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KR101325884B1 - Photosensitive resin composition and black matrix thereof - Google Patents

Photosensitive resin composition and black matrix thereof Download PDF

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KR101325884B1
KR101325884B1 KR1020060118713A KR20060118713A KR101325884B1 KR 101325884 B1 KR101325884 B1 KR 101325884B1 KR 1020060118713 A KR1020060118713 A KR 1020060118713A KR 20060118713 A KR20060118713 A KR 20060118713A KR 101325884 B1 KR101325884 B1 KR 101325884B1
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resin composition
photosensitive resin
phenyl
poly
isothiocyanate
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KR1020060118713A
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Korean (ko)
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KR20080048580A (en
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윤종국
안경원
박상욱
채헌승
윤경근
박종민
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코오롱인더스트리 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
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)

Abstract

본 발명은 액정 디스플레이 장치 중의 차광에 사용되는 감광성 수지 조성물 및 이를 이용한 블랙매트릭스에 관한 것으로, 바인더 수지, 광중합 개시제, 블랙안료, 용제를 포함하는 액정 디스플레이용 블랙매트릭스 감광성 수지 조성물에 있어서, 굴절률이 1.5 이상인 고굴절성 유기재료를 포함하는 것을 특징으로 하는 감광성 수지 조성물을 제공하는 바, 패턴 현상 후 광투과율을 낮추고 광학밀도를 증가시킬 수 있고, 이와 같은 고굴절성 유기재료를 반응시켰음에도 적합한 접착강도를 가지며, 또한 조액의 저장안정성 또한 우수하여 액정 디스플레이 패널의 초박막형 소자의 구현이 가능하고 플랙시블 디스플레이(Flexible display)와 같이 가볍고 작고 얇은 기능성 디스플레이 소자의 구현을 앞당길 수 있는 발명이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition used for light shielding in a liquid crystal display device and a black matrix using the same. The present invention provides a photosensitive resin composition comprising a high refractive index organic material, which can reduce light transmittance and increase optical density after pattern development, and has suitable adhesive strength even when the high refractive index organic material is reacted. In addition, the storage stability of the liquid solution is also excellent, it is possible to implement the ultra-thin device of the liquid crystal display panel and to accelerate the implementation of light, small and thin functional display device, such as a flexible display (Flexible display).

Description

감광성 수지 조성물 및 이를 이용한 블랙매트릭스{Photosensitive resin composition and black matrix thereof}Photosensitive resin composition and black matrix using the same

도 1은 본 발명의 감광성 수지 조성물을 유리기판에 도포하여 활성선을 조사하여 경화된 감광성 막의 일례를 도시한 것이다.1 shows an example of a photosensitive film cured by applying the photosensitive resin composition of the present invention to a glass substrate and irradiating active rays.

* 도면의 주요부호의 설명* Explanation of the main symbols in the drawings

10 : 유리기판 20 : 감광성 막10 glass substrate 20 photosensitive film

30 : 고굴절성 유기재료 40 : 블랙안료30: high refractive organic material 40: black pigment

본 발명은 액정 디스플레이 장치 중의 차광에 사용되는 감광성 수지 조성물 및 이를 이용한 블랙매트릭스에 관한 것이다.  The present invention relates to a photosensitive resin composition used for light shielding in a liquid crystal display device and a black matrix using the same.

액정 디스플레이(Liquid Crystal Display)는 유전체 이방성을 갖는 액정 재료에 인가되는 전계를 제어하여 광을 전송하거나 차단함으로써 텍스트 또는 이미지를 디스플레이하는 디바이스로서, 전계 발광(EL) 디바이스, 음극선관(CRT) 및 발광 다이오드(LED)와 같은 내부적으로 광을 발생하는 디스플레이 장치와는 달리 LCD는 외부 광원을 사용한다.  Liquid crystal displays are devices that display text or images by transmitting or blocking light by controlling an electric field applied to a liquid crystal material having dielectric anisotropy. An electroluminescent (EL) device, a cathode ray tube (CRT), and a light emission Unlike a display device that generates light internally, such as a diode (LED), the LCD uses an external light source.

이와 같은 액정 디스플레이는 경량화, 박형화, 저가, 저소비전력구동화 및 우수한 집적회로화의 접합성 등의 장점을 가지고 있어 랩톱 컴퓨터나 포켓 컴퓨터의 표시판 및 차량적재용 칼라 TV 화상용으로 그 사용범위가 확대되고 있다. 이와 같은 액정 디스플레이 장치는 블랙매트릭스, 칼라필터 및 ITO(Indium Tin Oxide) 화소전극이 형성된 하부기판과, 액정층, 박막트랜지스터, 축전캐패시터층으로 구성된 능동회로부와 ITO 화소전극이 형성된 상부의 기판을 포함하여 구성된다. Such liquid crystal displays have advantages such as light weight, thinness, low cost, low power consumption, and excellent integrated circuit bonding, and are widely used for display panels of laptop computers and pocket computers and color TV images for vehicle loading. have. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an indium tin oxide (ITO) pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an upper substrate on which an ITO pixel electrode is formed. It is configured by.

종래의 액정 디스플레이 장치에서 사용되어온 칼라필터는 플라스틱, 또는 유리로 된 기판 상부에 블랙매트릭스와 적, 녹, 청 삼색의 착색층이 반복되며, 그 위에 칼라필터의 보호와 표면평활성을 유지하기 위해 폴리이미드, 폴리아크릴레이트, 폴리우레탄 등과 같은 재료의 두께 1 ~ 3㎛의 오버코트층과 오버코트층 상부에 액정 구동을 위한 전압이 인가되는 ITO 투명전도막층이 형성되어 있다.The color filter used in the conventional liquid crystal display device has a black matrix and red, green, and blue color layers repeated on a plastic or glass substrate, and a poly filter is used to maintain the color filter protection and surface smoothness. An overcoat layer having a thickness of 1 to 3 μm and a layer of an ITO transparent conductive layer to which a voltage for driving a liquid crystal is applied are formed on the overcoat layer.

여기서 블랙매트릭스는 기판의 투명화소전극 이외로 투과되어 제어되지 않는 광을 차단하여 콘트라스트를 향상시키는 역할을 하며, 적, 녹, 청 착색층은 백색광 중 특정 파장의 빛을 투과시켜 색을 표현할 수 있도록 하며, 투명전도막층은 액정에 전계를 인가하기 위한 공통전극의 역할을 한다. Here, the black matrix serves to improve contrast by blocking uncontrolled light transmitted through the transparent pixel electrode of the substrate, and the red, green, and blue colored layers transmit light of a specific wavelength among white light to express colors. The transparent conductive film layer serves as a common electrode for applying an electric field to the liquid crystal.

이 중 블랙매트릭스는 크롬으로 제조되거나 수지를 재료로 하여 제조될 수 있다. 그러나, 크롬을 사용할 경우, 차광성능, 내환경성, 내화학성이 우수하나 공정이 복잡하고 설비비가 높아 생산원가가 높고, 반사율이 높아 전반사를 위한 별도 의 처리공정이 필요한 문제점이 있어 최근에는 수지를 사용한 블랙매트릭스가 활발하게 연구되고 있다. Among them, the black matrix may be made of chromium or made of resin. However, when chromium is used, it has excellent shading performance, environmental resistance, and chemical resistance, but has a problem of requiring a separate treatment process for total reflection due to its complicated process and high equipment cost, and high reflectance. Black Matrix is being actively researched.

