KR20000055255A - Photosensitive resin composition and black matrix - Google Patents
Photosensitive resin composition and black matrix Download PDFInfo
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- KR20000055255A KR20000055255A KR1019990003780A KR19990003780A KR20000055255A KR 20000055255 A KR20000055255 A KR 20000055255A KR 1019990003780 A KR1019990003780 A KR 1019990003780A KR 19990003780 A KR19990003780 A KR 19990003780A KR 20000055255 A KR20000055255 A KR 20000055255A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Abstract
Description
본 발명은 액정 디스플레이 장치의 차광에 사용되는 블랙매트릭스 제조용 감광성 수지조성물에 관한 것으로, 더욱 상세하게는 카도계 수지 및 에폭시기 또는 아미노기를 갖는 실란계 커플링제를 포함하는 것을 특징으로 하는 내열성, 내화학성 및 접착성이 우수한 블랙매트릭스 제조용 감광성 수지조성물 및 그로부터 제조되는 블랙매트릭스에 관한 것이다.The present invention relates to a photosensitive resin composition for producing a black matrix used for light shielding of a liquid crystal display device, and more particularly, to a heat resistant, chemical resistance and a silane coupling agent having a cardo resin and an epoxy group or an amino group. The present invention relates to a photosensitive resin composition for producing a black matrix having excellent adhesiveness and a black matrix prepared therefrom.
사무자동화기기, 휴대용 소형 텔레비젼, 비디오카메라의 뷰파인더 등에 사용되는 전자 디스플레이 장치로서 종래에는 브라운관이 주로 사용되었으나, 최근에는 액정디스플레이 장치(LCD), 플라즈마 디스플레이(PDP), 형광표시판(VFD) 등이 사용되고 있으며, 이들에 관련된 기술의 연구개발도 활발히 진행되고 있다.Conventionally, CRTs are mainly used for office automation equipment, portable small televisions, viewfinders of video cameras, etc., but recently, liquid crystal display (LCD), plasma display (PDP), fluorescent display panel (VFD), etc. It is being used, and the research and development of the technology related to them is also actively progressing.
상기 디스플레이 장치 중의 하나인 액정디스플레이 장치는 경량화, 박형화, 저가,저소비전력구동화 및 우수한 집적회로와의 접합성 등의 장점을 가지고 있어 랩톱 컴퓨터나 포켓컴퓨터의 표시판 및 차량적재용 칼라 TV 화상용으로 그 사용범위가 확대되고 있다. 이와 같은 액정디스플레이 장치는 블랙매트릭스, 칼라필터 및 ITO 화소전극이 형성된 하부 기판과, 액정층, 박막트랜지스터, 축전캐패시터층으로 구성된 능동회로부와 ITO 화소전극이 형성된 상부의 기판을 포함하여 구성된다.The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent bonding with an integrated circuit, and is suitable for display of a laptop computer or a pocket computer and color TV image for vehicle loading. The range of use is expanding. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an 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.
종래의 액정디스플레이 장치에서 사용되어 온 칼라필터는 플라스틱, 또는 유리로 된 기판 상부에 블랙매트릭스와 적, 녹, 청의 삼색의 착생층이 반복되며, 그 위에 칼라필터의 보호와 표면평활성을 유지하기 위해 폴리이미드, 폴리아크릴레이트, 폴리우레탄 등과 같은 재료의 두께 1 내지 3㎛의 오버코트층(OVERCOAT)과 이 오버코트층 상부에 액정 구동을 위한 전압이 인가되는 ITO(Indium Thin Oxide) 투명전도막층이 형성되어 있다.The color filter used in the conventional liquid crystal display device has a black matrix and a trichromatic layer of red, green, and blue repeated on a plastic or glass substrate, in order to maintain the protection and surface smoothness of the color filter thereon. An overcoat layer (OVERCOAT) having a thickness of 1 to 3 μm of a material such as polyimide, polyacrylate, polyurethane, etc. and an indium thin oxide (ITO) transparent conductive film layer to which a voltage for driving a liquid crystal is applied are formed on the overcoat layer. have.
상기 블랙매트릭스는 기판의 투명화소전극 이외로 투과되어 제어되지 않는 광을 차단하여 콘트라스트를 향상시키는 역할을 하며, 적, 녹, 청의 착색층은 백새광중 특정 파장의 빛을 투과시켜 색을 표현할 수 있도록 하며, 투명전도막층은 액정에 전계를 인가하기 위한 공통전극의 역할을 한다.The black matrix serves to improve contrast by blocking uncontrolled light transmitted through the transparent pixel electrode of the substrate, and the colored layer of red, green, and blue transmits light of a specific wavelength among white light so that color can be expressed. The transparent conductive film layer serves as a common electrode for applying an electric field to the liquid crystal.
상기와 같은 칼라필터 기판에 있어서, 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 별도의 처리공정이 필요한 문제점이 있어 최근에는 수지를 사용한 블랙매트릭스가 활발하게 연구되고 있다.In the color filter substrate as described above, 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 it has a problem of requiring a separate treatment process for total reflection due to complicated process and high equipment cost, high production cost, and high reflectance. Black Matrix is being actively researched.
