TW201142502A - Photosensitive resin composition and color filter using the same - Google Patents
Photosensitive resin composition and color filter using the same Download PDFInfo
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- TW201142502A TW201142502A TW100126952A TW100126952A TW201142502A TW 201142502 A TW201142502 A TW 201142502A TW 100126952 A TW100126952 A TW 100126952A TW 100126952 A TW100126952 A TW 100126952A TW 201142502 A TW201142502 A TW 201142502A
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- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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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
- 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
- G03F7/038—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
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
201142502 w 六、發明說明： 【發明所屬之技術領域】 本發明乃關於光硬化性組成物及採用該光硬化性組 成物的彩色濾光片，更詳細而言，乃關於適用於彩色濾光 片用油墨之感光性樹脂組成物。 【先前技術】 衫色液晶顯示裝置是以控制光的穿透量或是反射量 的液晶部及彩色濾光片為構成要素。該彩色濾光片的製造 方法一般為於玻璃或塑膠片等透明基板的表面上形成黑色 矩陣(black matrix)，接下來以長條狀或是馬賽克狀等顏色 圖案，依序形成紅、綠、藍等不同色相的方法。圖案尺寸 因彩色濾光片的用途及各個顏色的不同而不同，隨著紅、 、、彔i的晝素從200至300 " m往1〇〇 " m，黑色矩陣由2〇 //m往l〇#m薄線化，因而更進一步要求能夠達到高精密 尺寸的感光性樹脂材料。 最近幾年’於液晶電視、液晶顯示器、彩色液晶手機 等領域中，採用彩色液晶顯示裝置。彩色遽光片為決定彩 色液晶顯示裝置的視覺性的重要元件之一，視覺性的提 亦即為了獲得更為鮮m的晝像，構成彩色滤光片之紅、 、彔藍等晝素必須達到比目前更高的色純度，以及黑色矩 陣的馬遮光性，因而必須於感光性樹脂組成物當中添加較 以往更多的著色劑。 圖案的形成乃利用光反應性樹脂與光聚合起始劑的 反應所產生的光硬化作用，且主要以為水銀燈光線頻譜之 316123D01 5 201142502 w 的1線(365nm)做為使顏料分散系列負型彩色光阻層硬 化的曝光波長。紅、綠、藍及黑色的感光性樹脂組成物（亦 稱為油墨）中，著色劑本身吸收紫外線，且由於著色劑在感 光性樹脂組成物中所占的比例高，因此，基於下述理由， 感光性樹脂組成物的光硬化性及顯像性惡化，而難以獲得 圖案尺寸女疋性、顯像圖框、圖案密著性、及圖案輪廓之 形狀皆良好之彩色濾、光片。⑴於曝光部分上，在膜厚方向 上的父聯密度產生差距，即使於塗膜表面上達到足夠的光 硬化，於基板底面上亦難以進行光硬化，（2)曝光部分及未 曝光部分中的交聯密度難以達到差距，（3)由於添加多量不 溶於顯像液中的不溶性著色劑，因而使顯像性顯著下降。 而這些問越尤其在感光性樹脂組成物的分光特性上，及遮 光感光性樹脂組成物中更為顯著。 再者，最近幾年，為了提升生產效率及降低成本，彩 色遽光片生產線上的母玻璃基板有逐年增大的趨勢，甚至 於製造出超過lm的母玻璃基板。此外，為了降低作業時 間及提升生產效率，於曝光製程中要求較短的曝光時間， 亦即’要求可採用低曝光量來進行光硬化之彩色據光片用 感光性樹脂組成物。 由於如上述期求可使著色劑之含有比率高且光硬化 困難之彩色渡光片用感光性樹脂脂組成物於低曝光量下， 獲付圖案尺寸安定性、圖案密者性及圖案輪靡之形狀之清 晰度皆良好且顯像圖框寬之圖案，所以感光性樹脂組成物 的问感度為不可或缺。 316123D01 6 201142502 [專利文獻1]曰本特開平號公報 [專利文獻2]日本特開平7_278214號公報 [專利文獻3]日本特開2〇〇1_26453〇號公報 [專利文獻4]日本特開2〇〇2_323762號公報 [專利文獻5]日本特開2〇〇3-96118號公報 [專利文獻6]曰本特開平7-3122號公報 於專利文獻1中，提示為了提升顏料濃度而達到 的顏色再現性並防止感度降低，_甲基述二唑：良 合物及齒甲基列化合物來做為高：度光 始劑之例子。然而’這些化合物雖然藉由抑制因氧弓丨：： 反士而使表面平坦性降低的情形改善，但是就圖 精您度而言’仍無法達到令人滿意的程度。此外， 文獻2至5等中揭示於感光性樹脂級成物中採用月§酉旨 (〇職ester)系列的光聚合起始劑，來做為高感度光聚人 起始劑’但尚未達料人滿㈣程度。於專歡獻6中二 不採用含不飽和基的驗可溶性樹脂化合物之彩色渡光片用 感光性樹脂組成物。 【發明内容】 ,、因此，為了解決上述問題，本發明的目的在於提供可 形成圖案尺寸的安定性優良，顯像圖框寬，以及圖案密著 性及圖案輪廓之形狀之清晰度良好之圖案之彩色滤光片用 感光性樹脂組成物。此外，其他目的在於提供採用此彩色 濾光片用感光性樹脂組成物所形成的塗膜及彩色濾光片。 本發明者為了解決上述課題而探討之後的結果發 316123D01 7 201142502 現，將衍生自雙酴(bisphenol)的芳香族環氧化合物與（甲武)201142502 w VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable composition and a color filter using the photocurable composition, and more particularly to a color filter A photosensitive resin composition using an ink. [Prior Art] The shirt color liquid crystal display device is composed of a liquid crystal portion and a color filter that control the amount of light penetration or the amount of reflection. The method for manufacturing the color filter generally comprises forming a black matrix on a surface of a transparent substrate such as a glass or a plastic sheet, and then forming a red or green color in a color pattern such as a strip or a mosaic. A method of different hue such as blue. The size of the pattern varies depending on the use of the color filter and the color of each color. As the color of red, , and 彔i ranges from 200 to 300 " m to 1〇〇" m, the black matrix consists of 2〇// m is thinner than l〇#m, and thus it is further required to be able to achieve a photosensitive resin material of high precision. In recent years, color liquid crystal display devices have been used in fields such as liquid crystal televisions, liquid crystal displays, and color liquid crystal mobile phones. The color calender is one of the important components for determining the visuality of the color liquid crystal display device. The visual enhancement is to obtain a more vivid image, and the red, blue, and indigo molecules of the color filter must be formed. A color purity higher than the current and a horse shading property of the black matrix are achieved, and thus it is necessary to add more color formers to the photosensitive resin composition. The pattern is formed by the photohardening effect of the reaction of the photoreactive resin and the photopolymerization initiator, and is mainly used as the pigment dispersion series negative color of the 316123D01 5 201142502 w of the mercury light line spectrum. The exposure wavelength at which the photoresist layer is hardened. In the photosensitive resin composition (also referred to as ink) of red, green, blue, and black, the colorant itself absorbs ultraviolet rays, and since the colorant accounts for a high proportion in the photosensitive resin composition, it is based on the following reasons. In addition, the photocurability and developability of the photosensitive resin composition are deteriorated, and it is difficult to obtain a color filter or a light sheet having a good pattern size, a picture frame, a pattern adhesion, and a pattern outline. (1) On the exposed portion, the density of the parental bond in the film thickness direction is different, and even if sufficient light hardening is achieved on the surface of the coating film, it is difficult to perform photohardening on the bottom surface of the substrate, and (2) exposed portion and unexposed portion It is difficult to achieve the difference in the crosslink density, and (3) the significant decrease in the developability due to the addition of a large amount of the insoluble colorant which is insoluble in the developing liquid. Further, these problems are more remarkable particularly in the spectral characteristics of the photosensitive resin composition and in the photosensitive photosensitive resin composition. Furthermore, in recent years, in order to increase production efficiency and reduce costs, the mother glass substrate on the color polishing sheet production line has been increasing year by year, and even the mother glass substrate exceeding lm has been manufactured. Further, in order to reduce the working time and increase the production efficiency, a short exposure time is required in the exposure process, that is, a photosensitive resin composition for a color light-receiving sheet which is required to be photocured by a low exposure amount. The photosensitive resin composition for a color light-passing sheet having a high content ratio of a coloring agent and having difficulty in photohardening is obtained at a low exposure amount as described above, and the pattern size stability, pattern denseness, and pattern rim are obtained. Since the shape of the shape is good and the pattern is wide, the sensitivity of the photosensitive resin composition is indispensable. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Sexuality and prevention of reduced sensitivity, _methyl succinimide: a good compound and a dentate methyl group compound as an example of a high: photoinitiator. However, although these compounds have been improved by suppressing the decrease in surface flatness due to the oxygen bow::, they are still not satisfactory. Further, in the photosensitive resin grades disclosed in Documents 2 to 5, etc., a photopolymerization initiator which is a high-sensitivity photopolymerization initiator is used as a high-sensitivity photopolymerization initiator. The level of material is full (four). In the special offer, the photosensitive resin composition for the color light-passing sheet containing the unsaturated resin compound containing the unsaturated group is not used. SUMMARY OF THE INVENTION Therefore, in order to solve the above problems, an object of the present invention is to provide a pattern which is excellent in stability in pattern size, wide in image frame width, and in clearness in pattern adhesion and shape of a pattern outline. The color filter is made of a photosensitive resin composition. Further, another object is to provide a coating film and a color filter formed using the photosensitive resin composition for a color filter. The inventors of the present invention have studied the results of the above problems. 316123D01 7 201142502 Now, an aromatic epoxy compound derived from bisphenol and (A)