일반적으로 칼라필터의 기판은 염색법, 인쇄법, 안료분산법, 전착법 등의 방법에 의해 제조될 수 있는데, 블랙매트릭스는 주로 안료분산법에 의해 제조되고 있다. 안료분산법은 블랙매트릭스가 제공된 투명한 기재 위에 착색제를 함유하는 감광성 수지 조성물을 코팅하고, 형성하고자 하는 형태의 패턴을 노광한 후 비노광부위를 용제로 제거하여 열경화시키는 일련의 단계를 반복함으로써 칼라필터를 제조하는 방법이다. 이러한 안료분산법은 칼라필터의 가장 중요한 성질인 내열성 및 내구성을 향상시키며 필름의 두께를 균일하게 유지시킬 수 있다는 장점을 가지고 있어 블랙매트릭스의 제조에 많이 이용되고 있다. In general, the substrate of the color filter can be manufactured by a method such as dyeing, printing, pigment dispersion, electrodeposition, etc., the black matrix is mainly produced by the pigment dispersion method. The pigment dispersion method is a color filter by coating a photosensitive resin composition containing a colorant on a transparent substrate provided with a black matrix, exposing the pattern of the form to be formed, and then removing a non-exposed portion with a solvent and thermally curing the color filter by repeating a series of steps. It is a method of manufacturing. This pigment dispersion method is used in the manufacture of the black matrix has the advantage of improving the heat resistance and durability, which is the most important property of the color filter and maintaining the thickness of the film uniformly.

안료분산법에 의해 제조되는 블랙매트릭스는 크게, 지지체 역할 및 일정 두께를 유지하도록 하기 위한 고분자 화합물, 즉 바인더 수지와 노광시 광과 반응하여 포토레지스트상을 형성하는 광중합성 모노머의 2가지 성분으로 구성되고, 상기한 성분 외에 안료, 광개시제, 용제와 기타 첨가제 등을 포함하는 감광성 수지 조성물로부터 얻어진다. 이때 안료분산법에 사용되는 바인더 수지로는 폴리이미드 수지, 아크릴계 중합체와 아지드 화합물로 이루어진 감광성 수지, 페놀수지 등이 있으며, 비스페놀 플루오렌형 에폭시아크릴레이트 수지를 산무수물과 반응시켜 얻어진 수지인 카도계 바인더 수지를 이용한 컬러필터의 제조방법 등도 개시되어 있다.The black matrix produced by the pigment dispersion method is largely composed of two components, a polymer compound for maintaining a role and a constant thickness, that is, a binder resin and a photopolymerizable monomer which reacts with light during exposure to form a photoresist image. And a photosensitive resin composition containing a pigment, a photoinitiator, a solvent and other additives, etc., in addition to the above components. The binder resin used in the pigment dispersion method is a polyimide resin, a photosensitive resin composed of an acrylic polymer and an azide compound, a phenol resin, and the like, and a resin obtained by reacting a bisphenol fluorene type epoxy acrylate resin with an acid anhydride. Also disclosed are a method of manufacturing a color filter using a binder resin.

최근 LCD 및 컬러필터 제조 업체의 경박단소형 디스플레이 소자의 요청에 의해 보다 가볍고, 보다 얇은 디스플레이 재료에 관한 연구가 매우 활발하게 이루어 지고 있다. 따라서 감광성 수지재료의 근간을 이루고 있는 카본 블랙, 티탄블랙 밀베이스의 표면 구조 및 재료특성을 변화시켜 저항, 전도도, 광학밀도 등의 특성을 증진시키는 연구도 이루어지고 있으며, 포토레지스트 화합물의 조액공정(formulation process)중 첨가되는 바인더의 구조 및 첨가제를 이용하여 재료특성의 개선하고자하는 연구가 매우 활발하게 이루어지고 있다. Recently, research on lighter and thinner display materials has been actively conducted at the request of light and small display devices of LCD and color filter manufacturers. Therefore, researches to improve the properties of resistance, conductivity, optical density, etc. by changing the surface structure and material properties of carbon black and titanium black millbase, which are the basis of photosensitive resin materials, have been conducted. In order to improve the material properties by using the structure and additives of the binder added during the formulation process, much research is being actively conducted.

그러나 이와 같은 시도는 재료의 구조적인 변화를 시킴으로써 단위공정 이루어지는 포스트 베이크(post bake) 공정 후 패턴의 경화도가 낮아지고 후공정의 가혹조건에서의 신뢰성 불량의 원인으로 작용하는 문제점을 일으킬 수도 있다. However, such an attempt may cause a problem that the degree of cure of the pattern after the post bake process, which is performed in the unit process by changing the structural change of the material, may be a cause of poor reliability in the harsh conditions of the post process.

본 발명은 상기한 문제점을 해결하기 위한 것으로, 블랙매트릭스의 형성을 위한 감광성 수지 조성물에 유효 굴절률이 높은 유기재료를 조액 공정 중 더 포함한 결과, 경화된 블랙매트릭스의 광학밀도를 증진시킬 수 있음을 알게 되어 본 발명을 완성하게 되었다.The present invention has been made to solve the above-mentioned problems, and as a result of further including an organic material having a high effective refractive index during the liquid-liquid process in the photosensitive resin composition for forming the black matrix, it can be seen that the optical density of the cured black matrix can be improved. Thus, the present invention has been completed.

따라서 본 발명의 목적은 감광성 수지의 조액공정시 고굴절율을 갖는 유기재료를 분산시켜 컬러필터 공정을 거친 LCD의 차광특성을 증진시켜도 바람직한 접착강도를 보이면서 저장안정성이 우수하여 차세대 디스플레이인 얇은 디스플레이 등의 블랙매트릭스 등의 형성에 유용한 감광성 수지 조성물을 제공하는 데 있다. Accordingly, an object of the present invention is to disperse organic materials having a high refractive index during the liquid-liquid process of photosensitive resin to improve the light shielding characteristics of the LCD which has been subjected to the color filter process. It is providing the photosensitive resin composition useful for formation of a black matrix.

본 발명의 다른 목적은 상기 조성물을 이용한 블랙매트릭스를 제공하는 데도 있다.Another object of the present invention is to provide a black matrix using the composition.

상기와 같은 목적을 달성하기 위한 본 발명은 바인더 수지, 광중합 개시제, 블랙안료, 용제를 포함하는 액정 디스플레이용 블랙매트릭스 감광성 수지 조성물에 있어서, 굴절률이 1.5 이상인 고굴절성 유기재료를 포함하는 것을 특징으로 하는 감광성 수지 조성물을 제공한다.The present invention for achieving the above object is a black matrix photosensitive resin composition for a liquid crystal display comprising a binder resin, a photopolymerization initiator, a black pigment, a solvent, characterized in that it comprises a highly refractive organic material having a refractive index of 1.5 or more It provides a photosensitive resin composition.

상기 고굴절성 유기재료는 0.5 내지 10 중량% 포함하는 것을 특징으로 한다.The high refractive organic material is characterized in that it comprises 0.5 to 10% by weight.

