TW200947121A - Photosensitive resin composition being curable at low temperature - Google Patents
Photosensitive resin composition being curable at low temperature Download PDFInfo
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- TW200947121A TW200947121A TW098106402A TW98106402A TW200947121A TW 200947121 A TW200947121 A TW 200947121A TW 098106402 A TW098106402 A TW 098106402A TW 98106402 A TW98106402 A TW 98106402A TW 200947121 A TW200947121 A TW 200947121A
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
- 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
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
Description
200947121 六、發明說明： C 明 属 貝 3 發明領域 5 Ο 10 15 20 本發明是有關於可低溫硬化的扁平面顯示器之濾色板 (color filter)用感光性樹脂組成物。 C先前技術;1 發明背景 濾色板基板的製造，一般是由：利用Cr/CrOx形成黑矩 陣(black matrix)、藉顏料分散法形成濾色板、以及形成共 通電極(Common electrode)所組成。 與TFT-陣列(array)步驟同樣地，在被洗淨的玻璃基板 上藉由反應性濺鍵(reactive sputtering)蒸鍍Cr/CrOx形成黑 矩陣圖案後，利用光(photo)步驟技術形成用以實現顏色的 RGB圖案。通常，RGB圖案係使同一個光罩移動而形成， 當由曝光所致的光聚合反應到達一定水準時就會停止，因 此為了持續進行由熱所致的聚合反應，而必須另外實施硬 烤(post-bake)，顯影則係利用浸潰(dipping)、授煉(pUddle)、 射叢(shower)、噴霧(spray)法等。至於與形成於下部tft基 板的畫素電極(pixel electrode) —起令液晶晶胞(cell)動作的 共通電極的形成，則係在RGB圖案形成後進行，藉由藏鍵， 蒸鍍透過性與導電性佳且化學性、熱穩定性優異的透明電 極材料ITO，作為共通電極的ITO則不另外進行圖案形成。 基於RGB圖案的保護與平坦化，有時也會在共通電極形成 前’使用丙稀酸系或聚酿亞胺系樹脂來形成覆旗（〇ver 3 200947121 coat)。 在滤色板步驟中’ RGB圖案主要是利用旋轉式或狹縫 式塗佈機（slitecoater)進行塗佈，在預烤(pre_bake)之後曝光 進行顯影。繼顯影後，最後進行施加22〇。(：以上之熱能的硬 5 烤步驟，一般所使用的破璃在該溫度下幾乎不會變形，但 是使用於柔性（flexible)顯示器的塑膠在220。(：以上的溫度 下會引起嚴重變形。 結果，為了減少基板的變形，不得不降低硬烤步驟的 溫度，而一旦降低硬烤溫度，硬化無法完全發生，氣體產 10 生量增加，受此影響，不僅會有殘像出現，而且還會導致 耐化學性及耐熱性低劣化的問題。 下述專利文獻1中，揭示了一種感光性樹脂組成物，係 透過含有業經酸酐處理的環氧化物，而可提供優異的耐熱 性與耐化學性。但是，含有業經酸酐處理之環氧化物的前 15 述感光性樹脂組成物，其情況同樣是若在20〇°C以下的低溫 進行硬烤步驟，則耐化學性或财熱性未達到基準且氣體產 生量增加，因此會有殘像出現的問題點依然存在。 【習知技術文獻】 【專利文獻】 20 【專利文獻1】大韓民國專利公開第2002-〇〇48675號 【發明内容1 發明概要 發明欲解決之問題 因此，本發明的目的乃是提供一種適用於形成扁平面 4 200947121 顯示器之濾色板的感光性樹脂組成物，該感光性樹脂組成 物可提供一種硬化膜，該硬化膜可於低溫完全硬化，不僅 氣體產生量少，且具有優異的耐熱性及耐化學性。 用以欲解決問題之手段 5 10 15 Ο 為了達成前述目的，本發明係提供一種感光性樹脂組 成物，含有： (Α)鹼性可溶性樹脂，其係選自⑴環氧樹脂以及(Η)丙烯 酸醋樹脂、光聚合物樹脂及該等之混合物中之丨種以上，以 作為黏合劑樹脂之； (B) 環氧硬化劑； (C) 具有乙烯系雙鍵之交聯性單聚物； (D) 顏料； (E) 光聚合引發劑；及 (F) 溶劑。 發明效果 使用依據本發明之感光性樹脂組成物，可獲致即使在 200°C以下的低溫硬化步驟中，氣體產生量仍少且耐熱性及 耐化學性優異，並具可靠性的硬化膜。又，利用前述感光 性樹脂組成物’可以鹼性水溶液顯影，可獲致感度及解像 度優越並屬良好形狀的硬化膜圖案，可於產業性上有效率 地提供可靠性高的濾色板及含該濾色板的扁平面顯示器。 圖式簡單說明 第1圖是顯示實驗例中，由實施例丨及比較例1所製造之 感光性樹脂組成物所獲致的硬化膜，使之浸潰於NMP溶液 20 200947121 後，測定其溶出之物質的吸光度的結果。 【實施方式;j 用以實施發明之最佳形態 本發明的感光性樹脂組成物，其特徵係藉由與鹼可溶 5 性的丙稀酸酿樹脂或光聚合物樹脂一起含有環氧樹脂與環 氧硬化劑，而屬可使熱所致硬化度提升者。因此，本發明 的感光性樹脂組成物可透過低溫硬化步驟，提供與高溫硬 化步驟之物性毫無差異的埘熱性及耐化學性優異的硬化 膜。 10 本發明的感光性樹脂組成物中，前述環氧樹脂（成分 (A)(i))係達成使感光性樹脂組成物的硬化度提升的作用，依 據硬化劑的種類，不僅在低溫下亦可硬化，並且可提供使 硬化時間縮短等多種特性。還有，相較於其他樹脂，其硬 化收縮少，耐化學性或耐熱性等也报優異。200947121 VI. Description of the invention: C Ming Bei 3 Inventive field 5 Ο 10 15 20 The present invention relates to a photosensitive resin composition for a color filter of a low-temperature-curable flat-surface display. C Prior Art; 1 Background of the Invention The manufacture of a color filter substrate is generally composed of forming a black matrix using Cr/CrOx, forming a color filter by a pigment dispersion method, and forming a common electrode. In the same manner as the TFT-array step, a black matrix pattern is formed by vapor-depositing Cr/CrOx on a glass substrate to be cleaned by reactive sputtering, and then formed by a photo step technique. Implement the RGB pattern of the color. Generally, the RGB pattern is formed by moving the same mask, and stops when the photopolymerization reaction by exposure reaches a certain level. Therefore, in order to continue the polymerization reaction due to heat, it is necessary to additionally perform hard baking ( Post-bake), development uses dipping, pUddle, shower, spray, and the like. The formation of a common electrode that causes a liquid crystal cell to act on a pixel electrode formed on a lower tft substrate is performed after the RGB pattern is formed, and the vapor deposition permeability and the adhesion are performed. ITO, which is a transparent electrode material having excellent conductivity and excellent chemical and thermal stability, is not patterned separately for ITO which is a common electrode. Based on the protection and flattening of the RGB pattern, it is sometimes used to form a flag (Acver 3 200947121 coat) using an acrylic acid or a polyaniline resin before the formation of the common electrode. In the color filter step, the RGB pattern is mainly coated with a spin coat or a slite coater, and exposed to pre-bake after exposure. After development, 22 〇 was applied last. (: The hard 5 baking step of the above thermal energy, generally the broken glass is hardly deformed at this temperature, but the plastic used for the flexible display is 220. (: The above temperature will cause severe deformation. As a result, in order to reduce the deformation of the substrate, the temperature of the hard baking step has to be lowered, and once the hard baking temperature is lowered, the hardening cannot be completely occurred, and the gas production is increased, and not only the afterimage but also the residual image appears. The problem of low chemical resistance and heat resistance is deteriorated. Patent Document 1 below discloses a photosensitive resin composition which provides excellent heat resistance and chemical resistance by containing