丙婦酸的反應物，再與多元羧酸或是多元竣酸酐進行反 應，得到含不飽和基的化合物，於包含此含不餘和基的& 合物的感光性樹脂組成物的光聚合起始劑中，若添加具有 特定化學構造之◦-醯基后(〇-acyloxime)系列光聚合起始 劑’將可解決上述問題點，因而完成本發明。 本發明為一種彩色濾光片用感光性樹脂組成物，乃以 下列（A)至（D)成伤為必需成份：（A)將具有衍生自雙盼 (bisphenol)類之2個縮水甘油醚基之環氧化合物與（p基） 丙烯酸的反應物，再與多元羧酸或多元羧酸酐反應所得到 之含不飽和基的驗可溶性樹脂化合物，（叫具有至少1個以 上的乙烯性不飽和鍵結之光聚合性單體，（c)光聚合起始 劑，（D)著色劑；其特徵為，⑷成份與⑻成份的重量比例 (A)/(B)為20/80至9〇/1〇;相對於(A)成份與成份合計1〇〇 重量份’（C)成份之含量為2至30重量份；且以下列通式 (I)所表示的化合物做為成份(c)光聚合起始劑： 【化學式1】The reaction of a bupropion acid reaction with a polycarboxylic acid or a polybasic phthalic anhydride to obtain an unsaturated group-containing compound, and photopolymerization of a photosensitive resin composition containing the & Among the initiators, the addition of a fluorene-acyloxime series photopolymerization initiator having a specific chemical structure will solve the above problems, and thus the present invention has been completed. The present invention is a photosensitive resin composition for a color filter which is an essential component in the following (A) to (D): (A) will have two glycidyl ethers derived from bisphenol An unsaturated group-containing soluble resin compound obtained by reacting a reaction of an epoxy compound with (p-based) acrylic acid with a polycarboxylic acid or a polycarboxylic acid anhydride (referred to as having at least one or more ethylenic unsaturation) Bonded photopolymerizable monomer, (c) photopolymerization initiator, (D) colorant; characterized in that the weight ratio (A)/(B) of the component (4) to the component (8) is 20/80 to 9 〇 /1〇; a total of 1 part by weight of the component (A) and 2 parts by weight of the component (C); and a compound represented by the following formula (I) as a component (c) Photopolymerization initiator: [Chemical Formula 1]
8 316123D01 201142502 苯基或齒素原子取代）’碳數丨至20的烷基（可被丨個以上 羥基取代，且烷基鏈中間可具有丨個以上氧原子），碳數5 至8的環烷基，碳數2至2〇的烷醯基或苯甲醯基（可被碳 數1至6的烷基或苯基取代）；仏表示碳數2至12的烷醯 基(可被1個以上的鹵素原子或氰基取代），雙鍵與羰基非 呈共軛之碳數4至6的烯醯基，苯甲醯基（可被碳數j至6 的烷基、齒素原子或氰基取代碳數2至6的烷氧基羰基 或苯氧基羰基（可被1個以上碳數1至6的烷基或鹵素原子 取代）；R3、R4、R5、r6、r7、r8、r9 及 Rig 相互獨立，各 表示氬原子，鹵素原子，碳數1至12的烷基，環戊基，環 己基，苯基，苯甲基，苯曱醯基，碳數2至12的烷醯基， 碳數2至12的烷氧基羰基(烷氧基的碳數為2至u的情 況，主鏈碳原子間可具有1個以上氧原子，且可被1個以 上羥基取代）或苯氧基羰基。 本發明之彩色濾光片用感光性樹脂組成物中，具備有 衍生自雙酚類的2個縮水甘油醚基的環氧化合物為以下列 通式(II)所表示的環氧化合物： 【化學式2】8 316123D01 201142502 Substituted by phenyl or dentate atoms) 'Alkyl group having a carbon number of 20 to 20 (which may be substituted by more than one hydroxyl group and having more than one oxygen atom in the middle of the alkyl chain), a ring having 5 to 8 carbon atoms An alkyl group, an alkyl alkene group having a carbon number of 2 to 2 Å or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); 仏 represents an alkyl fluorenyl group having 2 to 12 carbon atoms (may be 1) More than one halogen atom or cyano group substituted), the double bond and the carbonyl group are not conjugated with an olefin group having 4 to 6 carbon atoms, a benzamyl group (a group having a carbon number of j to 6 or a dentate atom or a cyano group substituted with an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group (which may be substituted by one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom); R3, R4, R5, r6, r7, r8, R9 and Rig are independent of each other, each represents an argon atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoinyl group, and an alkane having 2 to 12 carbon atoms. Alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkoxy group is 2 to u, the main chain carbon atom may have one or more oxygen atoms and may be substituted by one or more hydroxyl groups) or benzene Oxycarbonyl group. In the photosensitive resin composition for a color filter of the present invention, the epoxy compound having two glycidyl ether groups derived from bisphenols is an epoxy compound represented by the following formula (II): 2】
9 316123D01 201142502 於通式（11)中’ R11及Ri2相互獨立’各表示氫原子， 碳數1至5的燒基或鹵素原子，· χ表示_c〇_，_s〇y， -C(CF3)2- ’ _Si(CH3)2- ’ _CH2_，-c(CH3)2_，_〇_，9 9·苟基 (fluorenyl)或不存在；n為〇至1〇的整數。 再者’本發明之彩色濾光片用感光性樹脂組成物中， 成份(C)光聚合起始劑為以下列通式(111)所表示的化合物： 【化學式3】9 316123D01 201142502 In the general formula (11), 'R11 and Ri2 are independent of each other' each represents a hydrogen atom, a burning group or a halogen atom having 1 to 5 carbon atoms, and χ represents _c〇_, _s〇y, -C(CF3) ) 2- ' _Si(CH3)2- ' _CH2_, -c(CH3)2_, _〇_, 9 9 · fluorenyl or non-existent; n is an integer from 〇 to 1〇. In the photosensitive resin composition for a color filter of the present invention, the component (C) photopolymerization initiator is a compound represented by the following formula (111): [Chemical Formula 3]
此外’本發明之彩色濾光片用感光性樹脂組成物中， 成伤（D)著色劑為遮光性分散顏料。再者，本發明之彩色渡 光片用感光性樹脂組成物中，遮光性分散顏料為碳黑分散 體。此外，本發明為使上述彩色濾光片用感光性樹脂組成 物硬化而形成之塗膜。再者，本發明為彩色濾光片，其具 備藉由於透明基板上塗佈上述彩色濾光片用感光性樹脂組 成物，刖烘烤之後，以紫外線曝光裝置進行曝光，用驗性 水溶液進行顯像，以及進行後烘烤而製作出之晝素或是黑 色矩陣（black matrix)。 以下詳細說明本發明。本發明的彩色濾光片用感光性 樹脂組成物（以下亦僅稱為組成物），乃以（A)至（D)成份為 必須成份’關於(B)成份及（D)成份及因應必要所加入的溶 316123D01Further, in the photosensitive resin composition for a color filter of the present invention, the wound (D) coloring agent is a light-shielding dispersible pigment. Further, in the photosensitive resin composition for a color light-emitting sheet of the present invention, the light-shielding dispersible pigment is a carbon black dispersion. Further, the present invention is a coating film formed by curing the above-mentioned color filter with a photosensitive resin composition. Furthermore, the present invention is a color filter comprising a photosensitive resin composition for applying the color filter on a transparent substrate, baked, exposed to an ultraviolet exposure apparatus, and exposed to an aqueous solution. Like, and post-baking to make a halogen or black matrix. The invention is described in detail below. The photosensitive resin composition for a color filter of the present invention (hereinafter also referred to simply as a composition) is characterized in that (A) to (D) are essential components (in terms of (B) component and (D) component and necessary The added solution 316123D01