일반적으로 칼라필터의 기판은 염색법, 인쇄법, 안료분산법, 전착법 등의 방법에 의해 제조될 수 있으며, 블랙매트릭스는 주로 안료분산법에 의해 제조되고 있다. 안료분산법은 블랙매트릭스가 제공된 투명한 기질 위에 착색제를 함유하는 광중합성 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. 예컨대, 일본특개소 63-309916호, 일본특개평1-152449호, 대한민국 특허공개 제 95-3135호 등에는 안료분산을 이용한 블랙매트릭스의 제조방법이 제안되어 있다.In general, the substrate of the color filter can be produced 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 photopolymerizable 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. For example, Japanese Patent Laid-Open No. 63-309916, Japanese Patent Laid-Open No. Hei 1-52449, Korean Patent Laid-Open No. 95-3135 and the like have proposed a method for producing a black matrix using pigment dispersion.
안료분산법에 의해 제조되는 블랙매트릭스는 크게 지지체 역할 및 일정 두께의 유지를 가능하게 하는 고분자화합물, 즉 바인더수지와 노광시 광과 반응하여 포토레지스트상을 형성하는 광중합성 모노머의 2 가지 성분으로 구성되고, 상기한 성분 이외에 안료, 중합개시제, 에폭시수지, 용제와 기타 첨가제 등을 포함하는 감광성 수지 조성물에 의해 제조된다. 안료분산법에 사용되는 바인더수지로는 예컨대, 일본특개소 60-237403호에 개시된 폴리이미드수지, 일본특개평 1-200353호, 동 평4-7373호, 동 4-91173호 등에 기재된 아크릴계중합체와 아지드 화합물로 이루어진 감광성수지, 대한민국특허 공개 제 93-20127호, 대한민국특허 공개 제 95-3135호 등에 기재된 아크릴계중합체로 이루어진 감광성수지, 일본특개평1-152449호에 기재된 아크릴레이트 단량체, 유기중합체 결합제, 및 광중합개시제로 이루어진 라디칼 중합형의 감광성 수지, 일본특개평 4-163552호와 대한민국특허 공보 제 92-5780호에 개시된 페놀수지, N-메틸올 구조를 갖는 가교제 및 광산발생제로 이루어진 감광성수지 등의 여러 가지가 제안되어 있다.The black matrix produced by the pigment dispersion method is composed of two components, a polymer compound that largely supports the role of a support and maintains a constant thickness, that is, a binder resin and a photopolymerizable monomer that reacts with light during exposure to form a photoresist image. And a photosensitive resin composition containing a pigment, a polymerization initiator, an epoxy resin, a solvent and other additives, etc., in addition to the above components. As the binder resin used in the pigment dispersion method, for example, an acrylic polymer described in polyimide resin disclosed in Japanese Patent Application Laid-Open No. 60-237403, Japanese Patent Application Laid-Open No. 1-200353, Japanese Patent Application No. 4-7373, Japanese Patent Application No. 4-91173 and the like; Photosensitive resin composed of an azide compound, Photosensitive resin composed of acrylic polymer described in Korean Patent Publication No. 93-20127, Korean Patent Publication No. 95-3135, etc. Radical photopolymerizable resin comprising a photopolymerization initiator, a phenolic resin disclosed in Japanese Patent Laid-Open No. 4-163552 and Korean Patent Publication No. 92-5780, a photosensitive resin comprising a crosslinking agent having a N-methylol structure, and a photoacid generator. Several are proposed.
그러나, 안료분산법에 따른 바인더수지로서 감광성 폴리이미드나 페놀계의 수지를 사용하는 것은 내열성은 높지만 감도가 낮으며 유기용매로 현상하는 등의 결점이 있다. 또한 아지드 화합물을 감광제로 하는 종래의 시스템은 감도가 낮고 내열성이 떨어지거나 노출시에 산소의 영향을 받는 문제가 있다. 이러한 문제점을 극복하기 위해 산소차단막을 설치하거나 불활성 가스중에 노출시키는 방법이 이용될 수 있으나, 이러한 방법을 적용하는 경우에는 공정이 복잡해지고 장치가 비싸지는 등의 문제가 있다.However, the use of a photosensitive polyimide or phenolic resin as a binder resin according to the pigment dispersion method has a disadvantage of high heat resistance but low sensitivity and development with an organic solvent. In addition, conventional systems using azide compounds as photosensitizers have problems of low sensitivity, poor heat resistance, and effects of oxygen upon exposure. In order to overcome this problem, a method of installing an oxygen barrier film or exposing it to an inert gas may be used. However, in the case of applying such a method, a process is complicated and an apparatus is expensive.
또한 노출로 인해 생성된 산을 이용하여 화상을 형성하는 감광성수지는 고감도이며 노출될 때 산소의 영향을 받지 않는 이점이 있지만, 노출과 현상하는 과정에서 가열공정이 필요하며 가열시간이 패턴 형성에 대해 민감한 반응을 보이므로 공정관리가 곤란하다는 문제점이 있다.In addition, the photosensitive resin which forms an image using the acid generated by the exposure has a high sensitivity and has the advantage of not being affected by oxygen when exposed, but a heating process is required in the process of exposure and development, and a heating time is required for pattern formation. There is a problem that process control is difficult because of the sensitive reaction.