an epoxide which is treated with an acid anhydride. However, in the case of the above-mentioned photosensitive resin composition containing the acid anhydride-treated epoxide, in the same manner, if the hard baking step is carried out at a low temperature of 20 ° C or lower, the chemical resistance or the heat resistance is not up to the standard. Since the amount of generated gas increases, there is still a problem that the afterimage appears. [Practical Technical Literature] [Patent Literature] 20 [Patent Document 1] Korean SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive resin composition suitable for forming a color filter of a flat surface 4 200947121 display. The photosensitive resin composition can provide a cured film which can be completely cured at a low temperature, has a small amount of gas generation, and has excellent heat resistance and chemical resistance. A means for solving the problem 5 10 15 Ο To achieve the above object, the present invention provides a photosensitive resin composition comprising: (Α) an alkali-soluble resin selected from the group consisting of (1) an epoxy resin and an (acrylic) vinegar resin, a photopolymer resin, and a mixture thereof. (B) an epoxy hardener; (C) a crosslinkable monomer having a vinyl double bond; (D) a pigment; (E) a photopolymerization initiator; And (F) a solvent. Advantageous Effects of Invention According to the photosensitive resin composition of the present invention, it is possible to obtain a small amount of gas generated in a low-temperature hardening step of 200 ° C or less, and heat resistance and resistance. A cured film having excellent sensibility and reliability. Further, the photosensitive resin composition can be developed with an alkaline aqueous solution, and a cured film pattern having excellent sensitivity and resolution and having a good shape can be obtained, which is industrially efficient. A highly reliable color filter and a flat surface display including the color filter are provided. Brief Description of the Drawings Fig. 1 is a view showing a photosensitive resin composition produced by the examples and comparative examples in the experimental example. The obtained cured film is immersed in the NMP solution 20 200947121, and the absorbance of the substance eluted is measured. [Embodiment] j The photosensitive resin composition of the present invention is characterized by the best mode for carrying out the invention. The epoxy resin and the epoxy hardener are contained together with the alkali-soluble acrylic acid styrene resin or the photopolymer resin, and the heat hardening degree is improved. Therefore, the photosensitive resin composition of the present invention can pass through the low-temperature curing step, and provides a cured film excellent in heat resistance and chemical resistance which does not differ from the physical properties of the high-temperature hardening step. In the photosensitive resin composition of the present invention, the epoxy resin (component (A) (i)) serves to improve the degree of hardening of the photosensitive resin composition, and depending on the type of the curing agent, not only at low temperatures It can be hardened and can provide various characteristics such as shortening the hardening time. Further, compared with other resins, the hardening shrinkage is small, and the chemical resistance or heat resistance is also excellent.
15 作為前述環氧樹脂者，可舉雙酚A型環氧樹脂、雙酚F 型環氧樹爿曰、本盼清漆型i衣氧樹脂、曱紛清漆型環氧樹脂 以及s亥專之混合物。市售品方面’雙紛a型環氧樹脂可舉 EPIKOTE1001、1002、1003、1004、1007、1〇〇9、1〇1〇、 828(油化设環氧（股）製造）等；雙盼f型環氧樹脂可舉 2〇 EPIKOTE807、834(油化殼環氧(股）製造）等；苯酚清漆型環 氧樹脂可舉EPIKOTE152、154、157H65(油化殼環氧(股）製 造）、EPPN-201、EPPN-501N、EPPN-501H、EPPN-502N、 EPPN-501HY、EOCN-1020(日本化藥（股）製造）等；甲酚清 漆型環氧樹脂可舉EOCN-102S、EOCN-103S、EOCN-104S、 200947121 EOCN-1020、EOCN-1025、EOCN-1〇27(日本化藥（股）製 造）、EPIKOTE180S75(油化殼環氧（股）製造）等，其他環氧 樹脂可舉NC-3000、NC-3000H(日本化藥（股）製造）、 CY175、CY177、CY179(汽巴-嘉基公司（CIBA-GEIGY AG) 5 ❹ 10 15 ❹ 製造）。 前述環氧樹脂係依據感光性樹脂組成物總重量為基 準，而使用1至30重量％之量為佳，若超過30重量％時，顯 影性會發生問題，而若小於1重量％時，低溫硬化度恐怕會 降低。 本發明的感光性樹脂組成物中，前述丙烯酸酯樹脂（成 分(A)(ii))係在已乾燥的感光性樹脂組成物之柔軟性方面而 言，適當為具有15〇。(：以下的玻璃轉移溫度。前述丙烯酸酯 树脂係藉由將不飽和羧酸、芳香族單體、賦予表面柔軟性 用單體及其他丙烯酸單體在溶劑聚合而獲得。 前述不飽和羧酸係基於鹼可溶性而使用之物，其具體 例子可舉丙烯酸、甲基丙烯酸、伊康酸、馬來酸、延胡索 酸、乙烯醋酸、該等之酸酐及該等之混合物等。前述不飽 和竣酸的高分子内含量適當為20至50重量％，這時，不飽 和緩酸的含量若超過5〇重量％時，則聚合時容易凝膠化致 使聚合度調節變得困難，感紐樹脂組成物的保存穩定性 〜、化，不飽和羧酸的含量小於2〇重量％時，會造成顯影步 驟時的顯影時間變長這個缺點。 前述芳香族單體係基於提升所形成的感光性樹脂組成 物之耐化學性與耐熱性而使用。前述芳香族單體之例子， 20 200947121 可舉苯乙烯、曱基丙烯酸苄酯、丙烯酸苄酯、丙烯酸苯酯、 甲基丙烯酸苯酯、2或4-丙烯酸硝苯酯、2或4-甲基丙烯酸硝 苯酯、2或4-硝苄基甲基丙烯酸酯、2或4-丙烯酸氯苯酯、2 或4-曱基丙烯酸氣苯酯以及該等的混合物等。前述芳香族 5 單體的高分子内含量適當為15至45重量％，更適當為20至 40重量％。前述芳香族單體的含量若超過45重量％，會造成 塗膜形成時的薄膜柔軟性低劣，對基板的耐久性惡化的缺 點，芳香族單體的含量若小於15重量％時，則顯影步驟時 與基板的密接性低劣，圖案的剝離現象變得嚴重，所形成 10 的圖案之直進性惡化，難以實現穩定的圖案實現。 前述賦予表面柔軟性用單體的例子，可舉乙氧基化脂 肪酸醇之甲基丙烯酸酯、異十三基曱基丙烯酸酯、曱基丙 烯酸硬脂酯、異癸基甲基丙烯酸酯、乙基己基甲基丙烯酸 酯、乙基三乙二醇甲基丙烯酸酯、甲氧基聚乙二醇甲基丙 15 烯酸酯、丁基二乙二醇甲基丙烯酸酯以及該等的混合物 等。前述具有賦予柔軟性之機能的單體在高分子内含量， 宜為3至15重量％，更宜為5至10重量％。前述具有賦予柔軟 性機能的單體之含量若超過15重量％時，顯影步驟時圖案 的剝離現象變得嚴重，所形成的圖案之直進性惡化。又， 20 其含量若小於3重量％，則高分子的玻璃轉移點變高，容易 損壞，導致所形成的感光性樹脂組成物之柔軟性惡化。 又，前述其他丙烯酸單體係用以調節高分子的極性。 這種丙烯酸單體之例子可舉2-羥乙基（甲基）丙烯酸乙酯、2-羥基（甲基）丙烯酸辛酯、（甲基）丙烯酸曱酯、（甲基）丙烯酸 200947121 乙s旨、丙稀酸正丁酯及該等之混合物等。這些單體的高分 子内含篁基於考量到高分子的耐熱性、分散性、與顯影液 之親水性等，較佳為10至30重量％。 前述丙烯酸酯高分子樹脂可藉由可防止前述4種單體 凝膠化之具有適當極性的溶劑聚合而獲得，所形成的低玻 璃轉移點丙烯酸酯樹脂的重量平均分子量，適當為10，〇〇〇 至35，000，更適當為20000附近。