S 10 201142502 劑及其他成份記載於專利文獻1至6中，可從其中加以選 擇使用。因此，簡單說明（A)成份及（C)成份之外的成份， 並詳細說明（A)成份及(C)成份。 (A)成份之含不飽和基的化合物，乃藉由（曱基）丙稀酸 (此意味丙稀酸及/或甲基丙烯酸），與具有衍生自雙齡類的 2個縮水甘油醚基的環氧化合物進行反應，然後將所獲得 之具羥基(hydroxy)的化合物與多元羧酸或多元羧酸酐進 行反應’而獲得環氧（甲基）丙烯酸醋加成物。該加成物的 化學式及製法的一例，記載於專利文獻6。所謂衍生自雙 盼類的環氧化合物係指使雙酚類與表鹵醇(epihal〇hydrin) 反應所獲得的環氧化合物或是與環氧化合物同等的化合 物。由於為（A)成份之含不飽和基的化合物同時具有烯性不 &和雙鍵及幾基’因此可賦予彩色濾光片用感光性樹脂組 成物優良的光硬化性、良好顯像性、圖案特性，並提升遮 光模的物性。 (A)成份’即含不飽和基的化合物，較佳衍生自通式（II) 所表不的環氧化合物。此環氧化合物衍生自雙酚類。由於 曰由說明雙盼類可明瞭含不飽和基的化合物，因此藉由雙 2類來說明較佳具體例。於通式(II)中，Ru及R12相互獨 各表不氫原子，碳數1至5的烷基或是鹵素原子，X 表示-CO-，en ^ 〇 〜2、’ -C(CF3)2-，-Si(CH3)2-，-CH2-，-C(CH3)2-， 9’9_苟基或是不存在，以9,9-芴基為較佳。n為〇至 0的整數，作I > 足較佳為0或是平均值在0至2之間的範圍。 此’ 9,9·苟基是指以下列化學式所表示的基。 11 316123D01 201142502 【化學式4】The agent and other components of S 10 201142502 are described in Patent Documents 1 to 6, and can be selectively used therefrom. Therefore, the components other than the components (A) and (C) will be briefly described, and the components (A) and (C) will be described in detail. The unsaturated group-containing compound of (A) is obtained by (mercapto)acrylic acid (this means acrylic acid and/or methacrylic acid) and having two glycidyl ether groups derived from the double age class. The epoxy compound is reacted, and then the obtained hydroxy compound is reacted with a polyvalent carboxylic acid or a polycarboxylic acid anhydride to obtain an epoxy (meth) acrylate acetal addition product. An example of the chemical formula and the production method of the adduct is described in Patent Document 6. The epoxy compound derived from the expectant type means an epoxy compound obtained by reacting a bisphenol with an epihalolhydrin or a compound equivalent to an epoxy compound. Since the unsaturated group-containing compound of the component (A) has both an olefinic group and a double bond and a plurality of groups, it can impart excellent photocurability and good developability to a photosensitive resin composition for a color filter. , pattern characteristics, and improve the physical properties of the shading mold. The component (A), i.e., the compound containing an unsaturated group, is preferably derived from an epoxy compound represented by the formula (II). This epoxy compound is derived from bisphenols. Since the compound containing an unsaturated group is clarified by the description of the double-anticipation type, a preferred specific example will be described by the double class. In the formula (II), Ru and R12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents -CO-, en ^ 〇 〜2, '-C(CF3) 2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, 9'9-fluorenyl or absent, preferably 9,9-fluorenyl. n is an integer from 〇 to 0, and I > is preferably 0 or an average value between 0 and 2. This '9,9· fluorenyl group means a group represented by the following chemical formula. 11 316123D01 201142502 [Chemical Formula 4]
做為供應較理想的含不飽和基的化合物之雙酚類，有 下列化合物。包含，雙(4-羥基苯基）酮、雙(4-羥基-3,5-二 曱基苯基）酮、雙(4-羥基-3,5-二氯苯基）酮、雙(4-羥基苯基) 楓、雙(4-羥基-3,5-二曱基苯基)楓、雙(4-羥基-3,5-二氯苯 基)楓、雙(4-羥基苯基）六氟丙烷、雙(4-羥基-3,5-二甲基苯 基）六氟丙烷、雙(4-羥基-3,5-二氯苯基）六氟丙烷、雙(4-羥 基苯基)二甲基矽烷、雙(4-羥基-3,5-二甲基苯基）二曱基矽 烷、雙(4-羥基-3,5-二氯苯基）二甲基矽烷、雙(4-羥基苯基) 甲烷、雙(4-羥基_3,5_二氯苯基）甲烷、雙(4-羥基-3,5-二溴 笨基）曱烷、2,2-雙(4-羥基苯基）丙烷、2,2-雙（4-羥基-3,5-二甲基苯基）丙烷、2,2-雙(4-羥基-3,5-二氯苯基）丙烷、2,2-雙(4-羥基-3-甲基苯基）丙烷、2,2-雙(4-羥基-3-氯苯基）丙 烷、雙(4-羥基苯基)醚、雙(4-羥基-3,5-二甲基苯基）醚、雙 (4-羥基-3,5-二氯苯基）醚等化合物；及X為上述的9,9-芴 基之9,9-雙(4-羥基苯基）芴、9,9-雙(4-羥基-3-甲基苯基） 芴、9,9-雙(4-羥基-3-氯苯基）芴、9,9-雙(4-羥基-3-溴苯基） 芴、9,9-雙(4-羥基-3-氟苯基）芴、9,9-雙(4-羥基-3-曱氧基苯 基）芴、9,9-雙(4-羥基-3,5-二甲基苯基）芴、9,9-雙(4-羥基 -3,5-二氯苯基）芴、9,9-雙(4-羥基-3,5-二溴苯基）芴等，此 12 316123D01 201142502 外，亦可舉出4,4’-雙酚類及3,3’-雙酚類等。 此含不飽和基的化合物’雖可由上述衍生自雙盼類的 環氧化合物獲得，但亦可使用除了含有該環氧化人彳勿< 外’亦含顯著量紛系紛路樹脂型環氧化合物及甲紛$紛^ 樹脂型（Cresylic Novolak)環氧化合物等具有2個縮水甘、，由 醚基的化合物。此外，將雙酚類予以縮水甘油鱗化之際: 若以寡聚物單位混入，即通式(π)中的η的平均值為〇τ'至 10(以0至2為較佳）’則本樹脂組成物的功能將無任何問 題。 此外，與「環氧化合物與（甲基）丙烯酸反應所獲得之 (曱基）丙烯酸環氧酯之羥基」反應之多元羧酸或多元緩酸 酐’例如有，順丁烯二酸、琥珀酸、衣康酸、苯二曱酸、 四氫苯二甲酸（tetrahydrophthalic acid)、六氫笨二曱酸 (hexahydrophthalic acid)、甲基内亞曱基四氫苯二曱酸 (methylendomethylene tetrahydrophthalic acid)，六氯内亞- 曱基四氫苯二甲酸(chlorendic acid)、甲基四氫苯二甲酸 (methyl tetrahydrophthalic acid)、偏苯三曱酸（trimellitic acid)’苯均四甲酸(pyromelliticAcid)等，及這些化合物的 酸針類，再者，一本甲闺四緩酸（benzophenone tetracarboxylic acid)、聚苯四羧酸、二苯醚四羧酸 (diphenylether tetracarboxylic acid)等芳香族多元竣酸及這 些酸的二酸酐類等。關於酸酐類及二酸酐類的使用比例， 可選擇適於在因鹼性液顯像操作時形成精密圖案之比例。 關於(A)成份之含不飽和基的化合物，可僅使用丨種， 13 316123D01 201142502 或是可使用2種以上的混合物。此外，使環氧化合物與（曱 基）丙烯酸反應，獲得的（中基）丙烯酸環氧酯與多元叛酸或 多元叛酸酐類反應，以製造(A)成份的含不飽和基的化合物 的方法’無特別限定，例如可採用下列方法製造。亦即， 首先使9,9-雙⑷經基苯基）芴與表氯醇(epichlorohydrin)反 應’合成以下列通式(IV)所表示的雙齡芴型環氧化合物， 然後使該通式(IV)表示的雙酚芴型環氧化合物與下列通式 (V)表示的（甲基）丙烯酸進行反應，獲得以下列通式（VI)表 承的丙烯酸雙酚芴型環氧酯，接下來於丙二醇單甲醚溶劑 笮，於加熱之下使通式(VI)表示的丙烯酸雙酚芴型環氧酯 樹脂，與上述多元羧酸或多元羧酸的酸酐類進行反應，而 製造出為目標之含不飽和基的化合物。於通式（IV)至(VI) 中，R11及R12與上述相同，R13為Η或CH3。 f牝學式5】As the bisphenol which supplies a preferable unsaturated group-containing compound, the following compounds are available. Containing, bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimercaptophenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis (4) -hydroxyphenyl) maple, bis(4-hydroxy-3,5-dimercaptophenyl) maple, bis(4-hydroxy-3,5-dichlorophenyl) maple, bis(4-hydroxyphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl) ) dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)didecyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis (4) -hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)decane, 2,2-bis(4- Hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2 , 2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4- a compound such as hydroxy-3,5-dimethylphenyl)ether or bis(4-hydroxy-3,5-dichlorophenyl)ether; and X is the above 9,9-fluorenyl 9,9-double (4-hydroxyphenyl)anthracene, 9,9 - bis(4-hydroxy-3-methylphenyl)indole, 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl) Ruthenium, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3-indolylphenyl)anthracene, 9,9-bis(4-hydroxy- 3,5-Dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromobenzene Base, 芴, etc., 12 316123D01 201142502 In addition, 4,4'-bisphenols and 3,3'-bisphenols are also mentioned. The unsaturated group-containing compound can be obtained from the epoxy compound derived from the above-mentioned dipoxide type, but can also be used in addition to the epoxidized human 彳 外 外 外 外 外 亦 亦 亦 亦 亦 亦Compounds and a variety of compounds, such as a resin-based (Cresylic Novolak) epoxy compound, have two glycosides and are ether-based compounds. Further, when bisphenols are subjected to glycidal squaring: if mixed in an oligomer unit, the average value of η in the general formula (π) is 〇τ' to 10 (preferably 0 to 2)' Then the function of the resin composition will be without any problem. Further, a polycarboxylic acid or a polybasic acid anhydride which reacts with "the hydroxyl group of the (meth)acrylic acid epoxy ester obtained by the reaction of the epoxy compound with (meth)acrylic acid", for example, maleic acid, succinic acid, Itaconic acid, benzoic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylene tetrahydrophthalic acid, hexachloro Neil-chlorinic acid, methyl tetrahydrophthalic acid, trimellitic acid, pyromellitic Acid, etc., and these compounds Acid needles, in addition, an aromatic polybasic acid such as benzophenone tetracarboxylic acid, polyphenylenetetracarboxylic acid, diphenyl ether tetracarboxylic acid, and dianhydride of these acids Classes, etc. Regarding the ratio of use of the acid anhydrides and the dianhydrides, a ratio suitable for forming a precise pattern upon operation by alkaline liquid development may be selected. As the unsaturated group-containing compound of the component (A), only hydrazine species, 13 316 123 D01 201142502 or a mixture of two or more kinds may be used. Further, a method of reacting an epoxy compound with (mercapto)acrylic acid, and reacting the obtained (intermediate) acrylate epoxy ester with a polyholeic acid or a polyhectoric anhydride to produce an unsaturated group-containing compound of the component (A) 'There is no particular limitation, and for example, it can be produced by the following method. That is, first, 9,9-bis(4)-p-phenylphenyl)anthracene is reacted with epichlorohydrin to synthesize a two-year-old oxime-type epoxy compound represented by the following general formula (IV), and then the general formula is made. The bisphenol fluorene type epoxy compound represented by (IV) is reacted with (meth)acrylic acid represented by the following general formula (V) to obtain an bisphenol fluorene type epoxy ester which is represented by the following general formula (VI), The bisphenol oxime epoxy ester resin represented by the formula (VI) is reacted with an acid anhydride of the above polycarboxylic acid or polycarboxylic acid under heating in a solvent of propylene glycol monomethyl ether solvent to produce The target unsaturated group-containing compound. In the general formulae (IV) to (VI), R11 and R12 are the same as defined above, and R13 is hydrazine or CH3. f牝学5]
14 316123D01 201142502 就該反應而言’較佳以環氧丙烯醆酯樹脂的OH基1 莫耳與酸酐類I/2莫耳進行定量反應為佳，反應溫度以90 °c至i3〇°c為較佳’以95°c至125°c為更佳。於此反應當 中，關於具備通式（I)的早位構造的化合物，全體均相同。 做為（B)成份之具有至少1個以上乙烯性不飽和鍵結 之光聚合性單體’例如有，（甲基）丙烯酸2-羥基乙酯、（甲 基）丙烯酸2-羥基丙酯、（曱基）丙烯酸2-乙基己酯等具備經 基的單體；及乙二醇一（甲基）丙稀'酸酿、二乙二醇二（甲基） 丙烯酸酯、三乙二醇二（曱基）丙烯酸酯、四乙二醇二（甲基） 丙烯酸酯、1，4-丁二醇二（曱基）丙烯醆酯、三羥甲基丙烷 (trimethylol propane)三（曱基）丙稀酸酯、三經甲基乙燒三 (曱基）丙烯酸酯、季戊四醇二（曱基）丙埽酸醋、季戊四醇三 (甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、季戊四醇四 (甲基）丙烯酸酯、雙季戊四醇六（甲基）丙烯酸酯、甘油 (glycerol)(甲基）丙烯酸酯等（甲基）丙烯酸酯類，這些化合物 可單獨採用1種，亦可併用2種以上。 這些（A)成份與（B)成份的重量調配比例（A)/(B)為 20/80至90/10，以40/60至80/20為較佳。（A)成份的調配 比例若少於20/80，由於光硬化後的硬化物容易變脆，且 未曝光部分中塗膜的酸價會降低，因此對鹼性顯像液的溶 解性會降低’使圖案輪廓產生鋸齒狀，而發生「不清晰」 的問題；此外，若多於90/10，由於光反應性官能基在樹 月a中所占的比例較少，無法形成足夠的交聯構造，且樹脂 成份中的酸價度將過高，曝光部份對鹼性顯像液的溶解性 316123D0114 316123D01 201142502 For the reaction, it is preferred to carry out quantitative reaction of OH group 1 molar of epoxy propylene acrylate resin with anhydride I/2 molar, and the reaction temperature is from 90 °c to i3〇°c. Preferably, it is more preferably from 95 ° C to 125 ° C. In the case of this reaction, the compounds having the early structure of the general formula (I) are all the same. The photopolymerizable monomer having at least one or more ethylenically unsaturated bonds as the component (B) is, for example, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. (mercapto) 2-ethylhexyl acrylate such as a monomer having a trans group; and ethylene glycol mono(methyl) propylene diacid, diethylene glycol di(meth) acrylate, triethylene glycol Di(indenyl) acrylate, tetraethylene glycol di(meth) acrylate, 1,4-butanediol bis(indenyl) propylene decyl ester, trimethylol propane tris(fluorenyl) Acrylate, trimethyl ethene tris(mercapto) acrylate, pentaerythritol di(indenyl) propionate vinegar, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, pentaerythritol IV A (meth) acrylate such as a (meth) acrylate, a dipentaerythritol hexa(meth) acrylate or a glycerol (meth) acrylate. These compounds may be used alone or in combination of two or more. . The weight ratio (A)/(B) of the component (A) to the component (B) is from 20/80 to 90/10, preferably from 40/60 to 80/20. (A) If the proportion of the components is less than 20/80, the cured product after photohardening tends to become brittle, and the acid value of the coating film in the unexposed portion is lowered, so the solubility in the alkaline developing solution is lowered. 'The pattern outline is jagged, and the problem of "unclear" occurs; in addition, if it is more than 90/10, since the photoreactive functional group accounts for a small proportion in the tree month a, sufficient cross-linking cannot be formed. Structure, and the acidity of the resin component will be too high, the solubility of the exposed part to the alkaline imaging solution 316123D01
S 15 201142502 會過高，因此使所形成的圖案線寬比希望的線寬度細，容 易產生圖案缺陷的問題。 做為（c)成份的光聚合起始劑，以上述通式⑴表示的化 合物做為必須成份，藉由紫外線光等的照射而產生自由基 (Radical) ’此等自由基與光聚合性的化合物進行加成反應 而引發自由基聚合，並硬化組成物。其中，於通式（I)中， Ri表示笨基（可被碳數1至6的烷基、苯基或鹵素原子取 代）’碳數1至20的烷基（可被1個以上羥基取代，烷基鏈 的中可具有1個以上的氧原子，亦可具有羥基與氧原子兩 者），碳數5至8的環烷基，碳數2至20的烷醯基或是苯 甲醯基（可被碳數1至6的烷基或苯基取代)。R2表示碳數 2至12的烷醯基（可被1個以上的鹵素原子或氰基取代）， 雙鏈與羰基非為共軛的碳數4至6的烷醯基、苯甲醯基(可 被碳數1至6的烧基、齒素原子或氰基取代），碳數2至6 的烷氧羰基或苯氧羰基(可被1個以上的碳數1至6的烧 基、苯基或鹵素原子取代），此等基總稱為醯基(acyl)。R3、 R4、R5、Re、R7、R8、R9及Ri〇相互獨立，各表示氫原子， 鹵素原子’碳數1至12的烧基’環戊基，環己基，苯基， 苯曱基，苯甲醯基，碳數2至12的烷醯基，碳數2至12 的烧氧基数基(烧氧基的破數為2至11的情況，該烧氧基 (於主鍵碳原子間可具有1個以上氧原子及/或被1個以上 羥基取代）或是苯氧基羰基。 該化合物的製造係參照專利文獻4記载的類似的化合 物的製造方法。於本發明中之以通式（I)表示的光聚合起始 316123D01 16 201142502 劑中，以上述通式(m)表示的化合物為較佳。 此外，於本發明中，可與通式(1)表示的光聚合起始劑 可與1種以上的其他光聚合起始劑或是感光劑（Sensitizer) 併用。上述其他光聚合起始劑或是感光劑，例如有，苯乙 酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二曱基胺 基苯丙g同、二氯苯乙酮、三氣苯乙酮、對_第三丁基苯乙酮 等本乙嗣類，及一本曱嗣（benzophenone)、2-氯二苯甲嗣、 p，p’-雙二甲基胺基二苯甲酮等二苯甲酮類；苯偶醯 (benzil);苯偶因（benz〇in)、苯偶因曱基醚、苯偶因異丙基 醚、苯偶因異丁基醚等苯偶因醚類；2_(鄰氣苯基>4,5_二 苯基聯嘧唑（2-(o-chlorophenyl)-4,5-diplienylbiimidazole)、 2-(鄰氯苯基)-4,5-二（間曱氧基苯基）聯嘧嗤、2_(鄰氟苯 基)-4,5-二苯基聯嘧唑、2-(鄰甲氧基苯基)_4,5-二苯基聯嘧 σ坐、2,4,5-二方香基聯π密n坐等聯嘴0坐系列化合物，三氯曱 基-5-苯乙烯基-1，3,4-噁二唑、2_三氯甲基_5-(對氰基苯乙烯 基）-1，3,4-嗯二嗤、2-三氣甲基_5_(對甲氧基苯乙烯 基）-1，3,4-β惡一嗤等鹵甲基。坐化合物類；2,4,6-三（三氯甲 基）-1，3,5-三畊、2，-甲基-4,6-雙（三氯甲基）_1,3,5_三畊、2,-苯基-4,6-雙(三氯曱基)-l，3,5-三畊、2-(4-氯苯基)-4,6-雙（三 氯甲基）-1，3,5-三畊、2-(4-甲氧基苯基）_4,6-雙（三氯甲 基;Μ，3,5-三畊、2·(4-甲氧基萘基)-4,6-雙（三氯f基)-1，3,5-三D并、2-(4-甲氧基苯乙烯基）_4,6_雙（三氯甲基） 哄、2·(3,4,5-三甲氧基苯乙烯基)_4,6_雙（三氯甲基） 三Π并、2-(4-曱基硫苯乙烯基)_4,6-雙（三氯甲基)_1，3,5_三畊 17 316123D01 201142502 等鹵甲基-S-三畊系列化合物類；1-[4-(苯硫基）苯基]-2-(〇-苯甲醯肟)-辛-1，2-二酮、1-(4-苯硫基苯基）丁-1，2-二酮-2-fc-O-笨曱酸酉旨（l-(4-phenylsulfanylphenyl)butane-l,2-dione -2-oxime-O-benzoate)、1-(4-甲硫基苯基）丁-1,2-二酮-2-月弓 -Ο-乙酸酯、1-(4-曱硫基苯基）丁-1-酮肟-〇_乙酸酯等上述通 式(I)未包含的範圍中之0-醯基肟系列化合物類；二甲醇縮 苯甲酮（benzyl dimethyl ketal);硫灿酮（thioxanthone)、2- 氣硫qjj嗣、2,4-二乙基硫酮、2-甲基硫灿酮、2-異丙基 硫灿酮等硫化合物；2-乙基蒽醌、八甲基蒽醌、ι，2-苯并 蒽醌、2,3-二苯基蒽醌等蒽醌類；偶氮雙異丁腈（az〇 bis-isobutylnitrile)、苯甲醯過氧化物、異丙苯（cumene)過 氧化物等有機過氧化物；2-硫醇基苯并咪唑、2-硫醇基苯 并噁吐、2-硫醇基苯并噻唑等硫醇化合物等。 這些光聚合起始劑或是感光劑，可採用單獨1種，亦 可併用2種以上。此外，可以添加本身雖無光聚合起始劑 或是感光劑之作用，但可藉由與上述化合物的組合，而可 增加光聚合起始劑或是感光劑能力的化合物。此等化合 物，例如為若與二笨甲酮組合使用將可發揮效果的三乙醇 胺等三級胺。 成伤（C)光聚合起始劑的使用量，若是以（a)成份與(b) 成份合計100重量份為基準，則較佳為2至3〇的重量份， 更佳為5至20的重量份。若（〇成份的添加比例未滿2， 則光聚合的速度變慢且感度降低，另一方面，若超過3〇 重量份’則感度過強，圖案線寬將比圖案光罩寬，而無法 316123D01 18 201142502 忠實地重現光罩的線寬，此外，圖案輪糕鑛齒狀，恐產 生不清晰的_。成份(Q光聚合起始劑以通式(1)所表示的 光聚合起始劑為必需成份，其之用量，於未添加其他⑹ 成份時，只要在可單獨發揮光聚合起始劑之作用之量以上 即可，該劑量，以⑷絲與⑻成份合計丨⑻重 準時，較佳為2至30重量份，更佳為3至15重量份。土 成份(D)著色劑之色調並未特別限定，可依彩色濾光片 的用途而適當的選定，顏料染料及天然色素均可。=於彩 色濾、光片要求尚精密的顏色顯現及耐熱性，因此一般乃採 用顏料，尤其較為理想者為採用有機顏料及碳黑。關於上 述有機顏料，就紅色顏料言之，可採用單一的紅色顏料系 列，亦可於紅色顏料系列之中混合黃色顏料系列來進行調 色。關於紅色顏料’例如有蒽醒(anthraquinone)系列顏料、 喹吖啶酮系列顏料，二酮基吡咯系列顏料、芘（perylene) 系列顏料等’以二酮吡咯并吡咯紅(Diketo Pyrrolo Pyrr〇le Red)(C.I.顏料紅254)及蒽醌紅（c.I.顏料紅177)等為尤佳。 