 바인더 수지(평균 분자량 30,000)를 사용하고, 조성물의 성분 및 함량을 하기에 기재된 조성에 따라서 변화시킨 것을 제외하고는 동일한 방법으로 컬럼 스페이서용 레지스트 조성물을 제조하였다.Instead of the binder resin of Example 1, a binder resin (average molecular weight 30,000) represented by the following general formula 3 was used, except that the components and content of the composition were changed according to the composition described below for the column spacer A resist composition was prepared.
<일반식 3><Formula 3>
상기 일반식 3에서, p는 0.3이고, q는 0.2이며, r은 0.5임.In Formula 3, p is 0.3, q is 0.2, r is 0.5.
여기서, 용매의 첨가량 balance는 1000g에서 바인더수지, 다기능모노머, 실란계에폭시화합물, 광개시제 및 첨가제를 합한 중량을 제외한 나머지 중량을 의미한다.Here, the addition amount balance of the solvent means the remaining weight excluding the combined weight of the binder resin, the multifunctional monomer, the silane epoxy compound, the photoinitiator and the additive in 1000g.
이상의 실시예 및 비교예에 있어서 레지스트 조성물의 평가는 실리콘 웨이퍼 또는 유리판 등의 기판 위에서 실시하였으며, 레지스트 조성물의 열적특성조사, 평탄성(Uniformity), 잔막율, 패턴 형성 등의 성능평가를 실시하였으며, 그 결과를 하기에 나타냈다.In the above Examples and Comparative Examples, the resist composition was evaluated on a substrate such as a silicon wafer or a glass plate, and performance evaluations of thermal properties, uniformity, residual film ratio, pattern formation, and the like of the resist composition were performed. The results are shown below.
(1) 열적특성조사(1) Thermal characteristic investigation
컬럼 스페이서용 레지스트 조성물의 열적 성질을 평가하기 위해 열중량분석기(Thermogravimetric analysis: TGA)를 이용하여 열분해 온도를 측정하였으며, 초기무게의 5%가 감소되는 온도를 초기분해 온도로 하여 비교하였다.In order to evaluate the thermal properties of the resist composition for the column spacer, the pyrolysis temperature was measured using a thermogravimetric analysis (TGA), and the temperature at which 5% of the initial weight was reduced was compared as the initial decomposition temperature.
(2) 평탄성(2) flatness
레지스트 조성물을 기판 위에 스핀 코터를 이용하여 600rpm의 속도로 13초간 도포한 후, 90℃에서 3분간 프리베이크(prebake)하고, 365nm에서 15초간 경화시킨 후, 220℃에서 30초간 포스트베이크(postbake)를 실시하여 레지스트 막을 형성하였다. 실리콘 웨이퍼 또는 유리판에 형성된 레지스트막을 두께 측정기를 이용하여 각각 다른 25곳의 위치에서 두께를 측정하여 최대 두께와 최소두께의 차를 구하였다.The resist composition was applied onto the substrate using a spin coater at a speed of 600 rpm for 13 seconds, then prebaked at 90 ° C. for 3 minutes, cured at 365 nm for 15 seconds, and then postbaked at 220 ° C. for 30 seconds. Was carried out to form a resist film. The thickness of the resist film formed on the silicon wafer or the glass plate was measured at 25 different locations using a thickness measuring device to determine the difference between the maximum thickness and the minimum thickness.
(3) 잔막율(3) residual film rate
컬럼 스페이서용 레지스트 조성물을 기판 위에 스핀 코팅하고, 프리베이크(Pre-Bake)를 한 후의 두께와 포스트베이크(Post-Bake)를 하여 용매를 제거한 후 형성된 막의 두께 비율(%)을 측정하였다.The resist composition for the column spacer was spin-coated on a substrate, and the thickness after pre-baking and post-baking to remove the solvent to measure the thickness ratio (%) of the formed film.
(4) 패턴 형성(4) pattern formation
레지스트 패턴을 형성한 실리콘 웨이퍼를 라인 패턴의 수직방향에서부터 절단하고, 패턴의 단면 방향에서 전자현미경으로 관찰한 결과를 나타냈다. 패턴 사이드 벽(side wall)이 기판에 대하여 80도 이상의 각도로 세워져 있고, 막이 감소되지 않은 것을 '양호'로 하고, 막의 감소가 인정된 것을 '막감(膜減)'으로 판정하였다.The silicon wafer in which the resist pattern was formed was cut from the vertical direction of the line pattern, and the result observed by the electron microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 80 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.
상기 결과에서 알 수 있듯이, 본 발명의 컬럼 스페이서용 레지스트 조성물은 종래의 레지스트 조성물과는 달리 내열성이 우수할 뿐만 아니라, 막형성시 잔막율, 평탄성이 양호하고 패턴안정성 또한 매우 우수함을 알 수 있다.As can be seen from the above results, the resist composition for a column spacer of the present invention is not only excellent in heat resistance, but also excellent in residual film ratio, flatness, and pattern stability when forming a film.
이상에서 살펴본 바와 같이 본 발명에 따른 레지스트 조성물은 내열성이 우수할 뿐만 아니라, 균일하고 적절한 두께로 패턴 형성이 가능하고 해상성, 잔막률 및 패턴 안정성이 양호하다. 따라서, 본 발명의 레지스트 조성물을 이용하여 컬럼 스페이서를 형성하면, 표시소자의 크기에 관계 없이 균일한 셀갭을 유지시킬 수 있으며 액정 패널의 이동이나 진동, 충격 등에 의한 셀갭의 변화를 방지할 수 있다.As described above, the resist composition according to the present invention is not only excellent in heat resistance, but also capable of forming a pattern with a uniform and appropriate thickness, and having good resolution, residual film ratio, and pattern stability. Therefore, when the column spacer is formed using the resist composition of the present invention, a uniform cell gap can be maintained regardless of the size of the display device, and a change in the cell gap due to movement, vibration, or impact of the liquid crystal panel can be prevented.
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| CN 02108748 CN1255467C (en) | 2001-03-31 | 2002-03-29 | Protective film composition for cylindrical shock insulator of liquid crystal display element |
| JP2002097720A JP3467488B2 (en) | 2001-03-31 | 2002-03-29 | Resist composition for column spacer of liquid crystal display device |
| TW91106401A TWI266146B (en) | 2001-03-31 | 2002-03-29 | Resist composition for column spacer of liquid crystal display element |
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| KR100588379B1 (en) * | 2004-09-06 | 2006-06-12 | 안성화인케미칼 주식회사 | Resist Composition For Forming Resin Black Matrix of LCD |
| KR101254206B1 (en) * | 2011-02-11 | 2013-04-18 | 한국생산기술연구원 | Acrylic binders having hydroxy group for color filter |
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| KR20010100808A (en) * | 2000-03-08 | 2001-11-14 | 고토 기치 | Photosensitive resin composition, spacer and liquid crystal display element |
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