15 As the epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a varnish type i oxyresin, a varnish type epoxy resin, and a mixture of s . In terms of commercial products, 'double-type a-type epoxy resin can be EPIKOTE 1001, 1002, 1003, 1004, 1007, 1〇〇9, 1〇1〇, 828 (made by oil-based epoxy). The f-type epoxy resin may be exemplified by 2〇EPIKOTE807, 834 (manufactured by oleocarbohydrate), and the phenol varnish-type epoxy resin may be EPIKOTE152, 154, 157H65 (manufactured by oleocarbohydrate) EPPN-201, EPPN-501N, EPPN-501H, EPPN-502N, EPPN-501HY, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc.; cresol-type epoxy resin can be EOCN-102S, EOCN-103S , EOCN-104S, 200947121 EOCN-1020, EOCN-1025, EOCN-1〇27 (manufactured by Nippon Kayaku Co., Ltd.), EPIKOTE180S75 (manufactured by oil-coated shell epoxy), other epoxy resins may be NC -3000, NC-3000H (manufactured by Nippon Kayaku Co., Ltd.), CY175, CY177, CY179 (manufactured by CIBA-GEIGY AG 5 ❹ 10 15 ❹). The epoxy resin is preferably used in an amount of from 1 to 30% by weight based on the total weight of the photosensitive resin composition, and if it exceeds 30% by weight, developability may occur, and if it is less than 1% by weight, low temperature The degree of hardening may be reduced. In the photosensitive resin composition of the present invention, the acrylate resin (component (A) (ii)) is suitably 15 Å in terms of flexibility of the dried photosensitive resin composition. (The following glass transition temperature. The acrylate resin is obtained by polymerizing an unsaturated carboxylic acid, an aromatic monomer, a monomer for imparting surface flexibility, and another acrylic monomer in a solvent. Specific examples of the substance to be used for alkali solubility include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, ethylene acetic acid, such acid anhydrides, mixtures thereof, etc. The above unsaturated citric acid is high. The content in the molecule is suitably from 20 to 50% by weight. In this case, when the content of the unsaturated slow acid exceeds 5% by weight, gelation tends to occur during polymerization, which makes it difficult to adjust the degree of polymerization, and the storage of the resin composition is stable. When the content of the unsaturated carboxylic acid is less than 2% by weight, the development time at the development step becomes long. This is a chemical resistance of the above-mentioned aromatic single system based on the photosensitive resin composition formed by the lift. For the purpose of heat resistance and heat resistance, examples of the above aromatic monomer, 20 200947121 include styrene, benzyl methacrylate, benzyl acrylate, phenyl acrylate, and A. Phenyl acrylate, 2 or 4-nitrophenyl acrylate, 2 or 4-nitrophenyl methacrylate, 2 or 4-nitrobenzyl methacrylate, 2 or 4-chlorophenyl acrylate, 2 or 4- a phenyl methacrylate, a mixture of the above, etc. The content of the aromatic 5 monomer in the polymer is suitably 15 to 45% by weight, more preferably 20 to 40% by weight. If the content of the aromatic monomer exceeds When the content of the aromatic film is less than 15% by weight, the adhesion to the substrate at the time of the development step is inferior, and the pattern is inferior in the case where the film is not softened and the durability of the substrate is deteriorated. The peeling phenomenon is severe, and the straightness of the pattern formed by 10 is deteriorated, and it is difficult to achieve stable pattern realization. Examples of the monomer for imparting surface flexibility include methacrylate of ethoxylated fatty acid alcohol, and different Tridecyl methacrylate, stearyl methacrylate, isodecyl methacrylate, ethylhexyl methacrylate, ethyl triethylene glycol methacrylate, methoxy polyethylene glycol Propylene 15 enoate, butyl diethylene The methacrylate, the mixture of the above, etc. The monomer having the function of imparting flexibility is preferably contained in the polymer in an amount of from 3 to 15% by weight, more preferably from 5 to 10% by weight. When the content of the monomer exceeds 15% by weight, the peeling phenomenon of the pattern at the development step becomes severe, and the straightness of the formed pattern is deteriorated. Further, if the content is less than 3% by weight, the glass transition point of the polymer It becomes high and is easily damaged, and the softness of the formed photosensitive resin composition is deteriorated. Further, the other acrylic single system is used to adjust the polarity of the polymer. An example of such an acrylic monomer is 2-hydroxyethyl. Ethyl (meth)acrylate, octyl 2-hydroxy(meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid 200947121, n-butyl acrylate, and mixtures thereof. The high molecular weight internal enthalpy of these monomers is preferably from 10 to 30% by weight based on the heat resistance, dispersibility, and hydrophilicity of the developer. The acrylate polymer resin can be obtained by polymerizing a solvent having a suitable polarity which prevents gelation of the above four kinds of monomers, and the weight average molecular weight of the formed low glass transition point acrylate resin is suitably 10, 〇〇 〇 to 35,000, more appropriate around 20,000.