此外，關於黃色的顏料，例如有，異吲哚啉黃(Is〇ind〇lineS 15 201142502 will be too high, so that the formed pattern line width is thinner than the desired line width, and the problem of pattern defects is easily generated. As a photopolymerization initiator of the component (c), a compound represented by the above formula (1) is used as an essential component, and radicals are generated by irradiation of ultraviolet light or the like. [The radicals and photopolymerizable substances. The compound undergoes an addition reaction to initiate radical polymerization and hardens the composition. Wherein, in the formula (I), Ri represents a styl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) and an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups) , the alkyl chain may have more than one oxygen atom, may also have both a hydroxyl group and an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or benzamidine A group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group). R2 represents an alkanoyl group having 2 to 12 carbon atoms (which may be substituted by one or more halogen atoms or a cyano group), a double-chain carbonyl group having 4 to 6 carbon atoms which is not conjugated with a carbonyl group, and a benzamidine group ( It may be substituted by a calcining group having 1 to 6 carbon atoms, a dentate atom or a cyano group, an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group (a calcined group or a benzene having 1 or more carbon atoms of 1 to 6) Substituted by a halogen atom or a halogen atom, these groups are collectively referred to as acyl. R3, R4, R5, Re, R7, R8, R9 and Ri〇 are independent of each other, each represents a hydrogen atom, a halogen atom 'alkyl 1 to 12 alkyl' cyclopentyl, cyclohexyl, phenyl, phenyl fluorenyl, a benzamidine group, an alkanoyl group having 2 to 12 carbon atoms, and an alkoxy group having 2 to 12 carbon atoms (in the case where the number of alkyloxy groups is 2 to 11, the alkoxy group (between the primary bond carbon atoms) The method of producing a compound similar to that described in Patent Document 4 is a method for producing a compound having one or more oxygen atoms and/or substituted by one or more hydroxyl groups or a phenoxycarbonyl group. In the present invention, a photopolymerization initiator represented by the above formula (1) is preferred. In the present invention, a photopolymerization initiator represented by the formula (1) is preferred. It can be used in combination with one or more other photopolymerization initiators or sensitizers. The above other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxybenzene Ketone, p-dimethylacetophenone, p-didecylamino phenylpropanol, dichloroacetophenone, tri-o-acetophenone, p-tert-butylacetophenone The acetoxime, and a benzophenone, 2-chlorobenzhydryl, p,p'-bisdimethylaminobenzophenone, etc.; benzoin (benzil) ; Benzene (benz〇in), benzoin decyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2_ (o-phenyl group> 4,5 2-(o-chlorophenyl)-4,5-diplienylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-decyloxyphenyl)-pyrimidine, 2_ (o-fluorophenyl)-4,5-diphenyl thiazolidine, 2-(o-methoxyphenyl)_4,5-diphenylbipyridinium, 2,4,5-diaryl π密n sits in a series of compounds, chloroformyl-5-styryl-1,3,4-oxadiazole, 2_trichloromethyl_5-(p-cyanostyryl)-1 , 3,4- 嗤 嗤, 2-trimethylmethyl _5_(p-methoxystyryl)-1,3,4-β oxime and the like halomethyl. Sit compound; 2, 4, 6-tris(trichloromethyl)-1,3,5-three tillage, 2,-methyl-4,6-bis(trichloromethyl)_1,3,5_three tillage, 2,-phenyl -4,6-bis(trichloroindenyl)-l,3,5-three tillage, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5- Three tillage, 2-(4-A Phenyl)_4,6-bis(trichloromethyl; anthracene, 3,5-three tillage, 2·(4-methoxynaphthyl)-4,6-bis(trichlorofyl)-1, 3,5-tri-D,2-(4-methoxystyryl)_4,6-bis(trichloromethyl)anthracene, 2·(3,4,5-trimethoxystyryl)_4 ,6_bis(trichloromethyl)triazino,2-(4-mercaptothiostyryl)_4,6-bis(trichloromethyl)_1,3,5_three tillage 17 316123D01 201142502 Methyl-S-three-plowed series of compounds; 1-[4-(phenylthio)phenyl]-2-(anthracene-benzoic acid)-octane-1,2-dione, 1-(4- Benzylthiophenyl)butane-1,2-dione-2-fc-O-l-(4-phenylsulfanylphenylbutane-l,2-dione-2-oxime-O-benzoate) , 1-(4-methylthiophenyl)butane-1,2-dione-2-monthly-purine-acetate, 1-(4-sulfonylphenyl)butan-1-one oxime- 0-acetate or the like in the range not included in the above formula (I); 0-fluorenyl hydrazine series; benzyl dimethyl ketal; thioxanthone, 2-sulfur Sulfur compounds such as qjj嗣, 2,4-diethylthione, 2-methylthioketone, 2-isopropylthioketone; 2-ethyl hydrazine, octamethyl hydrazine, ι, 2- Benzopyrene Anthraquinones such as 2,3-diphenylfluorene; azobisbisisobutyronitrile, benzamidine peroxide, cumene peroxide and other organic peroxides a thiol compound such as 2-thiol benzimidazole, 2-thiol benzoxepide or 2-thiol benzothiazole. These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. Further, a compound which does not have a photopolymerization initiator or a sensitizer, but which can increase the photopolymerization initiator or the sensitizer ability by a combination with the above compound can be added. These compounds are, for example, tertiary amines such as triethanolamine which are effective when used in combination with dimercaptoketone. The amount of the photoinitiator (C) photopolymerization initiator to be used is preferably from 2 to 3 parts by weight, more preferably from 5 to 20, based on 100 parts by weight of the total of the component (a) and the component (b). Parts by weight. If (the addition ratio of the bismuth component is less than 2, the speed of photopolymerization becomes slower and the sensitivity is lowered. On the other hand, if it exceeds 3 Å by weight, the sensitivity is too strong, and the pattern line width is wider than the pattern mask, and it is impossible to 316123D01 18 201142502 faithfully reproduces the line width of the reticle. In addition, the pattern of the ring is toothy, which may cause unclear _. The composition (the photopolymerization initiator represented by the general formula (1)) The agent is an essential component, and the amount thereof is not more than the amount of the photopolymerization initiator which can be used alone when the other component (6) is not added, and the dose is based on the total amount of (4) silk and (8) component (8). It is preferably 2 to 30 parts by weight, more preferably 3 to 15 parts by weight. The color tone of the earth component (D) coloring agent is not particularly limited, and may be appropriately selected depending on the use of the color filter, pigment dyes and natural pigments. Yes. = Color filter and light film require precise color display and heat resistance. Therefore, pigments are generally used. Especially, organic pigments and carbon black are used. Regarding the above organic pigments, the red pigments can be said. Use a single red color The series can also be mixed with the yellow pigment series in the red pigment series. For the red pigments, for example, anthraquinone series pigments, quinacridone series pigments, diketopipole series pigments, perylene (perylene) A series of pigments such as Diketo Pyrrolo Pyrr〇le Red (CI Pigment Red 254) and Eosin (cI Pigment Red 177) are preferred. ,isoporphyrin yellow (Is〇ind〇line
Yellow)(C.I.顏料黃 139)、錄偶氮黃(Nickel Azo Yell〇w)(C,I. 顏料黃150)、雙芳香醯笨胺黃(Diaryiide Yell〇w)(c.l.顏料 黃83)等。這些紅色顏料系列及黃色顏料系列各可混合2 種以上來使用。此外’於混合使用紅色顏料系列及黃色顏 料系列的情況，相對於紅色顏料系列與黃色顏料系列的總 量100重量份’黃色顏料系列以為90重量份以下為較佳。 關於綠色的顏料可採用單一的綠色顏料系列，亦可混合黃Yellow) (C.I. Pigment Yellow 139), Nickel Azo Yell〇w (C, I. Pigment Yellow 150), Diaryiide Yell〇w (c.l. Pigment Yellow 83), and the like. These red pigment series and yellow pigment series can be used in combination of two or more. Further, in the case of mixing the red pigment series and the yellow pigment series, it is preferably 90 parts by weight or less with respect to 100 parts by weight of the total amount of the red pigment series and the yellow pigment series. For green pigments, a single green pigment series can be used, or yellow can be mixed.