상기 고굴절성 유기재료는 폴리페닐설폰, [(폴리페닐이소시아네이트)-코-포름알데히드]([(polyphenyl isocyanate)-co-formaldehyde]), 폴리(비스페놀A 카보네이트)(poly(bisphenol A carbonate)), 2-플루오로-4-요오도페닐보론산(2-Fluoro-4-iodophenylboroic acid), 티오벤조익산(Thiobenzoic Acid), 4-비닐아닐린(4-vinylaniline), 폴리스티렌, 트리스(메틸티오)메탄(Tris(methylthio)methane), 트리페닐포스파이트(Triphenylphosphite), 2,3,5-트리메틸나프탈렌(2,3,5-Trimethylnaphthalene), 2,3,4-트리플루오로페닐 이소티오시아네이트(2,3,4-Trifluorophenyl isothiocyanate), 3-(트리플루오로메틸티오)페닐 이소시아네이트(3-(Trifluoromethylthio)phenyl isothiocyanate), 2,4,6-트리클로로벤조일 클로라이드(2,4,6-Trichlorobenzoyl chloride), 트리클로로아세틱산(Trichloroacetic acid), 1,1,2-트리브로모에탄(1,1,2-tribromoethane), 트리브로모아세트알데히드(Tribromoacetaldehyde), 트리브로모아세탈 클로라이드(Tribromoacetal Chloride), p-톨릴 이소티오시아네이트(p-Tolyl isothiocyanate), m-톨릴 이소티오시아네이트(m-Tolyl isothiocyanate), o-톨릴 이소티오시아네이트(o-Tolyl isothiocyanate), N-티오닐아닐린(N-Thionylaniline), 폴리비닐톨루엔(polyvinyl toluene), 폴리(비닐톨루엔-코-α-메틸스티렌) (Poly(vinyltoluene-co-α-methylstyrene), 폴리(1-비닐 나프탈렌)(Poly(1-vinyl naphthalene)), 폴리[(페닐글리시딜에테르)-코-(포름알데히드)](Poly[(phenyl glycidyl ether)-co-formaldehyde]), 2-페닐톨루엔(2-phenyl toluene), 3-페닐톨루엔(3-phenyl toluene), 2-(페닐티오)에탄올(2-(Phenylthio) ethanol), 2-[(페닐티오)메틸]-2-사이클로펜텐-1-온(2-[(Phenylthio) methyl]-2-cyclopenten-1-one), (페닐티오)아세틸클로라이드((Phenylthio)acetyl chloride), 1-페닐피라졸(1-Phenylpyrazole), 페닐 프로파길 알데히드(Phenyl propargyl aldehyde), 페닐이소티오시아네이트(Phenyl isothiocyanate), N-페닐 에틸렌디아민(N-Phenyl ethylenediamine), 페닐클로로디티오포르메이트(Phenyl chlorodithioformate), o-페닐클로로티오포르메이트(o-phenyl Chlorothionoformate) 중에서 선택된 1종 이상의 것임을 특징으로 한다.The high refractive organic material is polyphenylsulfone, [(polyphenylisocyanate) -co-formaldehyde] ([(polyphenyl isocyanate) -co-formaldehyde]), poly (bisphenol A carbonate), 2-fluoro-4-iodophenylboroic acid, thiobenzoic acid, 4-vinylaniline, polystyrene, tris (methylthio) methane ( Tris (methylthio) methane), Triphenylphosphite, 2,3,5-trimethylnaphthalene, 2,3,4-trifluorophenyl isothiocyanate (2, 3,4-Trifluorophenyl isothiocyanate), 3- (trifluoromethylthio) phenyl isocyanate (3- (Trifluoromethylthio) phenyl isothiocyanate), 2,4,6-trichlorobenzoyl chloride (2,4,6-Trichlorobenzoyl chloride), Trichloroacetic acid, 1,1,2-tribromoethane, Tribromoacetaldehyde taldehyde), Tribromoacetal Chloride, p-Tolyl isothiocyanate, m-tolyl isothiocyanate, o-tolyl isothiocyanate (o -Tolyl isothiocyanate, N-thionylaniline, polyvinyl toluene, poly (vinyltoluene-co-α-methylstyrene), poly ( 1-vinyl naphthalene) (Poly (1-vinyl naphthalene)), poly [(phenylglycidyl ether) -co- (formaldehyde)] (Poly [(phenyl glycidyl ether) -co-formaldehyde]), 2-phenyl Toluene (2-phenyl toluene), 3-phenyl toluene, 2- (phenylthio) ethanol, 2-[(phenylthio) methyl] -2-cyclopentene- 1-one (2-[(Phenylthio) methyl] -2-cyclopenten-1-one), (phenylthio) acetylchloride, 1-phenylpyrazole, phenyl propargyl Phenyl propargyl aldehyde At least one selected from Phenyl isothiocyanate, N-Phenyl ethylenediamine, Phenyl chlorodithioformate and o-phenyl Chlorothionoformate It is characterized by.

상기 바인더 수지는 아크릴계 수지, 폴리이미드 수지, 페놀수지 및 카도계 수지 중 선택된 수지인 것임을 특징으로 한다.The binder resin is characterized in that the resin selected from acrylic resin, polyimide resin, phenol resin and cardo resin.

또한 본 발명은 상기 감광성 수지 조성물을 포함하는 액정 디스플레이용 블랙매트릭스를 제공한다.The present invention also provides a black matrix for liquid crystal display comprising the photosensitive resin composition.

상기 블랙매트릭스는 광학밀도가 단위두께(1㎛) 당 4.5 이상인 것을 특징으로 한다.The black matrix has an optical density of 4.5 or more per unit thickness (1 μm).

이하, 본 발명을 더욱 상세하게 설명하면 다음과 같다. Hereinafter, the present invention will be described in more detail.

<바인더 수지><Binder Resin>

본 발명의 감광성 수지 조성물에 있어서, 바인더 수지로는 아크릴계 수지, 폴리이미드 수지, 페놀수지 및 카도계 수지 중 선택된 수지를 사용한다. In the photosensitive resin composition of this invention, resin selected from acrylic resin, polyimide resin, phenol resin, and cardo resin is used as binder resin.

일반적으로 분자량이 적으면 자외선 경화 후 패턴의 스웰링(swelling)현상에 의해 현상속도가 빨라지고, 반면 분자량이 증가할 경우 반대로 현상시간이 늦어지는 단점이 있을 수 있다. 따라서 적당한 현상 시작온도(breaking point)를 갖고, 현상 공정 중 일정한 현상마진(Process Window)을 유지하여 안정된 공정 상태(process condition)를 얻을 수 있도록 바인더 수지의 분자량은 3000 내지 15000 정도인 것이 바람직하다. 바인더 수지의 함량은 조성물의 현상패턴, 현상성, 감도 안정성을 고려하여 전체 감광성 수지 조성물 중 5 내지 25 중량%인 것이 바람직하다. In general, when the molecular weight is low, the development speed is increased by the swelling phenomenon of the pattern after UV curing, whereas when the molecular weight is increased, the development time may be delayed. Therefore, the molecular weight of the binder resin is preferably about 3000 to 15000 so as to have a suitable developing start temperature (breaking point), and to maintain a stable process window during the developing process to obtain a stable process condition (process condition). The content of the binder resin is preferably 5 to 25% by weight of the total photosensitive resin composition in consideration of the development pattern, developability, and sensitivity stability of the composition.

<다관능성 모노머><Polyfunctional monomer>

본 발명의 감광성 수지 조성물에 있어서 사용할 수 있는 다관능성 모노머는 통상적으로 사용되고 있는 다관능성 아크릴레이트계 모노머로서, 구체적으로는 에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 1,3-부탄디올디아크 릴레이트, 테트라메틸렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 1,4-시클로헥산디올디아크릴레이트, 트리메틸롤트리아크릴레이트, 트리메틸롤 프로판트리아크릴레이트, 펜타에리트리톨트리아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 디펜타에리트리톨트리아크릴레이트, 디펜타에리트리톨테트라아크릴레이트, 솔비톨트리아크릴레이트, 솔비톨테트라크릴레이트, 솔비톨펜타크릴레이트, 솔비톨헥사크릴레이트, 테트라메틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 트리메틸올프로판트리메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 트리메틸올에탄트리메타크릴레이트, 1,3-부탄디올디메타크릴레이트, 펜타에리트리톨디메타크릴레이트, 디펜타에리트리톨디메타크릴레이트, 펜타에리트리톨트리메타크릴레이트, 비스[p-(3-메타크릴옥시-2-히드록시-프로폭시)페닐]디메틸메탄, 비스[p-(메타크릴록시-에폭시)페닐]디메틸메탄, 솔비톨트리메타크릴레이트, 솔비톨테트라메타크릴레이트, 2-에틸헥실아크릴레이트, 2-하이드록시에틸아크릴레이트, 2-하이드록시프로필아크릴레이트, 디메틸아미노에틸아크릴레이트, 디에틸아미노에틸아크릴레이트, 이소보닐아크릴레이트, n-비닐피롤리돈, 1,4-부틸렌글리콜디아크릴레이트, 1,6-헥산디올디아크릴레이트, 디에틸렌글리콜디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 펜타에리트리톨디아크릴레이트, 디펜타에리트리톨헥사크릴레이트, 테트라히드로퍼푸릴메타크릴레이트, 글리시딜아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 비닐아세테이트, 트리알릴시아누레이트 등을 사용할 수 있으며, 이들 모노머 이외에 이량체 및 삼량체와 같은 프리폴리머도 효과적으로 사용할 수 있다.The polyfunctional monomer which can be used in the photosensitive resin composition of this invention is a polyfunctional acrylate monomer currently used normally, Specifically, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diac Relate, tetramethylene glycol diacrylate, propylene glycol diacrylate, 1,4-cyclohexanediol diacrylate, trimethylol triacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, tetraethylene glycol Diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tetramethylene glycol dimethacrylate, triethylene Glycol Dimethacrylate , Trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, trimethylolethane trimethacrylate, 1,3-butanedioldimethacrylate, pentaerythritol dimethacrylate, dipentaerythritol dimethacrylate Latex, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxy-propoxy) phenyl] dimethylmethane, bis [p- (methacryloxy-epoxy) phenyl] dimethylmethane, Sorbitol trimethacrylate, Sorbitol tetramethacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, isobonyl Acrylate, n-vinylpyrrolidone, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate , Tripropylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, tetrahydrofurfuryl methacrylate, glycidyl acrylate, pentaerythritol tetraacrylate , Vinyl acetate, triallyl cyanurate, and the like can be used. In addition to these monomers, prepolymers such as dimers and trimers can also be used effectively.