本發明的感光性樹脂組成物中，前述光聚合物樹脂(成 分(A)(ii))係達成使感光性樹脂組成物之感度提升的作用。 前述光聚合物樹脂係可溶解於鹼性水溶液之樹脂，較適當 者係以下述之化學式1或2所表示者： [化學式1]In the photosensitive resin composition of the present invention, the photopolymer resin (component (A) (ii)) serves to enhance the sensitivity of the photosensitive resin composition. The photopolymer resin is a resin which can be dissolved in an alkaline aqueous solution, and is preferably represented by the following Chemical Formula 1 or 2: [Chemical Formula 1]
[化學式2] ❹[Chemical Formula 2] ❹
0 上式中，Ri係分別獨立，表示氫或碳數1〜2的烷基’ 200947121 R2是由羥基取代或未取代之碳數2〜5的伸烷基， a+b+c =1 ’ 且〇.l<a<〇.4、0<b<0_5、〇·1< c <0.6。 前述光聚合物樹脂的重量平均分子量，宜為10,000至 80,000，更宜可為15,000至50,〇〇〇。前述光聚合物的重量平 5 均分子量若在前述範圍内時，在顯影時間與殘膜除去程度 上更優異。 如前述之環氧樹脂與丙烯酸醋樹脂及/或光聚合物樹 脂之鹼性可溶性樹脂的混合物，亦即，以感光性樹脂組成 物總重量為基準’以使用1至50重量％之量的黏合劑樹脂為 10 佳，其含量在前述範圍内時，可取得適當黏度的感光性樹 脂組成物，具有厚度調節上變得容易之優點。 本發明之感光性樹脂組成物中，作為前述環氧硬化劑 (成分(Β))者可使用胺系、酸酐系、咪唑系、異花青素系、 硫醇系化合物等’更具體而言，可使用二乙烯三胺(DETA)、 15 三乙烯四胺(TETA)、三乙烯五胺(ΤΕΡΑ)、二胺基二苯基曱 烧(DDM)、二胺二苯礙(DDS)、聚醯胺(p〇lyamide amine)、 二氰二胺等胺系化合物；聚醯胺樹脂、酞酸酐、偏苯三酸 肝、焦蜜石酸酐、馬來酸酐、四羥酞酸酐、甲基四羥酞酸 酐、六羥酞酸酐、甲基羥酞酸酐等酸酐系化合物；2甲基 20咪唑(2MZ)、2-乙基-4-甲基咪唑(2E4MZ)等咪唑系化合物； 異论青素系化合物；及聚硫醇等硫醇系化合物等。 則述環氧硬化劑係以組成物總重量為基準而以〇1至 1〇重量％之量使用為佳。 乂時，前述環氧硬化劑係相對於環氧樹脂之環氧基1當 10 200947121 量’而且使航5至1.5當量’更宜為使舰…2當量的量。 其含量若侧增或細·5當量㈣㈣得良好的硬 化度。 依據所使用的環氧硬化劑之種類，可任意使用促進與 5環氧樹脂之反應性的硬化促進劑作為催化劑。可使用的硬 化促進劑，可舉2·甲基咪唾、2•乙基咪唾、2乙基_4甲基嗦 唾等口米補；2-二甲基苯盼等第三級胺類；三苯鱗等鱗類； 辛酸亞錫（Stannous octoate)等金屬化合物。前述硬化促進劑 係以環氧樹脂100重量份為基準而可使用〇」至1〇重量份的 10 量。In the above formula, Ri is independently and represents hydrogen or an alkyl group having 1 to 2 carbon atoms. 200947121 R2 is an alkyl group having 2 to 5 carbon atoms substituted or unsubstituted by a hydroxyl group, a+b+c =1 ' And 〇.l <a<〇.4, 0 < b < 0_5, 〇 · 1 < c < 0.6. The photopolymer resin preferably has a weight average molecular weight of from 10,000 to 80,000, more preferably from 15,000 to 50, Å. When the weight average molecular weight of the photopolymer is within the above range, it is more excellent in development time and degree of residual film removal. a mixture of an epoxy resin and an alkali-soluble resin of an acrylic acrylate resin and/or a photopolymer resin, that is, a binder in an amount of from 1 to 50% by weight based on the total weight of the photosensitive resin composition. When the content of the resin is within the above range, a photosensitive resin composition having an appropriate viscosity can be obtained, which has an advantage that thickness adjustment becomes easy. In the photosensitive resin composition of the present invention, as the epoxy curing agent (component), an amine-based, an acid-based, an imidazole-based, an anthocyanin-based or a thiol-based compound can be used, and more specifically , can use diethylenetriamine (DETA), 15 triethylenetetramine (TETA), triethylene pentamine (ΤΕΡΑ), diaminodiphenyl fluorene (DDM), diamine diphenyl barrier (DDS), poly An amine compound such as p〇lyamide amine or dicyandiamide; polyamine resin, phthalic anhydride, trimellitic acid liver, carotenic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydroxyl An acid anhydride compound such as phthalic anhydride, hexahydrophthalic anhydride or methyl hydroquinone anhydride; an imidazole compound such as 2 methyl 20 imidazole (2MZ) or 2-ethyl-4-methylimidazole (2E4MZ); a compound; a thiol compound such as a polythiol or the like. The epoxy hardener is preferably used in an amount of from 1 to 1% by weight based on the total weight of the composition. In the case of ruthenium, the epoxy hardener is preferably in an amount of 10 2009 47121 and is preferably 5 to 1.5 equivalents per equivalent of the epoxy group of the epoxy resin. If the content is increased sideways or fine, 5 equivalents (four) (four) have a good degree of hardening. A curing accelerator which promotes reactivity with the epoxy resin can be optionally used as the catalyst depending on the type of the epoxy curing agent to be used. The hardening accelerator which can be used is exemplified by 2, methyl methicillin, 2 ethyl stilbene, 2 ethyl -4-methyl hydrazine saliva, etc.; second dimethylamine ; triphenyl scales and other scales; stannous octoate and other metal compounds. The hardening accelerator may be used in an amount of from 10% by weight to 10 parts by weight based on 100 parts by weight of the epoxy resin.