19 316123D01 S 201142502 色顏料系列於綠色顏料系列之令來進行調色。闕於綠色的 顏料，例如有，氯倾菁綠㈣，祕al〇cyanineg職)顏 料(C.I.顏料綠7)、演化酞綠顏料(C I顏料綠％)等。此外， 關於黃色的顏料’例如有異鴨啉黃(CI.顏料黃139)、雙 芳香醯苯胺黃(C.L顏料黃幻)等。這些綠色顏料系列及黃 色顏料系列各可混合2種以上來使用。此外，於混合使用 綠色顏料系列及黃色顏料系列而使用的情況，相對於綠色 顏料系列與黃色顏料系列的總量為100重量份，黃色顏料 系列較佳為90重量份以下。關於藍色的顏料可採用單一的 藍色顏料系列’亦可混合紫色㈣㈣於藍色顏料系列之 中來進行調色。關於藍色的顏料，例如有，酞菁系列顏料、 陰丹士林(Indamhrene)系列顏料等，尤其是較為理想者為 £ 型酞菁藍（Phthalocyanine Blue)顏料（C.I.顏料藍 15 : 〇 等。此外，關於紫色的顏料，例如有，二噁啡紫 Vi〇let)(C.I.顏料紫23) ’這些藍色顏料系列及紫色顏料系列 各可混合2種以上來使用。此外，於混合使用藍色顏料系 列及紫色顏料系列的情況，相對於藍色顏料系列及紫色顏 料系列的總量100重量份，紫色顏料系列的重量份為9〇 以下。 此外，關於遮光性分散顏料例如有黑色有機顏料、混 色有機顏料或是遮光材料等，關於黑色有機顏料，例如有 祐黑、花青素(cyanine)黑等。關於黑色有機顏料，例如可 從紅、藍、綠、紫、黃、花青素、洋紅(magenta)當中採用 2種以上的顏料來混而而成為近似黑色者。關於遮光材19 316123D01 S 201142502 The color pigment series is toned in the green pigment series. For green pigments, for example, chlorophthalocyanine (four), secret 〇cyanineg (manufactured by C.I. Pigment Green 7), and evolved 酞 green pigment (% of C I pigment green). Further, the pigment "yellow yellow" is, for example, iso-limbolin yellow (CI. Pigment Yellow 139), di-arylene anilide yellow (C.L pigment yellow illusion), and the like. These green pigment series and yellow pigment series can be used in combination of two or more. Further, when the green pigment series and the yellow pigment series are used in combination, the total amount of the green pigment series and the yellow pigment series is 100 parts by weight, and the yellow pigment series is preferably 90 parts by weight or less. For the blue pigment, a single blue pigment series can be used, and purple (4) and (4) can be mixed to color the blue pigment series. Examples of the blue pigment include, for example, a phthalocyanine series pigment, an Indamhrene series pigment, and the like, and particularly preferably a Phthalocyanine Blue pigment (CI Pigment Blue 15: 〇, etc.). In addition, as for the pigment of the purple color, for example, dioxin violet Vi〇let (CI Pigment Violet 23) 'These blue pigment series and the purple pigment series can be used in combination of two or more types. Further, in the case of mixing the blue pigment series and the violet pigment series, the weight ratio of the purple pigment series is 9 Å or less with respect to 100 parts by weight of the total of the blue pigment series and the purple pigment series. Further, the light-shielding dispersible pigment may be, for example, a black organic pigment, a mixed organic pigment or a light-shielding material, and the black organic pigment may, for example, be black or cyanine black. For the black organic pigment, for example, red, blue, green, purple, yellow, anthocyanin, and magenta may be used in a mixture of two or more kinds of pigments to form a black color. About shading materials
Si 316123D01 20 201142502 料’例如有，碳黑、氧化鉻、氧化鐵、鈦黑、苯胺(Aniline) 黑、花青素黑等，亦可適當地選擇2種以上來採用，在這 當中，較為理想者為具備良好的遮光性，表面平滑性及分 散安定性且與樹脂具相容性(compatability)之碳黑。 此外，著色劑視需要，可與分散劑合用。關於此等分 散劑，例如有陽離子系列、.陰離子系列、非離子系列、兩 性系列、矽酮系列、氟系列等界面活性劑。關於上述界面 活性劑的具體例，例如有聚氧伸乙基十二烷基醚、聚氧伸 乙基硬脂基醚等聚氧伸乙基院基喊。 本發明中之成份(D)的色素的使用量，若是以(A)成份 與(B)成份合計1〇〇重量份為基準，則以3〇至280重量份 為較佳，以50至230重量份為更佳。若未滿30重量份， 則不具足夠的顏色純度及遮光性，為了獲得所希望的對比 而必須增加膜厚’因而難以獲得具備平滑面的彩色濾光 片’相對的，若超過280重量份，則包含(D)成份的彩色濾 光片用感光性樹脂組成物的分散安定性下降，此外，由於 原先做為恭結劑的感光性樹脂的含量降低，因此可能產生 可能損及顯像特性並可能損及膜形成能力之問題。 於本發明的彩色濾光片用感光性樹脂組成物當中，較 理想除了上述(A)至(D)成份之外，亦採用溶劑。關於溶劑， 例如有，甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇 等醇類’ α •或是;5-松油醇(terpineol)等Jg類(terpene)、丙 酮、丁鲖、環己酮、N-甲基·2_吡咯烷酮 (N-Methyl-2-Pyrr〇iid〇ne)等嗣類；曱苯、二曱苯、四甲基 21 316123D01 201142502 本·#方香族破虱化合物類；赛路素（cell〇s〇lve)、乙二醇單 甲醚(methyl cellosolve)、乙二醇單乙醚(ethyl cell〇s〇lve)、 卡必醇(carbitol)、甲基卡必醇、乙基卡必醇、丁基卡必醇、 丙二醇單曱基鱗、丙二醇單乙基驗、二丙二醇單甲基鱗、 二丙二醇單乙基醚、三丙二醇單甲基醚、三乙二醇單乙基 醚等二元醇醚類；醋酸乙酯、醋酸丁酯、乙二醇單醋酸酯 (Cellosolve Acetate)、乙二醇單乙醚單醋酸酯、乙二醇單丁 醚單醋酸酯、卡必醇醋酸酯、乙基卡必醇醋酸酯、丁基卡 必醇醋酸酯、丙二醇單曱基醚乙酸酯、丙二醇單乙基醚乙 酸酯等醋酸酯類，藉由溶解並混合這些化合物，.可製作均 一的溶液狀組成物。 此外’於本發明的彩色濾光片用感光性樹脂組成物 中，可視需要添加硬化促進劑、熱聚合禁止劑、可塑劑、 填充材料、勻染劑、消泡劑等添加劑。關於熱聚合禁止劑， 例如有對苯二紛(hydroquinone)、對苯二盼單甲基謎、焦掊 酚(pyrogallol)、第三級 丁基鄰苯二酚(tert_ butylcatech〇1)、 啡噻畊(Phenothiazine)等；關於可塑劑，例如有鄰苯二曱酸 二丁酯（dibutyl phthalate)、鄭苯二曱酸二辛酯（di〇ctyl phthalate)、甲齡混合物（tricres〇i，鄰甲酴、間甲酴及對甲 鹼之混合物）等；關於填充材，例如有玻璃纖維、石夕膠、雲 母、氧化鋁等；此外’關於消泡劑及勻染劑，例如有矽系 列、氟系列、丙埽酸系列化合物。 此外’本發明彩色濾光片用感光性樹脂組成物以上述 (A)至Φ)成份或者(A)至(D)成份與溶劑為主成份。於去除 22 316123D01 201142502 溶劑的固形成份中’（A)至(D)成份合計為70wt%以上，較 佳為80wt%以上，更佳為9〇wt%以上。溶劑的量乃因目標 黏度的不同而改變，較佳為2〇至8〇wt%。本發明的彩色Si 316123D01 20 201142502 The material 'for example, carbon black, chromium oxide, iron oxide, titanium black, aniline black, anthocyanin black, etc., may be appropriately selected from two or more types, and among them, it is preferable. It is a carbon black which has good light-shielding property, surface smoothness, dispersion stability, and compatability with a resin. Further, the coloring agent may be used in combination with a dispersing agent as needed. Examples of such dispersing agents include surfactants such as a cationic series, an anionic series, a nonionic series, an amphoteric series, an anthrone series, and a fluorine series. Specific examples of the above surfactants include polyoxyethylene ethyl lauryl ether and polyoxyethylene ethyl stearyl ether. The amount of the pigment of the component (D) in the present invention is preferably from 3 to 280 parts by weight, based on 1 part by weight based on the total of the components (A) and (B), and is preferably from 50 to 230. The parts by weight are more preferred. If it is less than 30 parts by weight, it does not have sufficient color purity and light-shielding property, and in order to obtain a desired contrast, it is necessary to increase the film thickness 'and thus it is difficult to obtain a color filter having a smooth surface, and if it exceeds 280 parts by weight, The dispersion stability of the photosensitive resin composition for the color filter containing the component (D) is lowered, and since the content of the photosensitive resin which is originally used as a bonding agent is lowered, there is a possibility that the development characteristics may be impaired and possible. The problem of damage to film formation ability. Among the photosensitive resin compositions for color filters of the present invention, it is preferred to use a solvent in addition to the above components (A) to (D). The solvent may, for example, be an alcohol such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol or propylene glycol, or a Jp (terpene), acetone or butyl, such as 5-terpineol. Anthraquinones such as anthracene, cyclohexanone and N-methyl-2-pyrrolidone (N-Methyl-2-Pyrr〇iid〇ne); anthracene, diphenyl, tetramethyl 21 316123D01 201142502 Ben·#方香族Breaking compounds; cell 〇s素lve, methyl cellosolve, ethylene glycol monoethyl ether (ethyl cell〇s〇lve), carbitol, methyl Carbitol, ethyl carbitol, butyl carbitol, propylene glycol monothiol scale, propylene glycol monoethylate, dipropylene glycol monomethyl scale, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, three Glycol ethers such as ethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoacetate (Cellosolve Acetate), ethylene glycol monoethyl ether monoacetate, ethylene glycol monobutyl ether monoacetic acid Ester, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate, etc. Esters, by mixing and dissolving these compounds may be prepared in a form of a solution each composition. Further, in the photosensitive resin composition for a color filter of the present invention, an additive such as a curing accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a