이러한 문제를 해결하기 위해 일본특개평 7-64281호, 동7-64282호, 동8-278630호, 동6-1938호, 동5-339356호, 대한민국특허공개 95-702313호에는 카도계바인더수지를 이용한 컬러필터의 제조방법이 개시되어 있다. 일반적으로 카도계를 지닌 수지는 고감도이면서 산소의 영향을 받지 않고 내열성, 내수축성, 내화학성 등이 우수하다. 그러나, 이러한 감광성수지조성물은 벌키(bulky)한 분자구조로 인하여 접착성이 떨어지는 경향이 있다. 더욱이, 블랙매트릭스의 경우에는 요구되는 광학적 밀도를 맞추기 위해 블랙 안료의 함량이 다른 착색 감광성수지 조성물에 비해 많이 들어가므로 접착성의 저하가 더욱 심하게 나타나는 문제점이 있다.In order to solve this problem, Japanese Patent Laid-Open Nos. 7-64281, 7-64282, 8-278630, 6-1938, 5-339356, and Korean Patent Publication No. 95-702313 disclose a cardo binder binder resin. Disclosed is a method of manufacturing a color filter using. In general, a resin having a cardo-based resin is highly sensitive and is not affected by oxygen, and is excellent in heat resistance, shrinkage resistance, and chemical resistance. However, such photosensitive resin compositions tend to be inferior in adhesion due to the bulky molecular structure. Moreover, in the case of the black matrix, since the content of the black pigment is much higher than that of other colored photosensitive resin compositions in order to match the required optical density, there is a problem in that the deterioration of adhesion is more severe.
본 발명의 목적은 상술한 종래 기술의 문제점을 극복하기 위한 것으로, 에폭시기나 아미노기를 갖는 실란계 커플링제를 이용함으로써 광학적 밀도, 내열성,내화학성, 및 접착성이 우수한 블랙매트릭스 제조용 감광성 수지조성물을 제공하는 것이다.An object of the present invention is to overcome the problems of the prior art described above, by using a silane coupling agent having an epoxy group or an amino group to provide a photosensitive resin composition for producing a black matrix excellent in optical density, heat resistance, chemical resistance, and adhesion It is.
본 발명의 다른 목적은 상기 조성물에 의해 제조된 액정디스플레이 장치의 칼라필터 제조용 블랙매트릭스를 제공하는 것이다.Another object of the present invention is to provide a black matrix for producing a color filter of the liquid crystal display device produced by the composition.
즉, 본 발명의 하나의 양상은 하기 성분으로 조성된 블랙매트릭스 제조용 감광성수지조성물이다.That is, one aspect of the present invention is a photosensitive resin composition for producing a black matrix composed of the following components.
전체 감광성 수지 조성물을 100 중량부로 할 때,When the total photosensitive resin composition is 100 parts by weight,
(1) 카도계 바인더 수지 1∼40 중량부(1) 1 to 40 parts by weight of cardo binder resin
(2) 아크릴계 광중합성 모노머 1∼20 중량부(2) 1 to 20 parts by weight of an acrylic photopolymerizable monomer
(3) 광중합개시제 0.1∼10 중량부(3) 0.1 to 10 parts by weight of photopolymerization initiator
(4) 에폭시화물 0∼10 중량부(4) 0 to 10 parts by weight of epoxide
(5) 블랙안료 5∼20 중량부(5) Black pigment 5-20 parts by weight
(6) 용매 20∼80 중량부(6) 20 to 80 parts by weight of solvent
(7) 실란계 커플링제 0.01∼1 중량부(7) 0.01 to 1 part by weight of silane coupling agent
본 발명의 상기 조성물에는 조성물의 물성을 해하지 않는 범위내에서 분산제, 계면활성제, 안정제 등의 기타의 첨가제가 일정량 첨가될 수 있다.The composition of the present invention may be added a certain amount of other additives such as dispersants, surfactants, stabilizers, etc. within a range that does not impair the physical properties of the composition.
이하에서 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 블랙매트릭스 제조용 감광성 수지 조성물의 구성성분중 바인더 수지는 하기 화학식 1, 2 및 3으로 표현되는 성분 (A):(B):(C)를 1몰: 2∼4몰:2∼8몰의 비로 공중합한, 분자량이 1000∼20000인 카도계 바인더 수지이다. 이러한 바인더 수지의 바람직한 첨가비율은 전체 수지 조성물 100중량부당 1-40중량부이다.Among the components of the photosensitive resin composition for producing the black matrix of the present invention, the binder resin is a component (A) :( B) :( C) represented by the following general formulas (1), (2) and (3): 1 mol: 2-4 mol: 2-8 It is cardo-type binder resin whose molecular weight is 1000-20000 copolymerized by the ratio of mole. The preferable addition ratio of this binder resin is 1-40 weight part per 100 weight part of total resin compositions.
[화학식 1][Formula 1]
(A) (A)
[화학식 2][Formula 2]
(B) (B)
[화학식 3][Formula 3]
CH2=CRCOOH (C)CH 2 = CRCOOH (C)
상기 식에서,Where
R은 수소원자, 탄소수 1∼10의 알킬기, 알릴기, 페닐기, 벤질기, 탄소수 1∼8의 에폭시기로 구성되는 그룹으로부터 선택되고, X는 할로겐 원자이다.R is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group, and an epoxy group having 1 to 8 carbon atoms, and X is a halogen atom.