本發明的感光性樹脂組成物中，作為前述具有乙烯系 雙鍵的交聯性單聚物（成分(C))者可使用1，4·丁二醇二丙稀 酸酯、1,3-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、季戊四 醇四丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸 15 酯、二季戊四醇二丙烯酸酯、山梨酵三丙烯酸酯、雙酚A 二丙烯酸酯衍生物、三甲基丙烷三丙烯酸酯、二季戊四醇 聚丙烯酸酯、該等的曱基丙烯酸酯類及該等的混合物等。 前述具有乙烯系雙鍵的交聯性單聚物係以感光性樹脂 組成物總重量為基準’宜使用1至30重量％、更宜使用3至 2〇 20重量％的量。其含量若小於1重量％時，無法實現感光性 樹脂組成物的柔軟性’超過重量％時’顯影性及接着力 會降低。 本發明的感光性樹脂組成物中’作為前述顏料(成分(D)) 者可全部使用有機顏料或無機顏料’有機顏料的具體性例 11 200947121 子可舉C.I.黃色顏料83、C.I.黃色顏料150、C.I.黃色顏料 138、C.I.黃色顏料128、C.I.橘色顏料43、C.I.紅色顏料177、 C.I.紅色顏料202、C.I.紅色顏料209、C.I.紅色顏料254、C.I. 紅色顏料255、C.I.綠色顏料7、C.I.綠色顏料36、C.I.藍色顏 5 料15、C.I.藍色顏料15 : 3、C.I.藍色顏料15 : 4、C.I.藍色顏 料15 : 6、C.I.紫色顏料23、C.I.黑色顏料1、C.I.黑色顏料7 等。又，無機顏料的具體性例子可舉氧化鈦、酞黑色料(Titan black)、碳黑等。該等顏料係為了組合顏色而可混合使用1 種以上。 10 前述顏料係以感光性樹脂組成物總重量為基準，而宜 使用10至70重量％的量。 本發明的感光性樹脂組成物中，前述光聚合引發劑（成 分(E))之作用係藉由可視光線、紫外線、遠紫外線等波長使 前述交聯性單聚物的聚合開始。作為前述光聚合引發劑 15 者，可使用三氮雜苯系化合物、安息香系化合物、苯乙酮 系化合物、氧葱_系化合物、味°坐系化合物及該等的混合 物等，具體而言可使用2,4-雙三氯曱基-6-對-曱氧基苯乙烯 基對稱三氮雜苯、2-對-甲氧基苯乙烯基-4,6-雙三氣曱基對 稱三氮雜苯、2,4-三氯曱基-6-三氮雜苯、2,4-三氯曱基-4-20 曱萘基-6-三氮雜苯等的三氮雜苯系化合物；二苯基酮、對 -(二乙胺基)二苯基酮等的安息香系化合物；2,2-二氯-4-苯 氧苯乙酮、2,2-二乙氧苯乙酮、2,2-二丁氧苯乙酮、2-羥基 -2-甲基苯丙酮、對-第三-丁基三氣苯乙酮等苯乙酮系化合 物；氧葱酮、硫氧葱酮、2-甲基硫氧葱酮、2-異丁基硫氧葱 200947121 酮、2-十二基硫氧葱_、2,4_二甲基硫氧葱酮、2,4-二乙基 硫氧葱酮等的氧葱酮系化合物；以及2,2_雙_2-氣苯基 _4,5,4,5_四苯基-2-1,2-雙咪唑、2,2_雙（2,4,6-三氰苯 基)-4,4,5,5-四笨基-1，2-雙咪〇坐等的〇米唾系化合物等。 5 前述光聚合引發劑係以感光性樹脂組成物總重量為基 準’宜使用0.3至5重量％、更宜使用〇 5至2重量％的量。其 含量若小於0.3重量％時，硬化度會降低，因低感度而會導 0 致正常性形狀之圖案變得難以實現，且也有圖案的直進性 變差的問題。若超過5重量％時’保存穩定性上會有問題’ 10 因高硬化度而導致解像度變低，且在所形成的圖案以外的 - 部分容易有殘留物產生。 本發明的感光性樹脂組成物中，作為前述溶劑（成分(F)) 者’可使用在溶解性及塗佈性等方面適當之物，適當的溶 d之具體性例子可舉丙二醇單乙喊醋酸鹽、乙氧基乙基丙 15 酸酯、醋酸丁酯、乙二醇單甲醚醋酸鹽、丙二醇單曱醚、 〇 丙二醇甲醚醋酸鹽、二乙二醇二甲醚、二乙二醇甲基乙醚、 環己_、3-曱氧基乙基丙酸酯、3-乙氧基甲基丙酸酯及該等 的現合物等，尤其以使用丙二醇單乙醚醋酸鹽、乙氧基乙 基丙酸S旨、或醋酸丁醋為佳。 20 此 前述溶劑係依據黏度或組成物内總固形分含量而其含 量為例外，在將本發明感光性組成物所使用之固形分除去 後之剩餘殘量中所含，其含量以感光性樹脂組成物總重量 為基準而宜為5至60重量％。溶劑若脫逸前述範圍，則無法 克服厚度偏差，將導致感光性樹脂組成物的均勻性降低的 13 200947121 問題。 又，本發明的感光性樹脂組成物可依據需要，追加含 有界面活性劑、增減劑、催化劑等添加劑。尤其前述界面 活性劑可使用石夕系或氟系界面活性劑。 5 前述添加劑係以感光性樹脂組成物總重量為基準，最 大宜使用2重量％的量’其含量若超過2重量％時，恐有殘膜 產生或穩定性降低之虞。 依據本發明的其他實施形態，可提供將前述感光性樹 脂組成物硬化所獲得的硬化膜、含有前述硬化膜的濾色 10 板、及含有前述濾色板的面板顯示器。 使用依據本發明的感光性樹脂組成物，即使在200°C以 下的低溫硬化步驟，氣體產生量仍很少，可獲得耐熱性與 耐化學性優異之具可靠性的硬化膜。又，藉由利用前述感 光性樹脂組成物，可由驗性水溶液顯影，獲得感度及解像 15 度優異並形狀良好之硬化膜圖案，而能以產業性有效率地 提供可靠性高的濾色板及含有該濾色板的扁平面顯示器。 以下，依據下述實施例進一步詳細說明本發明。但是， 下述實施例僅為用以例示本發明者，本發明之範圍並不限 定於此。在下述實施例中，凡未特別言及之情況下，百分 20 率及混合比係以重量為基準。 [實施例] (實施例1)在丙二醇甲醚醋酸鹽（PGMEA)35g的溶劑 中，將作為光聚合引發劑的IRGACURE® 369 (汽巴精化公司 (Ciba Specialty Chemicals Inc·)製造）lg與DETX-S 0.6g在 200947121 5 Ο 10 15 ❹ 20 30分鐘常温下攪拌溶解後，加入作為鹼性可溶性光聚合物 樹脂之DJB250((股）東進半化學製造)5g、作為環氧樹脂的 NC-3000H(日本化藥(股）製造)2.5g、作為具有乙烯系雙鍵之 交聯性單聚物的DPHA(曰本化藥（股))5g、作為環氧硬化劑 的MCD(曰本化藥（股）製造）〇 7g，以丨小時在常溫攪拌之 後，放入作為顏料的C.I.藍色顏料15 : 6與C.I.紫色顏料23 之混合物50g、與添加劑〇.2g，以1小時在常溫下攪拌。 將如此獲得之組成物，使之經2次以上過濾以除去不純 物’而獲得本發明的感光性樹脂組成物。 (實施例2)使用C.I.紅色顏料254 50g作為顏料，除此之 外與實施例1相同方法’取得感光性樹脂組成物。 (實施例3)使用C.I.綠色顏料36 45g與C.I.黃色顏料 138 5g作為顏料，除此之外與實施例丨相同方法，取得感 光性樹脂組成物。 (實施例4)使用碳黑（20%溶液)5〇g作為顏料，除此之外 與實施例1相同方法，取得感光性樹脂組成物。 (實施例5)使用HIB((股）東進半化學製造)5§作為丙烯 酸酯樹脂，以此作為驗性可溶性樹脂，除此之外與實施例1 相同方法，取得感光性樹脂組成物。 (實施例6)混合使用DJB250((股）東進半化學製造)2 5g 作為光聚合物樹脂，及ΙΉΒ((股)東進半化學製造)2.5g作為 丙烯酸酯樹脂，以此作為鹼性可溶性樹脂，除此之外與實 施例1相同方法，取得感光性樹脂組成物。 (比較例1)除了不使用環氧樹脂與環氧硬化劑之外，與 15 200947121 實施例1相同方法獲得感光性樹脂組成物。 (比較例2)除了不使用環氧樹脂與環氧硬化劑之外，與 實施例5相同方法獲得感光性樹脂組成物。 (比較例3)除了不使用環氧硬化劑之外，與實施例1相同 5 方法獲得感光性樹脂組成物。 (比較例4)除了不使用環氧樹脂之外，與實施例丨相同方 法獲得感光性樹脂組成物。 將前述實施例1至6以及比較例〗至4的組成（g)顯示於下 [表1] 區分 實施例 比較例 — 1-4 5 6 ] 2 3 4 丙烯酸酯樹脂 0 5 2.5 0 5 0 0 光聚合物樹脂 5 0 2.5 5 0 5 5 環氧樹脂 2.5 2.5 2.5 0 0 2.5 0 環氧硬化劑 0.7 0.7 0.7 0 0 0 0.7 交聯性丙烯酸單聚物 5 5 5 5 5 5 5 顏料 50 50 50 50 50 50 50 光聚合 IRGACURE®369 1 1 1 1 1 1 1 引發劑 DETX-S 0.6 0.6 0.6 0.6— 0.6 0.6 0.6 溶劑 PGMEA 35 35 35 35— 35 35 35 添加劑 0.2 0.2 0.2 0.2 0.2 0.2 0.2 實驗例：硬化膜的物性評價 由前述實施例1至6及比較例1至4中所製造之感光性樹 15 脂組成物而取得之硬化膜的物性’依據氣體產生量、耐化 學性及耐熱性等方面，進行評價。 首先’將已製造之感光性樹脂組成物以旋轉塗佈使之 成為1至2"m之厚度以後，在80°C的熱板上乾燥2分鐘取得 塗佈膜。使光罩就定位於所取得的塗佈膜上後，利用發出 16 200947121 200nm到400nm波長的超高壓水銀燈，以365mn為基準，進 行既定時間曝光使之成為約l〇〇mj/cm2，利用koh顯影液 (DCD-260CF、（股)東進半化學製造），於既定時間通過嘴嘴 進行顯影之後，在15(TC、17CTC、190。(：及23CTC這4種溫度 5 之下，進行30分鐘硬烤步驟，製造硬化膜。 (1)氣體產生量測定 將前述進行之溫度所獲致的4種試驗片，以10mmx 7〇mm之大小切斷為10片，放入JTD_505自動採樣器 (Autosampler)(Jai社），於240。(：的真空條件下加熱30分鐘， 10 將所出現的氣體收集（collection)於-4(TC的冷卻管。將之通 過GC-MS分離而針對各個物質進行定量分析。如此評價所 得之結果顯示於下表2。 〇：氣體產生量對比所量產之感光性樹脂組成物小於100% △:氣體產生量對比所量產之感光性樹脂組成物在1〇〇至 15 200%範圍 X :氣體產生量對比所量產之感光性樹脂組成物超過200% [表2]In the photosensitive resin composition of the present invention, as the crosslinkable monomer (component (C)) having a vinyl double bond, 1,4-butanediol diacrylate and 1,3- can be used. Butanediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate 15 ester, dipentaerythritol diacrylate, sorbitan triacrylate, bisphenol A diacrylate derivative, trimethylpropane triacrylate, dipentaerythritol polyacrylate, these mercapto acrylates, and the like. The crosslinkable monomer having an ethylene double bond is preferably used in an amount of from 1 to 30% by weight, more preferably from 3 to 2% by weight based on the total mass of the photosensitive resin composition. When the content is less than 1% by weight, the flexibility of the photosensitive resin composition cannot be achieved. When the content exceeds % by weight, the developability and the adhesion are lowered. In the photosensitive resin composition of the present invention, the organic pigment or the inorganic pigment 'organic pigment can be used as the pigment (component (D)). Specific examples 11 200947121 include CI yellow pigment 83 and CI yellow pigment 150. CI yellow pigment 138, CI yellow pigment 128, CI orange pigment 43, CI red pigment 177, CI red pigment 202, CI red pigment 209, CI red pigment 254, CI red pigment 255, CI green pigment 7, CI green pigment 36 , CI Blue Yan 5 material 15, CI blue pigment 15 : 3, CI blue pigment 15 : 4, CI blue pigment 15 : 6, CI purple pigment 23, CI black pigment 1, CI black pigment 7 and so on. Further, specific examples of the inorganic pigment include titanium oxide, tantalum black, and carbon black. These pigments may be used in combination of one or more kinds in