이와 같은 다관능성 모노머의 함량은 전체 감광성 수지 조성물 중 0.5∼5 중량%가 바람직하다. 만일 그 함량이 0.5 중량% 미만일 경우에는 감광재료의 열분해 온도가 낮은 단점이 있고, 5 중량% 초과일 경우에는 보관성이 좋지 않은 문제가 있다.As for content of such a polyfunctional monomer, 0.5-5 weight% is preferable in the whole photosensitive resin composition. If the content is less than 0.5% by weight, there is a disadvantage in that the thermal decomposition temperature of the photosensitive material is low, and when the content is more than 5% by weight, there is a problem of poor storage.

<광중합 개시제> <Photopolymerization initiator>

본 발명의 감광성 수지 조성물에 있어서 광중합 개시제는 통상적으로 사용되는 것으로, 그 예로는, 2,2'-디에톡시아세토페논, 2,2'-디부톡시아세토페논, 2-히드록시-2-메틸프로피오페논, p-t-부틸트리클로로아세토페논, p-t-부틸디클로로아세토페논, 벤조페논, 4-클로로아세토페논, 4,4'-디메틸아미노벤조페논, 4,4'-디클로로벤조페논, 3,3'-디메틸-2-메톡시벤조페논, 2,2'-디클로로-4-페녹시아세토페논, 2-메틸-1-(4-메틸티오)페닐)-2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1온 등을 들 수 있다. In the photosensitive resin composition of this invention, a photoinitiator is used normally, For example, 2,2'- diethoxy acetophenone, 2,2'- dibutoxy acetophenone, and 2-hydroxy-2-methylpropy Ophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3 ' -Dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4-methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one, etc. are mentioned.

통상 광중합 개시제는 전체 감광성 수지 조성물 중 0.5 내지 7 중량%로 포함된다. Usually, a photoinitiator is contained in 0.5 to 7 weight% of the whole photosensitive resin composition.

<블랙안료><Black Pigment>

본 발명 감광성 수지 조성물에 있어서 블랙안료로는 특별히 한정되는 것은 아니며, 예컨대, 아닐린 블랙, 퍼릴렌 블랙, 티탄 블랙, 카본 블랙 등을 사용할 수 있으며, 색보정제로서 안트라퀴논계 안료, 페닐렌계 안료 등의 축합다환 안료, 프탈로시아닌 안료, 아조계 안료 등의 유기 안료를 사용할 수 있다. 이러한 블랙안료는 전체 감광성 수지 조성물 중 5 내지 30 중량%로 포함된다.In the photosensitive resin composition of the present invention, the black pigment is not particularly limited, and for example, aniline black, perylene black, titanium black, carbon black, and the like can be used, and anthraquinone pigments, phenylene pigments, etc. can be used as color correction agents. Organic pigments, such as a condensed polycyclic pigment, a phthalocyanine pigment, and an azo pigment, can be used. Such black pigment is included in 5 to 30% by weight of the total photosensitive resin composition.

<고굴절성 유기재료><High refractive organic material>

본 발명의 감광성 수지 조성물은 고굴절성의 유기재료를 포함한다. The photosensitive resin composition of this invention contains the highly refractive organic material.

고굴절성 유기재료는 입사광원의 전반사율을 증진시켜 궁극적으로 블랙매트릭스의 광학밀도(Optical Density)를 증진시킬 수 있다. High refractive organic materials can enhance the total reflectance of incident light sources and ultimately enhance the optical density of the black matrix.

상기 고굴절성 유기재료는 굴절률이 1.5 이상인 것으로, 폴리페닐설폰(n=1.672), [(폴리페닐이소시아네이트)-코-(포름알데히드)]([(polyphenyl isocyanate)-co-formaldehyde], n=1.634), 폴리(비스페놀A 카보네이트)(poly(bisphenol A carbonate), n=1.586), 2-플루오로-4-요오도페닐 보론산 (2-Fluoro-4-iodophenylboroic acid, n=1.615), 티오벤조익산(Thiobenzoic Acid, n=1.605), 4-비닐아닐린(4-vinylaniline, n=1.626), 폴리스티렌(n=1.59), 트리스(메틸티오)메탄(Tris(methylthio)methane, n=1.579), 트리페닐포스파이트(Triphenylphosphite, n=1.579), 2,3,5-트리메틸나프탈렌(2,3,5-Trimethylnaphthalene, n=1.608), 2,3,4-트리플루오로페닐 이소티오시아네이트(2,3,4-Trifluorophenyl isothiocyanate, n=1.577), 3-(트리플루오로메틸티오)페 닐 이소시아네이트(3-(Trifluoromethylthio)phenyl isothiocyanate, n=1.586), 2,4,6-트리클로로벤조일 클로라이드(2,4,6-Trichlorobenzoyl chloride, n=1.575), 트리클로로아세트산(Trichloroacetic acid, n=1.62), 1,1,2-트리브로모에탄(1,1,2-tribromoethane, n=1.593), 트리브로모아세트알데히드(Tribromoacetaldehyde, n=1.584), 트리브로모아세탈 클로라이드(Tribromoacetal Chloride, n=1.583), p-톨릴 이소티오시아네이트(p-Tolyl isothiocyanate, n=1.6345), m-톨릴 이소티오시아네이트(m-Tolyl isothiocyanate, n=1.6328), o-톨릴 이소티오시아네이트(o-Tolyl isothiocyanate, n=1.6361), N-티오닐아닐린(N-Thionylaniline, n=1.627), 폴리비닐톨루엔(polyvinyl toluene, n=1.59), 폴리(비닐톨루엔-코-α-메틸스티렌) (Poly(vinyltoluene-co-α-methylstyrene), n=1.58), 폴리(1-비닐 나프탈렌)(Poly(1-vinyl naphthalene), n=1.688), 폴리[(페닐글리시딜에테르)-코-(포름알데히드)](Poly[(phenyl glycidyl ether)-co-formaldehyde], n=1.598), 2-페닐톨루엔(2-phenyl toluene, n=1.591), 3-페닐톨루엔(3-phenyl toluene, n=1.602), 2-(페닐티오)에탄올(2-(Phenylthio) ethanol, n=1.592), 2-[(페닐티오)메틸]-2-사이클로펜텐-1-온(2-[(Phenylthio) methyl]-2-cyclopenten-1-one, n=1.6088), (페닐티오)아세틸클로라이드((Phenylthio)acetyl chloride, n=1.5825), 1-페닐피라졸(1-Phenylpyrazole, n=1.596), 페닐 프로파길 알데히드(Phenyl propargyl aldehyde, n=1.604), 페닐이소티오시아네이트(Phenyl isothiocyanate, n=1.6515), N-페닐 에틸렌디아민(N-Phenyl ethylenediamine, n=1.587), 페닐클로로디티오포르메이트(Phenyl chlorodithioformate, n=1.6688), o-페닐클로로티오포르메이트(o-phenyl Chlorothionoformate, n=1.581) 등을 들 수 있다. The high refractive organic material has a refractive index of 1.5 or more, polyphenylsulfone (n = 1.672), [(polyphenylisocyanate) -co- (formaldehyde)] ([(polyphenyl isocyanate) -co-formaldehyde], n = 1.634 ), Poly (bisphenol A carbonate), n = 1.586), 2-fluoro-4-iodophenylboroic acid (2-Fluoro-4-iodophenylboroic acid, n = 1.615), thiobenzo Ikic acid (Thiobenzoic Acid, n = 1.605), 4-vinylaniline (n = 1.626), polystyrene (n = 1.59), Tris (methylthio) methane (n = 1.579), tree Triphenylphosphite (n = 1.579), 2,3,5-trimethylnaphthalene (2,3,5-Trimethylnaphthalene, n = 1.608), 2,3,4-trifluorophenyl isothiocyanate (2, 3,4-Trifluorophenyl isothiocyanate, n = 1.577), 3- (trifluoromethylthio) phenyl isocyanate (3- (Trifluoromethylthio) phenyl isothiocyanate, n = 1.586), 2,4,6-trichlorobenzoyl chloride (2 , 4,6-Trichlorobenzoyl chloride, n = 1.575), Trichloroacetic acid (n = 1.62), 1,1,2-tribromoethane (1,1,2-tribromoethane, n = 1.593), Tribromoacetaldehyde (n = 1.584), Tribromoacetal Chloride (n = 1.583), p-Tolyl isothiocyanate (n = 1.6345), m-tolyl isothiocyanate, n = 1.6328), o-tolyl isothiocyanate (n = 1.6361), N-thionylaniline (n = 1.627), polyvinyl toluene (n = 1.59), poly ( Vinyltoluene-co-α-methylstyrene) (Poly (vinyltoluene-co-α-methylstyrene), n = 1.58), poly (1-vinyl naphthalene) (n = 1.688), poly [ (Phenylglycidyl ether) -co- (formaldehyde)] (Poly [(phenyl glycidyl ether) -co-formaldehyde], n = 1.598), 2-phenyl toluene, n = 1.591), 3 3-phenyl toluene (n = 1.602), 2- (phenylthio) ethanol (2- (Phenylt) hio) ethanol, n = 1.592), 2-[(phenylthio) methyl] -2-cyclopenten-l-one (2-[(Phenylthio) methyl] -2-cyclopenten-1-one, n = 1.6088), (Phenylthio) acetyl chloride (n = 1.5825), 1-phenylpyrazole (n = 1.596), phenyl propargyl aldehyde (n = 1.604), phenylisothio Cyanate (Phenyl isothiocyanate, n = 1.6515), N-Phenyl ethylenediamine (n = 1.587), Phenyl chlorodithioformate (n = 1.6688), o-phenylchlorothioformate ( o-phenyl Chlorothionoformate, n = 1.581).