본 발명의 감광성 수지 조성물은 빛의 조사에 의해 경화되고 알칼리성 수용액으로 현상가능한 알칼리 현상형이다. 감광성 수지조성물을 기판위에 라미네이션하시킨 다음 컬러필터에 필요한 패턴을 형성하도록 활성선을 조사하면 광에 의해 반응하게 되는데, 반응한 부위는 반응하지 않은 부위에 비해 용매에 대한 용해도가 급격히 떨어져 미반응 부위만 선택적으로 용해 가능하게 된다. 이와 같이 비노광부위를 제거하는 용액을 현상액이라 하는데, 이러한 현상액에는 유기 용제형과 알칼리 현상형의 2가지 타입이 있다. 이들 가운데 유기 용제형은 대기오염을 유발하고 인체에 유해하므로 바람직하지 않고, 환경 면에서 알칼리 현상형이 더욱 바람직하다. 본 발명의 감광성수지 조성물은 알칼리 현상형 잉크로 사용된다.The photosensitive resin composition of this invention is an alkali developing type which can be hardened by irradiation of light and developable with alkaline aqueous solution. When the photosensitive resin composition is laminated on the substrate and irradiated with active rays to form a pattern required for the color filter, the reaction is caused by light. Only it can be selectively dissolved. The solution for removing the non-exposed areas is called a developer, and there are two types of developer, an organic solvent type and an alkali developer type. Of these, the organic solvent type is not preferable because it causes air pollution and is harmful to the human body, and the alkali developing type is more preferable in terms of environment. The photosensitive resin composition of the present invention is used as an alkali developing ink.
본 발명에서 사용되는 아크릴계 광중합성 모노머는 일반적으로 사용되고 있는 에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 1,4-부탄디올디아크릴레이트, 1,6-헥산디올디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 펜타에리트리톨디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 펜타에리트리톨디아크릴레이트, 디펜타에리트리톨트리아크릴레이트, 디펜타에리트리톨아크릴레이트, 펜타에리트리톨헥사아크릴레이트, 비스페놀 A 디아크릴레이트, 트리메틸롤프로판트리아크릴레이트, 노블락에폭시아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 1,6-헥산디올디메타크릴레이트 모노머 등이 있다. 이러한 아크릴계 광중합성 모노머는 전체 감광성 수지조성물 100중량부당 1-20중량부 범위에서 첨가된다.The acrylic photopolymerizable monomer used in the present invention is generally used ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol di Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate Latex, trimethylolpropane triacrylate, noblock epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanedioldi Methacrylate, 1,6-hexanedioldimethacrylate monomer There is. Such acrylic photopolymerizable monomer is added in the range of 1-20 parts by weight per 100 parts by weight of the total photosensitive resin composition.
본 발명에서 상술한 광중합성 모노머는 알칼리 수용액에 용해되기 쉽게 하기 위해서 하기 화학식 4로 표현되는 산무수물로 처리되며, 이러한 처리에 의해 본 발명의 감광성 수지 조성물은 알칼리 현상가능한 감광성 수지조성물이 된다.The photopolymerizable monomer described above in the present invention is treated with an acid anhydride represented by the following formula (4) in order to be easily dissolved in an aqueous alkali solution, and by such treatment, the photosensitive resin composition of the present invention becomes an alkali developable photosensitive resin composition.
상기 식에서, R1, 및 R2는 수소원자, 탄소수 1∼10의 알킬기, 알릴기, 페닐기, 벤질기, 탄소수 1∼8의 에폭시기로 구성되는 군으로부터 선택된다.Wherein R 1 and R 2 are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group, and an epoxy group having 1 to 8 carbon atoms.
본 발명의 감광성 수지 조성물에 포함되는 광중합개시제는 일반적으로 사용되는 아세토페논계의 유도체로서, 구체적으로 예를 들면 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 등이 사용된다. 본 발명의 감광성 수지조성물중 광중합개시제는 전체 수지 조성물 100중량부당 0.1 내지 10 중량부 사용한다.The photoinitiator included in the photosensitive resin composition of the present invention is a derivative of acetophenone which is generally used. Specifically, for example, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2- Hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichloro Benzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4-methylthio) phenyl) -2-morpho Nopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one and the like are used. The photopolymerization initiator in the photosensitive resin composition of the present invention is used 0.1 to 10 parts by weight per 100 parts by weight of the total resin composition.
본 발명에서 감광성수지조성물의 내화학성을 향상시키기 위해 첨가되는, 에폭시화물로는 페놀노블락형에폭시, 크레졸노블락형에폭시, 폴리카르본산글리시딜에스테르, 폴리올폴리글리시딜에스테르, 지방족 또는 지환식 에폭시수지, 아민에폭시수지 등을 사용할 수 있고, 그 첨가비율은 전체 수지 조성물 100중량부당 0 내지 10 중량부이다.Epoxides added to improve the chemical resistance of the photosensitive resin composition in the present invention include phenol noblock type epoxy, cresol noblock type epoxy, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy Resin, an amine epoxy resin, etc. can be used, The addition ratio is 0-10 weight part per 100 weight part of all resin compositions.