order to combine colors. The above pigment is based on the total weight of the photosensitive resin composition, and is preferably used in an amount of 10 to 70% by weight. In the photosensitive resin composition of the present invention, the photopolymerization initiator (component (E)) functions to initiate polymerization of the crosslinkable monomer by wavelengths such as visible light, ultraviolet light, and far ultraviolet light. As the photopolymerization initiator 15, a triazabenzene compound, a benzoin compound, an acetophenone compound, an oxygen onion compound, a taste compound, a mixture thereof, or the like can be used. Using 2,4-bistrichloroindolyl-6-p-nonyloxystyryl symmetrical triazabenzene, 2-p-methoxystyryl-4,6-bistrimethyl sulfhydryl symmetrical trinitrogen a triazabenzene compound such as heterobenzene, 2,4-trichloroindenyl-6-triazabenzene or 2,4-trichloroindenyl-4-20 indolyl-6-triazabenzene; A benzoin compound such as diphenyl ketone or p-(diethylamino)diphenyl ketone; 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2 , acetophenone-based compounds such as 2-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tris-butyltrisacetophenone, oxolone, thioxanthone, 2 -methyl thioxanthene, 2-isobutyl thiosulfate 200947121 ketone, 2-dodecyl sulphate _, 2,4 dimethyl thioxanthene, 2,4-diethyl thio An onion ketone compound such as onion ketone; and 2,2_bis_2-gas phenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, 2,2-bis ( 2,4,6-tricyanobenzene A glutinous rice compound such as a base-4,4,5,5-tetraphenyl-1,2-biimidine or the like. The photopolymerization initiator is preferably used in an amount of from 0.3 to 5% by weight, more preferably from 5 to 2% by weight, based on the total mass of the photosensitive resin composition. When the content is less than 0.3% by weight, the degree of hardening is lowered, and the pattern of the normal shape is difficult to realize due to the low sensitivity, and the straightness of the pattern is also deteriorated. When it exceeds 5% by weight, there is a problem in storage stability. 10 The resolution is lowered due to the high degree of hardening, and residues are likely to be generated in portions other than the formed pattern. In the photosensitive resin composition of the present invention, as the solvent (ingredient (F)), a substance suitable for solubility and coating properties can be used, and an example of specific solubility can be exemplified by propylene glycol alone. Acetate, ethoxyethylpropane 15 acid ester, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoterpene ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ether, cyclohexyl, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, and the like, especially the use of propylene glycol monoethyl ether acetate, ethoxylate Ethylpropionate S or butyl acetate is preferred. The solvent is in the form of a viscosity or a total solid content in the composition, and is contained in the remaining residue after removing the solid component used in the photosensitive composition of the present invention, and the content thereof is a photosensitive resin. The total weight of the composition is preferably from 5 to 60% by weight based on the total weight. When the solvent is out of the above range, the thickness variation may not be overcome, and the uniformity of the photosensitive resin composition may be lowered. Further, the photosensitive resin composition of the present invention may further contain an additive such as a surfactant, a reducing agent or a catalyst as needed. In particular, the above surfactant may be a stone-based or fluorine-based surfactant. 5 The above-mentioned additive is preferably used in an amount of 2% by weight based on the total weight of the photosensitive resin composition. When the content exceeds 2% by weight, there is a fear that residual film generation or stability is lowered. According to another embodiment of the present invention, a cured film obtained by curing the photosensitive resin composition, a color filter plate containing the cured film, and a panel display including the color filter can be provided. According to the photosensitive resin composition of the present invention, even in the low-temperature curing step of 200 ° C or less, the amount of gas generated is small, and a cured film excellent in heat resistance and chemical resistance can be obtained. In addition, by using the photosensitive resin composition, it is possible to obtain a cured film pattern which is excellent in sensitivity and resolution and has a good shape by a developed aqueous solution, and can provide a highly reliable color filter industrially. And a flat surface display containing the color filter. Hereinafter, the present invention will be described in further detail based on the following examples. However, the following examples are merely illustrative of the inventors, and the scope of the invention is not limited thereto. In the following examples, the percentages and mixing ratios are based on weight unless otherwise specified. [Examples] (Example 1) In a solvent of 35 g of propylene glycol methyl ether acetate (PGMEA), IRGACURE® 369 (manufactured by Ciba Specialty Chemicals Inc.) lg as a photopolymerization initiator was used. DETX-S 0.6g at 200947121 5 Ο 10 15 ❹ 20 After 30 minutes of stirring at room temperature, DJB250 (manufactured by Dongjin Semi-Chemical Co., Ltd.) as an alkali-soluble photopolymer resin was added to 5 g of CO-based epoxy resin. 