상기 고굴절성 유기재료는 전체 감광성 수지 조성물 중 0.5 내지 10 중량%인 것이 바람직하다. 만일, 그 함량이 전체 감광성 수지 조성물 중 0.5 중량% 미만이면 사용하지 않은 경우의 굴절율과의 편차가 작아 광학밀도 향상의 전반사 특성이 나타나지 않아 광학밀도의 변화가 없다. 반대로 10 중량%를 초과하면 최종 조액된 조성물 중 카본 블랙밀베이스의 카본 입자와 함께 반응 불순물로 작용하여 현상 후 블랙매트릭스 패턴상의 잔사 및 돌기 등의 문제와 패턴 직진성, 현상성에 문제를 야기시킬 수 있다.The high refractive organic material is preferably 0.5 to 10% by weight of the total photosensitive resin composition. If the content is less than 0.5% by weight in the total photosensitive resin composition, the deviation from the refractive index when not used is small, and the total reflection characteristic of the optical density improvement does not appear, and there is no change in the optical density. On the contrary, if the content exceeds 10% by weight, it may act as a reaction impurity together with the carbon particles of the carbon black mill base in the final prepared composition, causing problems such as residues and protrusions on the black matrix pattern after development, and problems with pattern straightness and developability. .

<용제><Solvent>

본 발명에서 용제로는 통상적으로 사용되는 것으로, 예컨대 에틸렌글리콜 아세테이트, 에틸셀로솔브, 프로필렌글리콜메틸에테르아세테이트, 에틸락테이트, 폴리에틸렌글리콜, 시클로헥사논, 프로필렌글리콜메틸에테르 등을 사용할 수 있고, 이들 용제 중에서 선택하여 단독 또는 혼합하여 사용할 수 있다. 본 발명에서 사용되는 용제의 비율은 감광성 수지 조성물에 따라 달라질 수 있으므로 그 함량을 구체적으로 규정할 수는 없으나, 수지액이 기판에 도포될 수 있는 점도를 갖도록 용제의 비율을 선택하는 것이 바람직하다. 통상적으로 그 함량은 전체 수지 조성물 중 50 내지 88 중량%이다. In the present invention, as the solvent, those commonly used may include, for example, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like. It can select from a solvent and can use individually or in mixture. Since the proportion of the solvent used in the present invention may vary depending on the photosensitive resin composition, the content thereof cannot be specifically defined, but it is preferable to select the proportion of the solvent so that the resin solution has a viscosity that can be applied to the substrate. Typically the content is from 50 to 88% by weight of the total resin composition.

<기타><Others>

본 발명에서는 접착력을 고려하여 접착증진제(adhesion promoter)를 더 첨가할 수 있는데, 일 예로는 신에츠社의 KBM-403 (GPTMS, 3-glycidoxy propyl trimethoxy silane), KBE-603 (N-2(aminoethyl) 3-amino propyl triethoxy silane) 등을 들 수 있다. 이러한 접착증진제를 포함하는 경우 전체 감광성 수지 조성물 중 0.1 내지 0.5 중량% 첨가하는 것이 바람직하다.In the present invention, an adhesion promoter may be further added in consideration of adhesion. For example, KBM-403 (GPTMS, 3-glycidoxy propyl trimethoxy silane) of Shin-Etsu Corporation, KBE-603 (N-2 (aminoethyl) 3-amino propyl triethoxy silane), and the like. In the case of including such an adhesion promoter, it is preferable to add 0.1 to 0.5% by weight of the entire photosensitive resin composition.

또한, 혼합물 속에 안료를 분산시키는 데 있어서 바람직한 분산을 고려하여 분산제를 사용할 수 있는데, 미리 안료를 표면처리하는 형태로 안료 내부에 첨가시켜 사용하거나, 안료에 외부 첨가하는 방법으로 사용할 수 있다. 이러한 분산제로는 비이온성, 음이온성 또는 양이온성 분산제를 사용할 수 있는데, 구체적인 예로는 폴리알킬렌글리콜 및 이의 에스테르, 폴리옥시알킬렌 다가알콜 에스테르 알킬렌 옥사이드 부가물, 알콜알킬렌옥사이드 부가물, 설폰산 에스테르, 설폰산염, 카르복실산에스테르, 카르복실산염, 알킬아미드 알킬렌옥사이드 부가물, 알킬아민 등을 들 수 있다. 이들은 단독으로 첨가하거나 둘 이상 조합하여 첨가할 수 있다.In addition, a dispersant may be used in consideration of the desired dispersion in dispersing the pigment in the mixture, it may be used by adding the inside of the pigment in the form of surface treatment in advance, or may be used by the method of external addition to the pigment. Such dispersants may include nonionic, anionic or cationic dispersants, specific examples of which are polyalkylene glycols and esters thereof, polyoxyalkylene polyalcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, Phonic acid ester, sulfonate, carboxylic acid ester, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc. are mentioned. These may be added alone or in combination of two or more.

이외에도 본 발명 조성물에는 조성물의 물성을 저해하지 않는 범위 내에서 계면활성제, 산화방지제, 안정제 등 기타의 첨가제를 첨가할 수 있음은 물론이다. In addition, other additives such as surfactants, antioxidants, stabilizers and the like can be added to the composition of the present invention within a range that does not impair the physical properties of the composition.