본 발명에서 블랙안료로는 예컨대, 아닐린 블랙, 퍼릴렌 블랙, 티탄 블랙, 카본블랙 등이 사용될 수 있으며, 색보정제로 안트라퀴논계 안료, 페릴렌계 안료 등의 축합다환 안료, 프탈로시아닌 안료, 아조안료 등의 유기안료를 사용할 수 있다. 이러한 블랙안료는 전체 감광성 수지 조성물 100중량부에 대해 5-20중량부의 양으로 첨가된다.As the black pigment in the present invention, for example, aniline black, perylene black, titanium black, carbon black and the like can be used, and as a color correction agent, condensed polycyclic pigments such as anthraquinone pigments, perylene pigments, phthalocyanine pigments, azo pigments, etc. Organic pigments may be used. Such black pigment is added in an amount of 5-20 parts by weight based on 100 parts by weight of the total photosensitive resin composition.
본 발명에서 용제로는 에틸렌글리콜 아세테이트, 에틸셀로솔브, 프로필렌글리콜메틸에테르아세테이트, 에틸락테이트, 폴리에틸렌글리콜, 시클로헥사논, 프로필렌글리콜메틸에테르 등이 사용될 수 있고, 이들 용제들은 단독 또는 혼합하여 사용할 수 있다. 본 발명에서 사용되는 용제의 비율은 감광성 수지 조성물에 따라 상이하므로 구체적으로 규정할 수 없으나, 수지액이 기판에 도포될 수 있는 점도를 갖도록 용제의 비율을 선택하는 것이 바람직하고, 통상적으로는 전체 감광성 수지 조성물 100중량부당 20-80 중량부이다.In the present invention, the solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., these solvents may be used alone or in combination Can be. Since the ratio of the solvent used in the present invention differs depending on the photosensitive resin composition, it cannot be specified in detail, but it is preferable to select the ratio of the solvent so that the resin liquid has a viscosity that can be applied to the substrate, and in general, the overall photosensitive property It is 20-80 weight part per 100 weight part of resin composition.
또한 본 발명에서는 혼합물 속에 안료를 분산시키는데 분산제를 사용하는 것이 바람직하다. 미리 안료를 표면처리하는 형태로 안료에 내부 첨가시켜 사용하거나, 안료에 외부첨가하는 식으로 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, 알킬아미드알킬렌옥사이드 부가물, 알킬아민 등이 사용될 수 있다. 이들은 단독으로 첨가할 수 있으며, 둘 이상 조합하여 첨가할 수 있다. 분산제의 첨가량은 바람직하게는 안료 1 중량부에 대하여 0 내지 20중량%이다.It is also preferred in the present invention to use a dispersant to disperse the pigment in the mixture. It can be used by adding it internally to a pigment in the form which surface-treats a pigment previously, or it can add to the pigment externally. 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 esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. These may be added alone or in combination of two or more. The amount of the dispersant added is preferably 0 to 20% by weight based on 1 part by weight of the pigment.
본 발명의 감광성 수지조성물에는 유리기판과 감광성수지막 사이의 접착성을 향상시키기 위해 실란계 커플링제가 첨가된다. 이러한 실란계 커플링제로는 에폭시기 또는 아미노기를 갖는 실란계 커플링제가 바람직하고, 이들의 첨가비율은 전체 감광성 수지 조성물 100중량부에 대해 0.01∼1 중량부, 더욱 바람직하게는 0.05 내지 0.5 중량부인 것이 좋다.A silane coupling agent is added to the photosensitive resin composition of the present invention in order to improve the adhesion between the glass substrate and the photosensitive resin film. As such a silane coupling agent, the silane coupling agent which has an epoxy group or an amino group is preferable, These addition ratio is 0.01-1 weight part with respect to 100 weight part of all the photosensitive resin compositions, More preferably, it is 0.05-0.5 weight part good.
본 발명의 상기 조성물에는 조성물의 물성을 해하지 않는 범위내에서 계면활성제, 산화방지제, 안정제 등의 기타의 첨가제가 일정량 첨가될 수 있다.A certain amount of other additives such as surfactants, antioxidants, stabilizers, etc. may be added to the composition of the present invention within a range that does not impair the physical properties of the composition.
본 발명의 상술한 조성물은 액정 디스플레이의 칼라필터용 블랙매트릭스의 제조에 이용될 수 있다. 본 발명의 감광성수지조성물을 이용하여 블랙매트릭스를 제조하는 경우에는 유리기판 위에 스핀 도포, 롤러 도포, 스프레이 도포 등의 적당한 방법을 사용하여 예를 들면, 0.5 내지 10 ㎛의 두께로 감광성 수지조성물을 도포한다. 이어서, 컬러필터에 필요한 패턴을 형성하도록 활성선을 조사한다. 조사에 사용되는 광원으로는 예를 들면, 190㎚ 내지 450㎚, 바람직하게, 200 ㎚ 내지 400㎚ 영역의 UV 조사를 사용하며 전자선 및 X선 조사도 적당하다. 조사후, 도포층을 현상액으로 처리하면 도포층의 미노광 부분이 용해되고 컬러필터에 필요한 패턴이 형성된다. 이러한 공정을 필요한 색의 수에 따라 반복함으로써 원하는 패턴을 갖는 칼라필터를 수득할 수 있다. 또한 상기 공정에서 현상에 의해 수득된 화상 패턴을 다시 가열하거나 활성선 조사 등에 의해 경화시키면 내크랙성, 내용제성 등을 향상시킬 수 있다.The above-described composition of the present invention can be used for the production of black matrices for color filters of liquid crystal displays. When manufacturing the black matrix using the photosensitive resin composition of the present invention, for example, by applying a suitable method such as spin coating, roller coating, spray coating on a glass substrate, the photosensitive resin composition is applied to a thickness of 0.5 to 10 ㎛ do. Subsequently, the active line is irradiated to form a pattern necessary for the color filter. As a light source used for irradiation, UV irradiation of 190 nm-450 nm, preferably 200 nm-400 nm area is used, and electron beam and X-ray irradiation are also suitable. After the irradiation, when the coating layer is treated with a developer, the unexposed portion of the coating layer is dissolved to form a pattern necessary for the color filter. By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained. In addition, crack resistance, solvent resistance, and the like can be improved by reheating the image pattern obtained by the development in the above step or by curing by actinic radiation.