2.5 g (manufactured by Nippon Kayaku Co., Ltd.), 2.5 g of DPHA (Sakamoto Chemical Co., Ltd.) as a crosslinkable monomer having a vinyl double bond, and MCD as an epoxy curing agent. Manufactured by a drug (stock)) 7 g, after stirring at room temperature for 丨 hours, 50 g of a mixture of CI blue pigment 15 : 6 and CI violet pigment 23 as a pigment, and an additive 〇 2 g, at 1 hour at room temperature Stir. The composition thus obtained was subjected to filtration twice or more to remove impurities ' to obtain the photosensitive resin composition of the present invention. (Example 2) A photosensitive resin composition was obtained in the same manner as in Example 1 except that 50 g of C.I. red pigment 254 was used as the pigment. (Example 3) A photosensitive resin composition was obtained in the same manner as in Example 使用 except that C.I. green pigment 36 45 g and C.I. yellow pigment 138 5 g were used as the pigment. (Example 4) A photosensitive resin composition was obtained in the same manner as in Example 1 except that carbon black (20% solution) was used as a pigment. (Example 5) A photosensitive resin composition was obtained in the same manner as in Example 1 except that the acrylic acid resin was used as the acryl resin. (Example 6) 2 5 g of DJB250 (manufactured by Dongjin Semi-Chemical Co., Ltd.) was used as a photopolymer resin, and 2.5 g of ruthenium (manufactured by Tojin Semi-Chemical Co., Ltd.) was used as an acrylate resin as an alkali-soluble resin. A photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. (Comparative Example 1) A photosensitive resin composition was obtained in the same manner as in Example 1 of 15200947121 except that the epoxy resin and the epoxy hardener were not used. (Comparative Example 2) A photosensitive resin composition was obtained in the same manner as in Example 5 except that the epoxy resin and the epoxy hardener were not used. (Comparative Example 3) A photosensitive resin composition was obtained in the same manner as in Example 1 except that the epoxy curing agent was not used. (Comparative Example 4) A photosensitive resin composition was obtained in the same manner as in Example except that the epoxy resin was not used. The composition (g) of the foregoing Examples 1 to 6 and Comparative Examples 7-14 to 4 is shown below [Table 1] Example of Comparative Example - 1-4 5 6 ] 2 3 4 Acrylate Resin 0 5 2.5 0 5 0 0 Photopolymer Resin 5 0 2.5 5 0 5 5 Epoxy Resin 2.5 2.5 2.5 0 0 2.5 0 Epoxy Hardener 0.7 0.7 0.7 0 0 0 0.7 Crosslinkable Acrylic Monomer 5 5 5 5 5 5 5 Pigment 50 50 50 50 50 50 50 Photopolymerization IRGACURE® 369 1 1 1 1 1 1 1 Initiator DETX-S 0.6 0.6 0.6 0.6- 0.6 0.6 0.6 Solvent PGMEA 35 35 35 35- 35 35 35 Additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 The physical properties of the cured film obtained from the photosensitive tree 15 lipid compositions produced in the above-described Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated in terms of gas generation amount, chemical resistance, heat resistance, and the like. , for evaluation. First, the photosensitive resin composition to be produced was spin-coated to have a thickness of 1 to 2 " m, and then dried on a hot plate at 80 ° C for 2 minutes to obtain a coating film. After positioning the mask on the obtained coating film, an ultrahigh pressure mercury lamp emitting 16 200947121 200 nm to 400 nm wavelength is used for a predetermined time exposure to be about l〇〇mj/cm 2 on the basis of 365 nm, using koh The developing solution (DCD-260CF, manufactured by Dongjin Semi-Chemical Co., Ltd.) is developed through the nozzle at a predetermined time, and then subjected to 30 minutes under 15 (TC, 17 CTC, 190. (: and 23 CTC). Hard-bake step to produce a cured film. (1) Measurement of gas generation The four test pieces obtained by the above-mentioned temperature were cut into 10 pieces at a size of 10 mm x 7 〇 mm, and placed in a JTD_505 automatic sampler (Autosampler). (Jai), heated at 240 (under vacuum for 30 minutes, 10) Collecting the gas present in a -4 (TC cooling tube. Separating it by GC-MS to quantify each substance The results obtained in this evaluation are shown in the following Table 2. 〇: The amount of gas generated is less than 100% compared with the mass of the photosensitive resin composition Δ: The amount of gas generated is compared with the amount of the photosensitive resin composition produced by the sample. To 15 200% range X: gas production Compare the amount of production of photosensitive resin composition 200% [Table 2]
實施例 比較例 1 2 3 4 5 6 1 2 3 4 230〇C 〇 〇 〇 Ο ο 〇 〇 〇 〇 〇 190°C 〇 〇 〇 ο 〇 Δ X Δ Δ 170°C Ο 〇 〇 ο ο 〇 X X X X 150°C 〇 〇 〇 〇 Δ 〇 X X X X 20 (2)耐熱性評價 將前述進行之溫度所獲致的4種試驗片，在230度再次 進行3小時熱處理，評價圖案之變化、色度之變化及厚度之 17 200947121 變化，其結果顯示於下表3。 〇：無圖案之變化，色差（AEab)在3.0以下 △:稍有圖案之變化，色差（AEab)在3.0至5.0範圍 X :圖案之變化大，色差（AEab)在5.0以上 5 ※圖案之變化：圖案表面上的再結晶現象、圖案膨脹 [表3]EXAMPLES Comparative Example 1 2 3 4 5 6 1 2 3 4 230〇C 〇〇〇Ο ο 〇〇〇〇〇190°C 〇〇〇ο 〇Δ X Δ Δ 170°C Ο 〇〇ο ο 〇XXXX 150 °C 〇〇〇〇Δ 〇XXXX 20 (2) Evaluation of heat resistance The four test pieces obtained by the above-mentioned temperature were heat-treated again at 230 degrees for 3 hours to evaluate the change of the pattern, the change of the chromaticity, and the thickness. 17 200947121 Change, the results are shown in Table 3 below. 〇: no pattern change, AEab is below 3.0 △: slight pattern change, AEab in the range of 3.0 to 5.0 X: pattern change is large, AEab is 5.0 or more 5 ※ pattern change : Recrystallization on the surface of the pattern, pattern expansion [Table 3]
實施例 比較例 1 2 3 4 5 6 1 2 3 4 230〇C 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 190。。 〇 〇 〇 〇 〇 〇 X X Δ X 170°C 〇 〇 〇 〇 〇 〇 X X X X 150°C 〇 Δ 〇 〇 〇 〇 X X X XEXAMPLES Comparative Example 1 2 3 4 5 6 1 2 3 4 230 〇C 〇 〇 〇 〇 〇 〇 〇 〇 〇 190. . X 〇 〇 〇 〇 〇 X X Δ X 170°C 〇 〇 〇 〇 〇 〇 X X X X 150°C 〇 Δ 〇 〇 〇 〇 X X X X
(3)耐化學性評價 10 將前述進行之溫度所獲致的4種試驗片，分別浸潰於 5%的HC1水溶液、5%的NaOH水溶液、NMP、二甲苯、異 丙醇中60分鐘後使之乾燥，評價圖案之變化與色度之變 化，其結果顯示於下表4。(3) Evaluation of chemical resistance 10 The four test pieces obtained by the above-mentioned temperature were each immersed in a 5% aqueous HCl solution, a 5% aqueous NaOH solution, NMP, xylene, and isopropyl alcohol for 60 minutes. After drying, the change in pattern and the change in chromaticity were evaluated, and the results are shown in Table 4 below.