이와 같이 얻어진 감광성 수지 조성물은 액정 디스플레이 장치의 컬러필터용 블랙매트릭스 제조에 사용될 수 있다. 본 발명의 감광성 수지 조성물을 이용하여 블랙매트릭스를 제조하는 경우에는 컬러필터용 유리기판 위에 스핀 도포, 롤러 도포, 스프레이 도포 등의 적당한 방법을 사용하여 0.5 내지 10㎛ 두께로 감광성 수지 조성물을 도포한다. 그리고 90 내지 120 ℃에서 소프트 베이크(soft bake)한다. 그리고 나서, 컬러필터에 필요한 패턴을 형성하도록 활성선을 조사한다. 조사에 사용되는 광원으로는 190 내지 450nm, 바람직하게는 200 내지 400nm 영역의 UV를 사용하며, 전자선 및 X선 조사도 적당하다. 조사 후, 도포층을 현상액으로 처리하면 도포층의 미노광 부분이 용해되고 컬러필터에 필요한 패턴이 형성된다. 그 다음, 이러한 공정을 필요한 색의 수에 따라 반복함으로써 원하는 패턴을 갖는 컬러필터를 수득할 수 있다. The photosensitive resin composition thus obtained can be used for producing the black matrix for color filters of the liquid crystal display device. When manufacturing a black matrix using the photosensitive resin composition of this invention, the photosensitive resin composition is apply | coated to 0.5-10 micrometer thickness on the glass substrate for color filters using a suitable method, such as spin coating, roller coating, and spray coating. And soft bake at 90 to 120 ° C. Then, the active line is irradiated to form a pattern required for the color filter. As the light source used for the irradiation, UV of 190 to 450 nm, preferably 200 to 400 nm is used, and electron beam and X-ray irradiation are also suitable. After the irradiation, when the coating layer is treated with a developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the color filter is formed. This process can then be repeated according to the number of colors required to obtain a color filter with the desired pattern.

도 1은 본 발명의 감광성 수지 조성물을 유리기판(10)에 도포하여 활성선을 조사하여 경화된 감광성 막(20)의 일례를 도시한 것이다.FIG. 1 shows an example of the photosensitive film 20 cured by applying the photosensitive resin composition of the present invention to the glass substrate 10 and irradiating active rays.

고굴절성 유기재료(30) 및 블랙안료(40)가 분산되어 있는 감광성 수지 조성물은 경화 후에도 고굴절성 유기재료(30)로 인하여 전체 감광성 수지 조성물의 굴절률이 증가하게 되며, 따라서 컬러필터의 제조공정을 통과하여 최종제품으로 완성된 후의 디스플레이 장치의 화소에 광이 입사되면 고굴절성 유기재료(30)에 의해 전반사 빈도가 증가하게 된다. 전반사의 빈도가 증가함에 따라 감광성 수지조성물의 광차단효과가 증가하여 광투과도(Transmittance)는 감소하는 결과를 얻는다.In the photosensitive resin composition in which the high refractive index organic material 30 and the black pigment 40 are dispersed, the refractive index of the entire photosensitive resin composition is increased due to the high refractive index organic material 30 even after curing. When light is incident on the pixel of the display apparatus after passing through and finished as a final product, the total reflection frequency is increased by the highly refractive organic material 30. As the frequency of total reflection increases, the light blocking effect of the photosensitive resin composition increases, resulting in a decrease in the light transmittance.

광투과도와 광학밀도의 관계는 하기의 식 1과 같이 표시되며, 반비례하는 것을 알 수 있다.The relationship between the light transmittance and the optical density is expressed as in Equation 1 below, and it can be seen that it is inversely proportional.

<식 1><Formula 1>

Figure 112006088206846-pat00001
Figure 112006088206846-pat00001

이에 따라서, 본 발명의 감광성 수지 조성물의 경우는 입사광의 흡수 및 반사계수를 증가시켜 높은 광학밀도(Optical Density)를 갖는 고기능성 디스플레이용 감광성 수지 조성물의 제조를 가능하게 하였다. Accordingly, in the case of the photosensitive resin composition of the present invention, the absorption and the reflection coefficient of incident light are increased to enable the production of the photosensitive resin composition for a high-functional display having a high optical density.

이는 높은 광학특성을 보유한 초 박막형 디스플레이 소자의 제조를 가능하게 함과 동시에 플랙시블 디스플레이(Flexible Display)와 같은 보다 가볍고, 작고, 얇은 기능성 소자의 구현도 앞당길 수 있는 발명이다. 특히, 온화한 경화조건을 요하는 가요성 디스플레이 등의 블랙매트릭스 형성용 수지 조성물로 유용하다. This enables the manufacture of ultra-thin display devices having high optical properties and at the same time accelerates the implementation of lighter, smaller and thinner functional devices such as flexible displays. It is especially useful as resin composition for black matrix formation, such as a flexible display which requires mild hardening conditions.

또한, PDP, 패시베이션(passivation), 드라이 필름 포토레지스트 및 그 밖의 유기 반도체의 감광성 수지 조성물로서도 유용하다.It is also useful as a photosensitive resin composition of PDP, passivation, dry film photoresist and other organic semiconductors.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

<실시예 1> &Lt; Example 1 >

9, 9-비스-(4-히드록시 페닐)플루오렌과 에폭시 수지를 공중합하여 산무수물 반응한 바인더 수지 25중량%, 블랙안료 32중량%, 용제로서 PGMEA 30 중량%, 다관능성 모노머 5 중량%, 광중합 개시제 3 중량%, 접착증진제로써 신에츠사의 KBM-403, 2중량%, 고굴절성 유기재료로써 Polyphenyl Sulfone (n=1.672) 3중량%를 첨가하여 감광성 수지 조성물을 조액하였다.25 weight% of binder resin copolymerized with 9, 9-bis- (4-hydroxyphenyl) fluorene and an epoxy resin to react with acid anhydride, 32 weight% of black pigment, 30 weight% of PGMEA as a solvent, 5 weight% of polyfunctional monomer , Photopolymerization initiator 3% by weight, Shin-Etsu Co., Ltd. KBM-403, 2% by weight, and 3% by weight of polyphenyl sulfate (n = 1.672) as a highly refractive organic material was added to prepare a photosensitive resin composition.

<실시예 2> <Example 2>

상기 실시예 1에서 고굴절성 유기재료로써 Poly(1-vinylnaphthalen) (n=1.6818)를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.A photosensitive resin composition was prepared in the same manner as in Example 1 except that Poly (1-vinylnaphthalen) (n = 1.6818) was added as the highly refractive organic material.

<실시예 3><Example 3>

상기 실시예 1에서 고굴절성 유기재료로써 Poly[(phenyl isocyanate)-co-formaldehyde] (n=1.634)를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.The photosensitive resin composition was prepared in the same manner as in Example 1 except that Poly [(phenyl isocyanate) -co-formaldehyde] (n = 1.634) was added as the highly refractive organic material.

<실시예 4> <Example 4>

상기 실시예 1에서 고굴절성 유기재료로써 2-Fluoro-4-iodophenylboroic acid) (n=1.615)를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.A photosensitive resin composition was prepared in the same manner as in Example 1, except that 2-Fluoro-4-iodophenylboroic acid (n = 1.615) was added as the highly refractive organic material.

<실시예 5> <Example 5>

상기 실시예 1에서 고굴절성 유기재료로써 Phenyl isothiocyanate (n=1.6515)를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.A photosensitive resin composition was prepared in the same manner as in Example 1 except that Phenyl isothiocyanate (n = 1.6515) was added as the highly refractive organic material.