이하에서 실시예를 들어 본 발명을 더욱 구체적으로 설명하나, 이들은 단지 설명의 목적만을 위한 것으로, 어떠한 의미로든 본 발명을 제한하는 것으로 해석되어서는 안된다.Hereinafter, the present invention will be described in more detail with reference to Examples, but these are only for the purpose of explanation and should not be construed as limiting the present invention in any sense.
[실시예]EXAMPLE
본 발명의 실시예에서는 아래의 성분들을 이용하여 감광성 수지 조성물을 제조하였다.In the embodiment of the present invention, a photosensitive resin composition was prepared using the following components.
* 용제Solvent
프로필렌글리콜모노메틸에테르 50g50 g of propylene glycol monomethyl ether
시클로헥사논 10g10 g of cyclohexanone
* 광중합성 모노머* Photopolymerizable monomer
펜타에리트리톨트리아크릴레이트 10gPentaerythritol triacrylate 10 g
* 광중합성 개시제* Photopolymerization initiator
Igacure 907 (시바-가이기사) 1gIgacure 907 (Shiba-Gaiisa) 1g
4,4'-디메틸벤조페논 0.5g0.5 g of 4,4'-dimethylbenzophenone
* 비인더 수지* Non-Inder Resin
카도계수지 [(A):(B):(C)=1/2/2 몰비] 20gCardo Resin [(A) :( B) :( C) = 1/2/2 Molar Ratio] 20g
(A) 9,9'-비스(4-히드록시페닐)플루오렌(A) 9,9'-bis (4-hydroxyphenyl) fluorene
(B) 에피클로로히드린(B) epichlorohydrin
(C) 아크릴산(C) acrylic acid
분자량(Mw) = 4000Molecular weight (Mw) = 4000
* 안 료* Fee
위국색소 CF-TCR 8gGastric Color CF-TCR 8g
* 실란계 커플링제* Silane coupling agent
에폭시변성 실란 커플링제[SF-8421EG(도레이사 제품)] 0.1g0.1g epoxy-modified silane coupling agent [SF-8421EG (Toray Corporation)]
* 기타 첨가제* Other additives
계면활성제(로진산염) 0.2g0.2 g of surfactant (rosin)
산화방지제(Irganox 1010, 시바가이기사 제품) 0.2g0.2g of antioxidant (Irganox 1010, product of Shivagai Corporation)
실시예 1Example 1
용제에 광중합개시제를 녹인 후 2시간 동안 상온에서 교반한다음, 광중합성 모노머, 바인더수지를 첨가하여 2시간 동안 상온에서 교반한다. 이어서 상기 반응물에 안료, 기타 첨가제 등을 넣고 1시간 동안 상온에서 교반한다. 3회에 걸친 여과에 의해 불순물을 제거하여 본 발명의 감광성 수지조성물을 제조하고 후술하는 물성 평가 방법에 따라 광학밀도, 내열성, 내화학성 및 접착성을 평가하여 그 결과를 하기 표 1에 나타내었다.After dissolving the photopolymerization initiator in the solvent, the mixture is stirred at room temperature for 2 hours, and then the photopolymerizable monomer and the binder resin are added and stirred at room temperature for 2 hours. Subsequently, a pigment, other additives, and the like are added to the reactant and stirred at room temperature for 1 hour. The impurities were removed by three times of filtration to prepare the photosensitive resin composition of the present invention, and optical density, heat resistance, chemical resistance and adhesion were evaluated according to the physical property evaluation method described below, and the results are shown in Table 1 below.
실시예 2Example 2
아민계 커플링제(BY16-853, 도레이사)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 본 발명의 감광성 수지조성물을 제조하고 제반 물성을 평가하여 그 결과를 하기 표 1에 함께 나타내었다.The photosensitive resin composition of the present invention was prepared in the same manner as in Example 1, except that the amine coupling agent (BY16-853, Toray Industries, Inc.) was used. The results are summarized in Table 1 below. It was.
비교예 1Comparative Example 1
커플링제를 첨가하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 감광성 수지조성물을 제조하고 제반 물성을 평가하여 그 결과를 하기 표 1에 함께 나타내었다.Except not adding a coupling agent was carried out in the same manner as in Example 1 to prepare a photosensitive resin composition and to evaluate the overall physical properties and the results are shown in Table 1 together.