又，測定NMP溶液中所溶出的物質之吸光度，顯示於 15 第1圖。 〇：無圖案之變化，色差（AEab)在3.0以下 △:稍有圖案之變化，色差（△Eab)在3.0至5.0範圍 X :圖案之變化大，色差（ΔΕαϊ»)在5.0以上 圖案之變化：圖案的剝離現象或溶融現象、圖案膨脹 18 20 200947121 5Further, the absorbance of the substance eluted in the NMP solution was measured and shown in Fig. 1 . 〇: no pattern change, color difference (AEab) is below 3.0 △: slight pattern change, color difference (ΔEab) in the range of 3.0 to 5.0 X: pattern change is large, color difference (ΔΕαϊ») is more than 5.0 pattern change : Pattern peeling or melting phenomenon, pattern expansion 18 20 200947121 5
10 [表4]10 [Table 4]
實施例 比較例 1 2 3 4 5 6 1 2 3 4 〇 〇 〇 〇 〇 〇 〇 〇 ο ΤΓ 19〇°c 〇 〇 〇 〇 〇 〇 X X Λ X 〇 〇 〇 〇 υ Ο X X X χ ~Ϊ5〇^~~ 〇 Δ 〇 △ υ 〇 X X X X 從前述表2至4、及第1圖之結果可得知，由本發明的實 施例1至6所製造之樹脂組成物而獲得的硬化膜，相較於比 較例1至4的情況，即使在200°C以下的低溫將之硬化，仍具 有低氣體產生量，具備優異的耐熱性與财化學性。 【圖式簡單說明】 第1圖是顯示實驗例中，由實施例丨及比較例1所製造之 感光性樹脂組成物所獲致的硬化膜，使之浸潰於NMP溶液 後，測定其溶出之物質的吸光度的結果。 【主要元件符號說明】 (無）EXAMPLES Comparative Example 1 2 3 4 5 6 1 2 3 4 〇〇〇〇〇〇〇〇ο ΤΓ 19〇°c 〇〇〇〇〇〇XX Λ X 〇〇〇〇υ Ο XXX χ ~Ϊ5〇^~ ~ 〇 Δ 〇 Δ υ 〇 XXXX From the results of the above Tables 2 to 4 and 1 , the cured films obtained from the resin compositions produced in Examples 1 to 6 of the present invention were compared with the comparative examples. In the case of 1 to 4, even if it is hardened at a low temperature of 200 ° C or lower, it has a low gas generation amount and has excellent heat resistance and chemical properties. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a cured film obtained from the photosensitive resin compositions produced in Examples 丨 and Comparative Example 1 in an experimental example, which was immersed in an NMP solution, and then measured for dissolution. The result of the absorbance of the substance. [Main component symbol description] (none)
1919
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| KR101202044B1 (en) * | 2009-11-04 | 2012-11-16 | 제일모직주식회사 | Liquid adhesive composition of semiconductor device and semiconductor device using the same |
| JP5736718B2 (en) * | 2010-10-18 | 2015-06-17 | Jsr株式会社 | Radiation-sensitive resin composition, cured film and method for forming the same |
| JP5771944B2 (en) * | 2010-10-18 | 2015-09-02 | Jsr株式会社 | Manufacturing method of color filter |
| CN102692661B (en) * | 2011-03-24 | 2016-01-06 | Jsr株式会社 | The manufacture method of colored filter, colored filter and liquid crystal display cells |
| JP5786451B2 (en) * | 2011-05-19 | 2015-09-30 | Jsr株式会社 | Color filter, liquid crystal display element, and method of manufacturing color filter |
| JP5884325B2 (en) * | 2011-07-15 | 2016-03-15 | Jsr株式会社 | Color filter, liquid crystal display element, and method of manufacturing color filter |
| JP5966268B2 (en) * | 2011-07-22 | 2016-08-10 | Jsr株式会社 | Array substrate, liquid crystal display element, and method of manufacturing array substrate |
| JP5741331B2 (en) * | 2011-09-01 | 2015-07-01 | Jsr株式会社 | Array substrate, liquid crystal display element, and method of manufacturing array substrate |
| US10042253B2 (en) | 2016-01-11 | 2018-08-07 | Samsung Display Co., Ltd. | Photosensitive resin composition, film prepared by using the photosensitive resin composition, and organic light-emitting display device including the film |
| KR102329943B1 (en) * | 2016-03-16 | 2021-11-22 | 동우 화인켐 주식회사 | Negative photosensitive resin composition and photo-cured pattern prepared from the same |
| CN106526726B (en) * | 2016-11-28 | 2019-02-19 | 海安浩驰科技有限公司 | A kind of diffusion barrier and preparation method thereof of high luminance |
| KR102393376B1 (en) * | 2017-04-10 | 2022-05-03 | 삼성디스플레이 주식회사 | Photosensitive resin composition, and electronic device comprising cured product of composition for forming pattern comprising the same |
| KR102157366B1 (en) | 2017-12-15 | 2021-03-29 | 주식회사 엘지화학 | Dye compound and photopolymer composition |
| CN109188865B (en) * | 2018-09-03 | 2022-03-15 | 浙江福斯特新材料研究院有限公司 | Photosensitive covering film composition and application thereof |
| CN110628372A (en) * | 2019-11-06 | 2019-12-31 | 厦门宏晨电子产品有限公司 | Flame-retardant adhesive |
| KR20210104956A (en) | 2020-02-17 | 2021-08-26 | 동우 화인켐 주식회사 | A black photo sensitive resin composition, a color filter comprising a black metrics by using the composition, and a display comprising the color filter |
| KR20210111492A (en) | 2020-03-03 | 2021-09-13 | 동우 화인켐 주식회사 | A curable resin comopsition, a pattern and a display device |
| KR20210131560A (en) | 2020-04-24 | 2021-11-03 | 동우 화인켐 주식회사 | A curable resin comopsition, a pattern and a display device |
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