<실시예 6> <Example 6>

아크릴계 공중합체 바인더 수지 25중량%, 블랙안료 32중량%, 용제로서 PGMEA 30 중량%, 다관능성 모노머 5 중량%, 광중합 개시제 3 중량%, 접착증진제로써 신에츠사의 KBM-403, 2중량%, 고굴절성 유기재료로써 Polyphenyl Sulfone (n=1.672) 3중량%를 첨가하여 감광성 수지 조성물을 조액하였다.25% by weight of acrylic copolymer binder resin, 32% by weight of black pigment, 30% by weight of PGMEA as solvent, 5% by weight of polyfunctional monomer, 3% by weight of photopolymerization initiator, KBM-403, 2% by weight of Shinetsu as adhesion promoter, high refractive index 3 wt% of Polyphenyl Sulfone (n = 1.672) was added as an organic material to prepare a photosensitive resin composition.

<실시예 7> &Lt; Example 7 >

상기 실시예 1에서 고굴절성 유기재료로써 Polyphenyl Sulfone (n=1.672) 0.2 중량%를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.2 wt% of Polyphenyl Sulfone (n = 1.672) was added as the highly refractive organic material.

<실시예 8> &Lt; Example 8 >

상기 실시예 1에서 고굴절성 유기재료로써 Polyphenyl Sulfone (n=1.672) 12중량%를 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.A photosensitive resin composition was prepared in the same manner as in Example 1, except that 12 wt% of Polyphenyl Sulfone (n = 1.672) was added as the highly refractive organic material.

<비교예 1>&Lt; Comparative Example 1 &

감광성 수지 조성물로서 Kolon社에서 제조한 Onlymer BM-4050를 사용하여 평가를 진행하였다. 고굴절성 유기재료를 사용하지 않은 재료이다. Evaluation was performed using Onlymer BM-4050 manufactured by Kolon as a photosensitive resin composition. This material does not use high refractive organic material.

<비교예 2> Comparative Example 2

감광성 수지 조성물로서 TOK 社에서 제조한 BK-4707SL을 사용하여 평가를 진행하였다. 고굴절성 유기재료를 사용하지 않은 재료이다. Evaluation was performed using BK-4707SL manufactured by TOK Corporation as a photosensitive resin composition. This material does not use high refractive organic material.

<비교예 3> &Lt; Comparative Example 3 &

TOK 社에서 제조한 범용 감광성 수지조성물로써 BK-4700을 사용하여 평가를 진행하였다. 고굴절성 유기재료를 사용하지 않은 재료이다. Evaluation was performed using BK-4700 as a general photosensitive resin composition manufactured by TOK. This material does not use high refractive organic material.

<비교예 4>&Lt; Comparative Example 4 &

상기 실시예 1에서 굴절률이 1.396인 폴리 디메틸실록산-코-메틸드로실록산 (Poly(dimethylsiloxane-co-methyldrosiloxane) 을 폴리페닐설폰 대신 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.In Example 1, a photosensitive resin composition was prepared in the same manner, except that polydimethylsiloxane-co-methyldrosiloxane (Poly (dimethylsiloxane-co-methyldrosiloxane)) having a refractive index of 1.396 was added instead of polyphenylsulfone.

<비교예 5>&Lt; Comparative Example 5 &

상기 실시예 1에서 굴절률이 1.461인 폴리옥시에틸렌 트리데실에테르 (Polyoxyethylene tridecyl ether)를 폴리페닐설폰 대신 첨가한 것을 제외하고 동일한 방법으로 감광성 수지 조성물을 조액하였다.The photosensitive resin composition was prepared in the same manner as in Example 1, except that polyoxyethylene tridecyl ether having a refractive index of 1.461 was added instead of polyphenylsulfone.

<실험예><Experimental Example>

상기 실시예 및 비교예에 따라 조액한 감광성 수지 조성물을 다음과 같은 포토리소그래피 공정을 통해 제조하고 평가를 수행한다.The photosensitive resin composition prepared according to the above Examples and Comparative Examples was prepared through the following photolithography process and evaluated.

포토리소그래피 공정은, 먼저 컬러필터용 유리기판 위에 상기 감광성 수지 조성물 각각을 스핀 코팅하여 두께 1.2㎛ 되도록 도포하였다. 이와 같이 얻어진 컬러필터에 필요한 패턴을 형성하기 위해 자외선을 광원으로 하여 활성선을 조사하였다. 이때의 조사량은 75 mJ 이었다. 그리고 도포층을 알칼리 현상액(KOH)으로 현상 처리하여 도포층의 미노광 부분을 용해시키고 컬러필터에 필요한 패턴을 형성하였다. In the photolithography process, first, each of the photosensitive resin compositions was spin-coated on a glass substrate for color filters to apply a thickness of 1.2 μm. In order to form the pattern required for the color filter thus obtained, ultraviolet rays were used as the light source and irradiated with active rays. The irradiation dose at this time was 75 mJ. And the application layer was developed by alkaline developing solution (KOH), the unexposed part of the application layer was melt | dissolved, and the pattern required for a color filter was formed.

1) 광학밀도 (Optical Density)1) Optical Density

광학밀도는 25 ℃에서 현상을 마친 유리 기판위의 감광성 수지조성물을 200 ℃ 컨벡션 오븐에서 30 분간 포스트 베이크(Post Bake)한 후, MCPD 3000 색차계와 PMT (Photo Multiplier Tube, 오츠카전자 제품)을 이용하여 550nm 파장에서 투과율을 측정하여 상기 식 1의 공식에 의해 광학밀도를 측정하였다. The optical density is 30 minutes post-baked photosensitive resin composition on a glass substrate developed at 25 ℃ in a 200 ℃ convection oven, using MCPD 3000 colorimeter and PMT (Photo Multiplier Tube, Otsuka Electronics) The transmittance was measured at a wavelength of 550 nm, and the optical density was measured by the formula of Formula 1.

2) 접착강도 2) adhesive strength

ASTM D3359 법을 이용하여 Cross-cutting Tape Test를 시행하여 테스트하고 사용기기는 Elcometer를 사용하였다. Cross-cutting Tape Test was conducted using ASTM D3359 method and the elcometer was used.

3) 저장안정성 3) Storage stability

저장안정성은 영상 5℃보관상태로 매 10시간마다 점도 및 입자크기를 측정하여 초기값의 ±2% 범위내 있는 경우의 일자를 계산하였다.Storage stability was calculated by measuring the viscosity and particle size every 10 hours in the image storage state of 5 ℃ to calculate the date when the range of ± 2% of the initial value.

광학밀도, 접착강도 및 저장안정성 측정결과를 다음 표 1에 나타내었다.Optical density, adhesive strength and storage stability measurement results are shown in Table 1 below.

구분division 광학밀도 (/㎛) Optical Density (/ ㎛) 접착강도 Adhesive strength 저장안정성(일)Storage stability (days) 실시예 1Example 1 5.125.12 5B (100%)5B (100%) 9797 실시예 2Example 2 5.035.03 5B (100%)5B (100%) 9393 실시예 3Example 3 4.884.88 5B (100%)5B (100%) 9191 실시예 4Example 4 4.904.90 5B (100%)5B (100%) 9898 실시예 5Example 5 4.804.80 5B (100%)5B (100%) 9797 실시예 6Example 6 5.075.07 5B (100%)5B (100%) 9595 실시예 7Example 7 4.204.20 5B (100%)5B (100%) 102102 실시예 8Example 8 5.225.22 4B (95%)4B (95%) 8585 비교예 1Comparative Example 1 4.124.12 5B (100%)5B (100%) 102102 비교예 2Comparative Example 2 3.903.90 5B (100%)5B (100%) 9595 비교예 3Comparative Example 3 3.503.50 5B (100%)5B (100%) 9393 비교예 4Comparative Example 4 3.703.70 5B (100%)5B (100%) 9898 비교예 5Comparative Example 5 3.563.56 5B (100%)5B (100%) 9595