비교예 2Comparative Example 2
티올계 커플링제(BX16-838A, 도레이사)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 감광성 수지조성물을 제조하고 제반 물성을 평가하여 그 결과를 하기 표 1에 함께 나타내었다.Except for using a thiol-based coupling agent (BX16-838A, Toray Corporation) was carried out in the same manner as in Example 1 to prepare a photosensitive resin composition and to evaluate the overall physical properties and the results are shown in Table 1 together.
[물성 측정 방법][Measurement Method]
1) 광학밀도:1) Optical Density:
두께 1 ㎜의 유리기판상에 0.8㎛의 두께로 감광성수지조성물을 도포하고 열풍순환식 건조로안에서 80℃하에서 1분간 건조시켜 도막을 수득하였다. 이것을 상온까지 식힌 후에, 열풍순환식 건조로 안에서 230℃에서 30분 동안 건조시킨 뒤 도막의 광학밀도를 Color Analyzer(MK-1800, 도쿄 덴슈쿠사)를 이용하여 측정하였다.A photosensitive resin composition was applied to a glass substrate having a thickness of 1 mm at a thickness of 0.8 μm, and dried for 1 minute at 80 ° C. in a hot air circulation drying furnace to obtain a coating film. After cooling to room temperature, the mixture was dried at 230 ° C. for 30 minutes in a hot air circulation drying furnace, and the optical density of the coating film was measured using a color analyzer (MK-1800, Tokyo Denshuku Co., Ltd.).
○: 광학밀도가 2.5 이상, △: 광학밀도가 2-2.5; ×: 광학밀도가 2 이하(Circle): Optical density is 2.5 or more, (triangle | delta): Optical density is 2-2.5; X: optical density is 2 or less
2) 내열성:2) Heat resistance:
두께 1 ㎜의 유리기판상에 1-2㎛의 두께로 감광성수지조성물을 도포하고, 열풍순환식 건조로 안에서 80℃하에서 1분간 건조시킨 후, 365 ㎚의 파장을 초고압 수은 램프로 조사하고, 계속해서 열풍순환식 건조로 안에서 230℃에서 30분 동안 건조하여 도막을 수득하였다. 이 도막을 다시 열풍순환식 건조로 안에서 1분간 25℃로 가열한 후, 도막의 색차(ΔE)를 측정하여 내열성을 평가하였다.The photosensitive resin composition was applied to a glass substrate having a thickness of 1 mm at a thickness of 1-2 μm, dried at 80 ° C. for 1 minute in a hot air circulation drying furnace, and then irradiated with an ultrahigh pressure mercury lamp at a wavelength of 365 nm. It dried in 230 degreeC in hot-air circulation drying furnace for 30 minutes, and obtained the coating film. After heating this coating film at 25 degreeC for 1 minute in a hot-air circulation type drying furnace, the color difference ((DELTA) E) of a coating film was measured and heat resistance was evaluated.
○: 색차(ΔE)가 3 이하, △: 색차(ΔE)가 3∼5, ×: 색차(ΔE)가 5 이상(Circle): Color difference ((DELTA) E) is 3 or less, (triangle | delta): Color difference ((DELTA) E) is 3-5, ×: Color difference ((DELTA) E) is 5 or more
3) 내화학성:3) Chemical resistance:
두께 1㎜의 유리기판상에 1~2㎛의 두께로 감광성수지조성물을 도포하고, 열풍순환식 건조로 안에서 80℃, 1분동안 건조시켜 도막을 수득하였다. 계속해서 365 ㎚의 파장을 가진 초고압 수은 램프로 조사하고, 1% KOH 수용액을 사용하여 30℃, 상압하에서 80초동안 현상을 행하고, 다시 열풍순환식 건조로 안에서 230℃, 30분동안 건조하여 패턴을 수득하였다. 이 패턴을 5% HC1, NaOH 수용액과 크실렌, NMP, IPA, 아세톤 용액에 30분간 침지한 후 원샘플과의 색차를 측정하여 내화학성을 평가하였다.A photosensitive resin composition was applied to a glass substrate having a thickness of 1 mm to a thickness of 1 to 2 μm, and dried in a hot air circulation drying furnace at 80 ° C. for 1 minute to obtain a coating film. Subsequently, it was irradiated with an ultra-high pressure mercury lamp having a wavelength of 365 nm, developed for 30 seconds at 80 ° C. under atmospheric pressure using a 1% aqueous KOH solution, and dried at 230 ° C. for 30 minutes in a hot air circulation drying furnace. Obtained. The pattern was immersed in a 5% HC1, NaOH aqueous solution, xylene, NMP, IPA, acetone solution for 30 minutes, and the color difference with the original sample was measured to evaluate chemical resistance.