상기 표 1의 결과로부터, 본 발명의 감광성 수지 조성물에 고굴절성 유기재료를 더 포함하는 경우, 포토레지스트 패턴의 수득 후 광학밀도가 단위두께(㎛) 당 4.5 이상으로, 비교예의 광학밀도보다 현저히 증가했음을 볼 수 있다. 또한 온화한 경화조건에서도 양호한 접착강도를 얻을 수 있으며, 추가적인 모노머가 첨가되었으나 감광성 수지 조성물의 저장안정성도 적절함을 알 수 있다. From the results of Table 1, when the photosensitive resin composition of the present invention further comprises a high refractive organic material, the optical density after obtaining the photoresist pattern is 4.5 or more per unit thickness (µm), which is significantly increased than the optical density of the comparative example. You can see that. In addition, even in mild curing conditions, good adhesion strength can be obtained, and additional monomers have been added, but it can be seen that the storage stability of the photosensitive resin composition is also appropriate.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 바인더 수지를 포함하는 감광성 수지 조성물에 고굴절성의 유기재료를 분산시킨 결과, 패턴 현상 후 광투과율을 낮추고 광학밀도를 증가시킬 수 있고, 이와 같은 고굴절성 유기재료 분산시켰음에도 적합한 접착강도를 가지며, 또한 조액의 저장안정성 또한 우수하여 액정 디스플레이 패널의 초박막형 소자의 구현이 가능하고 플랙시블 디스플레이(Flexible display)와 같이 가볍고 작고 얇은 기능성 디스플레이 소자의 구현을 앞당길 수 있는 발명이다. As described above in detail, as a result of dispersing a high refractive organic material in a photosensitive resin composition comprising a binder resin according to the present invention, it is possible to lower the light transmittance and increase the optical density after pattern development, such a high refractive organic material Even though it has been dispersed, it has suitable adhesive strength and storage stability of liquid solution is also excellent, so that it is possible to realize ultra-thin device of liquid crystal display panel and to accelerate the implementation of light, small and thin functional display device such as flexible display. Invention.

Claims (6)

바인더 수지, 광중합 개시제, 블랙안료, 용제를 포함하는 액정 디스플레이용 블랙매트릭스 감광성 수지 조성물에 있어서, In the black matrix photosensitive resin composition for liquid crystal displays containing a binder resin, a photopolymerization initiator, a black pigment, and a solvent, 폴리페닐설폰, [(폴리페닐이소시아네이트)-코-포름알데히드]([(polyphenyl isocyanate)-co-formaldehyde]), 폴리(비스페놀A 카보네이트)(poly(bisphenol A carbonate)), 2-플루오로-4-요오도페닐보론산(2-Fluoro-4-iodophenylboroic acid), 티오벤조익산(Thiobenzoic Acid), 4-비닐아닐린(4-vinylaniline), 트리스(메틸티오)메탄(Tris(methylthio)methane), 트리페닐포스파이트(Triphenylphosphite), 2,3,5-트리메틸나프탈렌(2,3,5-Trimethylnaphthalene), 2,3,4-트리플루오로페닐 이소티오시아네이트(2,3,4-Trifluorophenyl isothiocyanate), 3-(트리플루오로메틸티오)페닐 이소시아네이트(3-(Trifluoromethylthio)phenyl isothiocyanate), 2,4,6-트리클로로벤조일 클로라이드(2,4,6-Trichlorobenzoyl chloride), 트리클로로아세틱산(Trichloroacetic acid), 1,1,2-트리브로모에탄(1,1,2-tribromoethane), 트리브로모아세트알데히드(Tribromoacetaldehyde), 트리브로모아세탈 클로라이드(Tribromoacetal Chloride), p-톨릴 이소티오시아네이트(p-Tolyl isothiocyanate), m-톨릴 이소티오시아네이트(m-Tolyl isothiocyanate), o-톨릴 이소티오시아네이트(o-Tolyl isothiocyanate), N-티오닐아닐린(N-Thionylaniline), 폴리비닐톨루엔(polyvinyl toluene), 폴리(비닐톨루엔-코-α-메틸스티렌) (Poly(vinyltoluene-co-α-methylstyrene), 폴리(1-비닐 나프탈렌)(Poly(1-vinyl naphthalene)), 폴리[(페닐글리시딜에테르)-코-(포름알데히드)](Poly[(phenyl glycidyl ether)-co-formaldehyde]), 2-페닐톨루엔(2-phenyl toluene), 3-페닐톨루엔(3-phenyl toluene), 2-(페닐티오)에탄올(2-(Phenylthio) ethanol), 2-[(페닐티오)메틸]-2-사이클로펜텐-1-온(2-[(Phenylthio) methyl]-2-cyclopenten-1-one), (페닐티오)아세틸클로라이드((Phenylthio)acetyl chloride), 1-페닐피라졸(1-Phenylpyrazole), 페닐 프로파길 알데히드(Phenyl propargyl aldehyde), 페닐이소티오시아네이트(Phenyl isothiocyanate), N-페닐 에틸렌디아민(N-Phenyl ethylenediamine), 페닐클로로디티오포르메이트(Phenyl chlorodithioformate), o-페닐클로로티오포르메이트(o-phenyl Chlorothionoformate) 중에서 선택된 1종 이상인 고굴절성 유기재료를 포함하는 것을 특징으로 하는 감광성 수지 조성물.Polyphenylsulfone, [(polyphenylisocyanate) -co-formaldehyde] ([(polyphenyl isocyanate) -co-formaldehyde]), poly (bisphenol A carbonate), 2-fluoro-4 2-Fluoro-4-iodophenylboroic acid, Thiobenzoic Acid, 4-vinylaniline, Trismethyl, Tri Triphenylphosphite, 2,3,5-trimethylnaphthalene, 2,3,4-trifluorophenyl isothiocyanate, 3- (Trifluoromethylthio) phenyl isothiocyanate, 2,4,6-trichlorobenzoyl chloride, Trichloroacetic acid , 1,1,2-tribromoethane, tribromoacetaldehyde, tribromoacetal chloride (1,1,2-tribromoethane) Tribromoacetal Chloride, p-Tolyl isothiocyanate, m-Tolyl isothiocyanate, o-Tolyl isothiocyanate, N-thionyl N-Thionylaniline, polyvinyl toluene, poly (vinyltoluene-co-α-methylstyrene), poly (1-vinyl naphthalene) (Poly (1 -vinyl naphthalene)), poly [(phenylglycidyl ether) -co- (formaldehyde)] (Poly [(phenyl glycidyl ether) -co-formaldehyde]), 2-phenyl toluene, 3 3-phenyl toluene, 2- (phenylthio) ethanol, 2-[(phenylthio) methyl] -2-cyclopenten-l-one (2-[(Phenylthio) ) methyl] -2-cyclopenten-1-one), (phenylthio) acetyl chloride, 1-phenylpyrazole, phenyl propargyl aldehyde, phenyliso Phenyl isothiocyanate, N N-Phenyl ethylenediamine, Phenyl chlorodithioformate, o-phenyl Chlorothionoformate characterized in that it comprises a high refractive organic material selected from at least one The photosensitive resin composition. 제 1 항에 있어서,The method of claim 1, 고굴절성 유기재료는 0.5 내지 10중량% 포함하는 것을 특징으로 하는 감광성 수지 조성물. The highly refractive organic material is 0.5 to 10% by weight of the photosensitive resin composition characterized in that it comprises. 삭제delete 제 1 항에 있어서,The method of claim 1, 바인더 수지는 아크릴계 수지, 폴리이미드 수지, 페놀수지 및 카도계 수지 중 선택된 수지인 것임을 특징으로 하는 감광성 수지 조성물.The binder resin is a photosensitive resin composition, characterized in that the resin selected from acrylic resin, polyimide resin, phenol resin and cardo resin. 제1항, 제2항 및 제4항 중 어느 한 항의 감광성 수지 조성물을 포함하는 액정 디스플레이용 블랙매트릭스.The black matrix for liquid crystal display containing the photosensitive resin composition of any one of Claims 1, 2, and 4. 삭제delete
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US6852397B2 (en) 2001-11-05 2005-02-08 Dai Nippon Printing Co., Ltd. Counterfeit-proof volume hologram multilayer structure, and counterfeit-proof volume hologram seal
JP2005208572A (en) * 2004-01-19 2005-08-04 Qimei Industry Co Ltd Photosensitive resin composition for black matrix

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