○: 색차(ΔE)가 3 이하, △: 색차(ΔE)가 3∼5, ×: 색차(ΔE)가 5 이상(Circle): Color difference ((DELTA) E) is 3 or less, (triangle | delta): Color difference ((DELTA) E) is 3-5, ×: Color difference ((DELTA) E) is 5 or more
4) 접착성4) Adhesive
크롬이 코팅된 두께 1㎜의 유리기판상에 1-2㎛의 두께로 감광성수지조성물을 도포하고, 열풍순환식 건조로 안에서 1분간 80℃로 건조시켜 도막을 수득하였다. 365㎚의 파장을 가진 초고압 수은 램프로 300mj의 노광량을 조사하고, 계속해서 열풍순환식 건조로 안에서 230℃에서 30분 동안 가열한 후, 1㎜×1㎜의 100개의 바둑판을 새기고, 접촉테이프에 의한 박리실험후의 박리상태를 육안으로 판정하였다.The photosensitive resin composition was applied to a glass substrate having a thickness of 1 mm and coated with chromium to a thickness of 1-2 μm, and dried at 80 ° C. for 1 minute in a hot air circulation drying furnace to obtain a coating film. The exposure dose of 300mj was irradiated with an ultrahigh pressure mercury lamp having a wavelength of 365 nm, then heated in a hot air circulation drying furnace at 230 ° C. for 30 minutes, and then 100 pieces of checkerboards of 1 mm × 1 mm were carved, and the contact tape was The peeling state after peeling test by the test was visually determined.
○: 100/100(박리된 블록수/총 블록수)- 전혀 박리되지 않았음○: 100/100 (number of peeled blocks / total blocks)-no peeling at all
△: 80/100∼99/100△: 80/100 to 99/100
×: 0/100∼79/100×: 0/100 to 79/100
상기 표 1의 결과를 통해서 확인되는 바와 같이, 본 발명의 블랙매트릭스 제조용 감광성 수지조성물은 바인더수지로 카도계 수지를 사용하므로 내열성, 내화학성이 우수하고, 더욱이 실란계 커플링제를 포함하므로 유리기판과의 접착성이 우수한 효과를 갖는다.As can be seen from the results in Table 1, the photosensitive resin composition for preparing the black matrix of the present invention uses cardo resin as a binder resin, and thus has excellent heat resistance and chemical resistance, and furthermore includes a silane coupling agent. It has the effect of excellent adhesiveness.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019990003780A KR100574321B1 (en) | 1999-02-04 | 1999-02-04 | Photosensitive resin composition and black matrix |
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| KR1019990003780A KR100574321B1 (en) | 1999-02-04 | 1999-02-04 | Photosensitive resin composition and black matrix |
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| KR100574321B1 KR100574321B1 (en) | 2006-04-26 |
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| KR100655064B1 (en) * | 2005-05-27 | 2006-12-06 | 제일모직주식회사 | Hardmask composition having antireflective property |
| KR100671107B1 (en) * | 2004-12-29 | 2007-01-17 | 제일모직주식회사 | Photosensitive resin composition and black matrix thereof |
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| KR100787715B1 (en) * | 2005-12-29 | 2007-12-21 | 제일모직주식회사 | Photosensitive resin composition and black matrix thereof |
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| KR100937201B1 (en) | 2007-11-30 | 2010-01-19 | 제일모직주식회사 | Black photosensitive resin composition |
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| JP3148429B2 (en) * | 1992-02-04 | 2001-03-19 | 新日本製鐵株式会社 | Photopolymerizable unsaturated compound and alkali-developable photosensitive resin composition |
| JP3293924B2 (en) * | 1993-01-19 | 2002-06-17 | 日本化薬株式会社 | Radiation-curable resin composition, resin composition for optical material, and cured product thereof |
| JPH06220131A (en) * | 1993-01-22 | 1994-08-09 | Nippon Kayaku Co Ltd | Radiation-setting resin composition, resin composition for optical material and cured product therefrom |
| JP2998880B2 (en) * | 1993-09-28 | 2000-01-17 | 凸版印刷株式会社 | Photosensitive coloring composition, color filter and method for producing color filter |
| JP3998797B2 (en) * | 1998-02-10 | 2007-10-31 | 東京応化工業株式会社 | Photopolymerizable resin composition and method for producing color filter using the photopolymerizable resin composition |
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| US7611826B2 (en) | 2002-10-04 | 2009-11-03 | Samsung Electronics Co., Ltd. | Photosensitive resin composition controlling solubility and pattern formation method of double-layer structure using the same |
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| KR100671106B1 (en) * | 2004-12-29 | 2007-01-17 | 제일모직주식회사 | High photosensitive resin composition and black matrix thereof |
| KR100655064B1 (en) * | 2005-05-27 | 2006-12-06 | 제일모직주식회사 | Hardmask composition having antireflective property |
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| WO2010038978A2 (en) * | 2008-09-30 | 2010-04-08 | Kolon Industries, Inc. | Photopolymer resin composition |
| WO2010038978A3 (en) * | 2008-09-30 | 2010-07-15 | Kolon Industries, Inc. | Photopolymer resin composition |
| CN102216852B (en) * | 2008-09-30 | 2014-09-10 | 可隆工业株式会社 | Photopolymer resin composition |
| CN102460300A (en) * | 2009-06-26 | 2012-05-16 | 可隆工业株式会社 | Photopolymerizable resin composition |
| CN102460300B (en) * | 2009-06-26 | 2013-11-06 | 可隆工业株式会社 | Photopolymerizable resin composition |
| KR20170124207A (en) * | 2016-05-02 | 2017-11-10 | 에이엠씨주식회사 | Photosensitive adhesive film and method of manufacturing the same |
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