leveling agent, or an antifoaming agent may be added as needed. Regarding thermal polymerization inhibitors, for example, hydroquinone, p-phenylene monomethyl mystery, pyrogallol, tert-butyl catechol (tert_butylcatech〇1), thiophene Phenothiazine, etc.; for plasticizers, for example, dibutyl phthalate, dioctyl phthalate, and a mixture of ages (tricres〇i, neighboring For the filler, for example, glass fiber, shijiao, mica, alumina, etc.; in addition, 'for defoamers and leveling agents, for example, bismuth series, fluorine Series, propionate series compounds. Further, the photosensitive resin composition for a color filter of the present invention contains the above components (A) to Φ or the components (A) to (D) and a solvent as a main component. In the solid content of the solvent of 22 316123D01 201142502, the total of the components (A) to (D) is 70% by weight or more, preferably 80% by weight or more, more preferably 9% by weight or more. The amount of the solvent varies depending on the target viscosity, and is preferably from 2 to 8 % by weight. Color of the invention
濾光片用感光性樹脂組成物雖適合用於黑色及R、G、B 用光阻層（油墨），但更適合用於黑色用光阻層（遮光用油 墨）。 接下來說明採用感光性樹脂組成物的彩色濾光片的 製造方法。首先，視需要，於基板表面上形成用於區隔形 成畫素之部分之遮光層，於此基板上塗佈例如分散有紅色 的顏料的感光性樹脂組成物的液狀組成物，之後進行前烘 烤使溶劑蒸發形成塗膜。接下來於此塗膜上通過光罩來曝 光’之後採用鹼性顯像液顯像，溶解以去除塗膜的未曝光 部分之後’藉由後烘烤，形成紅色晝素圖案按預定排列而 配置的晝素陣列（array)。之後，採用分散有綠色或藍色顏 料的感光性樹脂組成物的液狀組成物，進行與上述相同之 各個液狀組成物的塗佈、前烘烤、曝光、顯像及後烘烤， 以於同一基板上依序形成綠色的晝素陣列及藍色的晝素陣 列’藉此獲得紅色、綠色及藍色的晝素陣列被配置於基板 上的彩色濾光片。 於基板上塗佈感光性樹脂組成物的液狀組成物之 際’除了可採用眾所皆知的溶液浸泡法及喷灑法之外，亦 可採用依據滾輪塗佈機，圓盤塗佈機及旋床(spinner)之方 法等。根據這些方法，於塗佈所希望的厚度之後，去除溶 劑（前烘烤）而形成覆臈。前烘烤可藉由烤箱、加熱板等來 23 316123D01 201142502 進行。前’中的加熱溫度及加熱時間，可視所使用的溶 劑種類而適當選擇，例如於财12代的溫度 至1〇 分鐘。 關於製作彩色濾光片之際所使用的放射線，例如可使 用可見光紫外線、遠紫外線、電子束、X射線等，較佳 為波長250至45〇11111範圍内的放射線。此外，關於適用於 此驗性顯像的顯像液’例如錄金屬及驗土金屬之碳酸鹽 的水溶液，鹼金屬氫氧化物水溶液等，其中，以採用包含 〇5至10重量％的碳酸鈉、碳酸妈、碳酸裡等碳酸鹽之 弱鹼，水溶液，於20至30Ϊ下顯像為佳，並採用市面上 j販貝的顯像機及超音波洗淨機，而可精密的形成纖細的 像於驗性顯像之後，進行清洗。關於顯像處理法，例 如可適用沖淋顯像法、喷灑顯像法、浸泡（浸液）顯像法、 攪拌顯像法等。顯像條件較佳為於常溫下進行10至120 秒。 、如此顯像之後，可於180至250。(：的溫度及20至100 $鐘的條件下進行熱處理（後烘烤）。進行後烘烤的目的為 提升形成圖案後的塗膜與基板之間的密著性。後烘烤與前 、’、烤相同，可藉由烤箱、加熱板等來進行。本發明之形成 ，案後的塗膜，乃經由依據上述光微影(ph〇t〇lith〇graphy) 製程法之各個步驟而形成。 ^ 、此外，黑色矩陣(black matrix)可採用遮光感光性樹脂 、、且成物，並以與上述晝素陣列相同之方式形成。 形成具有晝素及/或黑色基質之彩色濾光片之際所使 316123D01The photosensitive resin composition for a filter is suitably used for a resistive layer (ink) for black and R, G, and B, but is more suitably used for a resist layer for black (an ink for light-shielding). Next, a method of producing a color filter using a photosensitive resin composition will be described. First, if necessary, a light-shielding layer for partitioning a pixel is formed on the surface of the substrate, and a liquid composition of a photosensitive resin composition in which a red pigment is dispersed is applied onto the substrate, and then performed. Baking causes the solvent to evaporate to form a coating film. Next, the film is exposed by a reticle on the coating film, and then imaged by an alkaline developing solution to dissolve the unexposed portion of the coating film. After the post-baking, the red phenolic pattern is arranged in a predetermined arrangement. Arbitrary array (array). Thereafter, the liquid composition of the photosensitive resin composition in which the green or blue pigment is dispersed is applied, and the same liquid composition as described above is applied, pre-baked, exposed, developed, and post-baked. A green halogen array and a blue halogen array are sequentially formed on the same substrate, thereby obtaining color filters in which red, green, and blue pixel arrays are disposed on the substrate. When the liquid composition of the photosensitive resin composition is coated on the substrate, a roller coating machine or a disk coating machine may be used in addition to the well-known solution soaking method and spraying method. And the method of a spinner. According to these methods, after the desired thickness is applied, the solvent (prebaking) is removed to form a coating. The pre-baking can be carried out by means of an oven, a heating plate, etc. 23 316123D01 201142502. The heating temperature and the heating time in the front portion can be appropriately selected depending on the type of the solvent to be used, for example, the temperature of the 12th generation to 1 minute. For the radiation used in the production of the color filter, for example, visible light ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 250 to 45 〇 11111 is preferable. Further, regarding a developing liquid suitable for this qualitative imaging, for example, an aqueous solution of a carbonate of a metal and a soil metal, an aqueous alkali metal hydroxide solution, or the like, wherein 5 to 10% by weight of sodium carbonate containing cerium is used. A weak base of carbonates such as carbonic acid mothers and carbonated carbonates, and an aqueous solution, which is preferably imaged at 20 to 30 Torr, and is equipped with a jade imager and an ultrasonic cleaning machine on the market, and can be precisely formed into a slender shape. After the test, the cleaning is performed. Regarding the development processing method, for example, a shower imaging method, a spray imaging method, a soaking (immersion) development method, a stirring development method, or the like can be applied. The developing condition is preferably carried out at normal temperature for 10 to 120 seconds. After such visualization, it can be from 180 to 250. The heat treatment (post-baking) is carried out under the conditions of (: temperature and 20 to 100 $ clock). The purpose of post-baking is to improve the adhesion between the coating film and the substrate after the pattern is formed. ', the same baking, can be carried out by oven, heating plate, etc. The formation of the present invention, the film after the case is formed according to the various steps of the above-mentioned photolithography process. Further, a black matrix may be formed of a light-shielding photosensitive resin and formed in the same manner as the above-described halogen matrix. A color filter having a halogen and/or a black matrix is formed. 316123D01
S 24 201142502 用的基板，例如為於玻璃或透明薄膜（例如聚碳酸酯、聚對 苯二甲酸丁 二酉旨（polyethylene terephthalate)、聚醚楓等）上 蒸鍍ITO、金等透明電極或鍍上圖案等者。此外，可視需 要，預先於這些基板上，適當地施以矽烷偶合處理劑等藥 品處理、電漿處理、離子蒸鍍、濺鍍、氣相反應法、真空 蒸鍍等前處理。 [發明之效果] 本發明的彩色濾光片用感光性樹脂組成物可以形成 圖案尺寸安定性優異，且顯像圖框（margin)、圖案密著性 及圖案之輪廓形狀丧好的圖案，因此，本發明的彩色濾光 片用感光性樹脂組成物，可適當的用做彩色液晶顯示裝 置、彩色傳真機、影像感測器等各種多色彩顯示器及光學 機器等之彩色濾、光片用的著色油墨，又，藉由該感光樹脂 組成物形成之具有黑色基質之彩色濾光片適合用於電視、 視訊顯示器、或是電腦的顯示器等。此外，如此獲得的彩 色濾光片極適合用於例如穿透型或是反射型的彩色液晶顯 示裝置、彩色影像管元件及色彩感測器等。 【實施方式】 以下根據實施例及比較例，具體說明本發明，但是本 發明並不限定於此。其中，於實施例及比較例的彩色濾光 片的製造中所採用的原料及省略符號如下所述。 (A)-l :具備芴骨架的環氧丙烯酸酯的酸酐類聚縮合物 的丙二醇單曱基醚乙酸酯溶液(樹脂固形成份濃度=56.1重 量％，日本新日鐵化學公司製造，商品名稱為V259ME) 25 316123D01 § 201142502 (A)-2 : Mw8800，酸價130的N-苯基醯亞胺/甲基丙烯 酸/甲基丙烯酸苯曱酯共聚合物的丙二醇單甲基醚乙酸酯 溶液(樹脂固形成份濃度=37.9重量％)(N-苯基醯亞胺：曱 基丙烯酸：曱基丙烯酸苯甲酯=26 : 34 : 40莫耳％) (A) -3 : Mwl60000，酸價95的N-苯基醯亞胺/甲基丙 烯酸/曱基丙烯酸苄酯共聚合物的丙二醇單甲基醚乙酸酯 溶液(樹脂固形成份濃度=38.1重量％)(N-苯基醯亞胺：甲 基丙烯酸：曱基丙烯酸苄酯=36 : 25 : 39莫耳％) (B) :雙季戊四醇六丙烯酸酯及雙季戊四醇五丙烯酸酯 的混合物（日本化葯公司製造，商品名稱為DPHA) (C) -l :上述通式(I)所表示的化合物 (C)-2 : ρ,ρ’-雙乙基胺基二苯甲酮 (C)-3 : 2-(4-曱氧基苯乙烯基)-4,6-雙（三氯甲基)-l,3,5- 三啡 (C)-4 : 2-苯甲基-2-二曱基胺基-1-(4-嗎啉基苯基）丁-1- (C)-5 : 2-曱基-1-[4-(曱基硫）苯基]-2-嗎啉基丙-1-酮 (〇-6 : 1-[4-(苯硫基）苯基]-2-(0-苯曱醯肟)-辛-1,2二 酮（化學式如下） 【化學式6】For the substrate used in S 24 201142502, for example, a transparent electrode such as ITO or gold is deposited on a glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether maple, etc.) or a pattern is plated. And so on. Further, pretreatment such as drug treatment such as decane coupling treatment agent, plasma treatment, ion deposition, sputtering, gas phase reaction method, or vacuum vapor deposition may be appropriately applied to these substrates as needed. [Effects of the Invention] The photosensitive resin composition for a color filter of the present invention can form a pattern having excellent pattern dimensional stability and a good image frame, pattern adhesion, and contour shape of the pattern. The photosensitive resin composition for a color filter of the present invention can be suitably used as a color filter or a light sheet for various multi-color displays and optical devices such as a color liquid crystal display device, a color facsimile machine, and an image sensor. The colored ink, in addition, the color filter having a black matrix formed by the photosensitive resin composition is suitable for use in a television, a video display, or a display of a computer or the like. Further, the color filter thus obtained is extremely suitable for use in, for example, a transmissive or reflective type color liquid crystal display device, a color image tube element, a color sensor, and the like. [Embodiment] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. Here, the raw materials and the omission symbols used in the production of the color filters of the examples and the comparative examples are as follows. (A)-l: a propylene glycol monodecyl ether acetate solution of an acid anhydride-based polycondensate of an epoxy acrylate having an anthracene skeleton (resin solid content concentration = 56.1% by weight, manufactured by Nippon Steel Chemical Co., Ltd., trade name is V259ME) 25 316123D01 § 201142502 (A)-2 : Mw8800, a propylene glycol monomethyl ether acetate solution of an acid valence of N-phenyl quinone imine/methacrylic acid/benzoic acid methacrylate copolymer ( Resin solid content concentration = 37.9 wt%) (N-phenyl quinone imine: mercaptoacrylic acid: benzyl methacrylate = 26: 34: 40 mol %) (A) -3 : Mwl60000, acid value of 95 Propylene glycol monomethyl ether acetate solution of N-phenyl quinone imine / methacrylic acid / benzyl methacrylate copolymer (resin solid concentration = 38.1% by weight) (N-phenyl quinone imine: A Acrylic acid: benzyl methacrylate = 36 : 25 : 39 mole %) (B) : a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA) (C) -l : Compound (C)-2 represented by the above formula (I): ρ,ρ'-diethylaminobenzophenone (C)-3 : 2-( 4-decyloxystyryl-4,6-bis(trichloromethyl)-l,3,5-triphthyl(C)-4: 2-benzyl-2-didecylamino- 1-(4-morpholinylphenyl)butan-1-(C)-5: 2-mercapto-1-[4-(indolylthio)phenyl]-2-morpholinylpropan-1-one (〇-6 : 1-[4-(phenylthio)phenyl]-2-(0-benzoquinone)-octane-1,2dione (the chemical formula is as follows) [Chemical Formula 6]
26 316123D01 201142502 (D)-l : ε型酞菁藍顏料（c.l顏料藍15 : 6)濃度η 7 重量％，咼分子分散劑濃度5.4重量％的丙二醇單甲基醚 乙酸酯分散液（固形成份19.1%) (D)-2:溴氯化酞菁綠顏料(c j顏料綠36)濃度15丨重 量％，高分子分散劑濃度4.0重量％的丙二醇單甲基醚乙 酸酯分散液（固形成份19.1%) (D)-3 :二酮基吡咯并吡咯紅顏料(C.I.顏料紅254)濃度 15.0重量％，高分子分散劑濃度53重量％的丙二醇單甲 基醚乙酸酯分散液（固形成份18 (D)-4 :鎳偶氮黃顏料(c.i.顏料黃15〇)濃度13 3重量 % ’南分子分散劑濃度4.4重量％的丙二醇單曱基醚乙酸 酯分散液（固形成份17.7%) (D) _5 :碳黑濃度20韋量％，高分子分散劑濃度5重 置％的丙二醇單甲基醚乙酸酯分散液（固形成份25.0%) (E) -l :丙二醇單甲基醚乙酸酯 (E) -2 :乳酸乙醋（ethyl lactate) (F) 環氧樹月a (日本環氧樹脂公司（japan Epoxy Resin) 製造，商品名稱為YX4000H) (G) :矽烷(Siiane)偶合劑 (H) :界面活性劑 [實施例] 按第1表所記載的比例來添加上述添加成份 ^而調製 出實施例1至8的組成物。於表中所謂的p/B，係顯示（分 散液中的顏料重量)/((A)、（B)、（F)成份中的固形成份合計26 316123D01 201142502 (D)-l : ε-type phthalocyanine blue pigment (cl pigment blue 15 : 6) concentration η 7 wt%, 咼 molecular dispersant concentration 5.4% by weight of propylene glycol monomethyl ether acetate dispersion (solid form Ingredients 19.1%) (D)-2: bromochlorophthalocyanine green pigment (cj pigment green 36) concentration 15% by weight, polymer dispersant concentration 4.0% by weight of propylene glycol monomethyl ether acetate dispersion (solid form) Ingredients 19.1%) (D)-3: Diketopyrrolopyrrole red pigment (CI Pigment Red 254) concentration 15.0% by weight, polymer dispersant concentration 53% by weight of propylene glycol monomethyl ether acetate dispersion (solid form) Ingredient 18 (D)-4: Nickel azo yellow pigment (ci pigment yellow 15 〇) concentration 13 3% by weight 'South molecular dispersant concentration 4.4% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 17.7%) (D) _5 : carbon black concentration 20 vol%, polymer dispersant concentration 5 reset % propylene glycol monomethyl ether acetate dispersion (solid content 25.0%) (E) -l : propylene glycol monomethyl Ether acetate (E) -2 : ethyl lactate (F) Epoxy resin a (made by Japan Epoxy Resin) The product name is YX4000H) (G): silane (Siiane) coupling agent (H): surfactant [Examples] The components of Examples 1 to 8 were prepared by adding the above-mentioned additive components in the ratios shown in Table 1. The so-called p/B in the table shows (the weight of the pigment in the dispersion) / (the total solid content in the (A), (B), (F) components
316123D01 S 27 201142502 重量）。 [第1表] 實施例(添加量) 1 2 3 4 5 6 7 8 (A)成份 (A)-l 107 107 107 107 124 124 124 124 (B)成份 (B) 40 40 40 40 30 30 30 30 (C)-l 0.40 0.40 1.10 0.60 0.70 0.70 1.20 1.20 (C)-2 0.10 0.10 (C)成份 (C)-3 0.10 (C)-4 0.30 (C)-5 0.20 (D)-l 626 (D)-2 107.7 107.7 (D)成份 (D)-3 183.3 (D)-4 5.1 5.1 (D)-5 84.5 84.5 84.5 84.5 (E)成份 (E)-l 400 400 300 400 400 400 400 400 (E)-2 __—----- ' (F)成份 (F) 1.0 1.0 1.0 1.0 (G)成份 (〇) 0.30 0.30 0.30 0.30 0.25 0.25 0.25 0.25 (H)成份 (H) 0.42 0.42 0.40 0.40 0.25 0.25 0.25 0.25 ~固形 成份 (%) 20.6 20.6 20.7 20.3 20.7 20.8 21.0 21.1 P/B 1.55 1.55 2.50 0.78 1.70 1.70 1.70 1.70 28 316123D01 201142502 採用旋轉塗佈機，將混合這些組成物所得到的彩色濾 光片用感光性樹脂組成物，以使前烘烤後的膜厚成為10 Vm或疋之方式’來塗佈於i25mmxl25mm的玻璃 基板上，於90°C下前烘烤2分鐘》之後，調整曝光間距 為80/zm’於乾燥塗膜上方配置線/空間為2()/zin/20/zm， 100em/100#m的負型光罩’以I線明度3〇mw/cm2的超 高壓水銀燈照射l〇〇mj/cm2的紫外線，而進行感光部分的 光硬化反應。接下來，以0.04%的氫氧化鉀水溶液，於23 C以1 kgf/ cm壓力沖淋曝光後的塗膜板.$ 〇秒或§ 〇秒以使 之顯像，並進行lkgf/cm2壓力的喷灑水洗，去除塗膜的未 曝光部分後，於玻璃基板上形成晝素圖案，之後採用熱烘 乾機，於進行230°C的熱後烘烤30分鐘之後，評估圖案線 寬、圖案直線性及塗膜表面粗糙度。 再者，於121°C、100%RH、2atm、24小時的條件下， 對後供烤後的圖案形成後的基板實施PCT(Pressure Cooker Test ’高壓水氣測試）’並於20 e m的圖案部上面貼附玻璃 紙膠帶(Cellophane Tape)，藉由進行剝落試驗來評估圖案 密著性。 實施例、比較例中的圖案晝素之圖案評估項目及方法 如下所述。 膜厚：採用觸針式高度差形狀測定器（美商科磊公司 (KLA_Tencor)製造，商品名稱為P-10)來測定。 圖案線寬：採用長度測定顯微鏡（日本尼康（Nikon)公 司製造，商品名稱為XD-20)，對於紅、綠、黃色感光性樹 29 316123D01 201142502 脂組成物’光罩寬度為1〇〇 “ m，對於 物，光罩寬度為20//m，若是線 ^黑色感光性樹脂組成 (良好），超過±10%之際為χ(不率未超過±10%之際為〇 圖案直線性：以顯微鏡觀察 觀察到從基板剝落及圖案輪廓邻八後的晝素圖案，若未 好），若觀察到從基板剝落及圖宏:呈鋸齒狀，則為〇（良 x(不良）。 ㈡案邊緣部分呈鑛齒狀，則為 塗膜表面粗糙度：顯像、執& 度(Ra)之值，若未滿150 A，目。之後的塗膜表面粗链 入，則為x(不良U〇（良好），若超過150 將結果示於第2表中。於第 攔為顯像時間5G秒的例子，古 + ’各個實施例的左 的結果^如第2表㈣，均^攔:。顯像時間_、的例子 [第2表] 實施例1 膜厚(/zm) 1.5 線寬(μ m) 線粗率(％) 判定 圖案直線性 表面粗糖度 Ra(A) 密著性 106.4 106.8 6.02 5.48 〇 〇 〇(6〇)〇 〇 〇 〇 (76)〇 108.3 7.66 〇 〇 〇 (75) 〇 Η 2 ----- 實施例3 ---——_ 實施例4 1.5 1.5 107.4 102.3 98.6 105.3 103.2 6.89 2.25 -1.42 5.03 3.10 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 (83) (106) (110) (80) (92) 〇 〇 〇 〇 〇 316123D01 30 201142502 實施例5 實施例6 實施例7 實施例8 膜厚(//m) 1.0 1.0 1.0 1.0 線寬(//m) 20.32 18.98 20.89 19.50 21.67 19.67 21.80 20.78 線粗率(％) 1.57 - 5.88 4.26 -2.56 7.71 -1.68 8.26 3.75 判定 〇 〇 〇 〇 〇 〇 〇 〇 圖案直線性 〇 〇 〇 〇 〇 〇 〇 〇 表面凹凸 〇 〇 〇 〇 〇 〇 〇 〇 Ra(A) (94) (110) (93) (100) (86) (93) (83) (80) 密著性 〇 〇 〇 〇 〇 〇 〇 〇 比較例1 關於(C)成份，除了（C)-4變更為0.3重量份及(C)-6變 更為1.5重量份之外，其他以與實施例1相同的條件來形 成晝素圖案，評估之後，觀察到圖案輪廓呈鋸齒狀，因此 圖案直線性為不良(X)。 比較例2 除了將(A)成份變更為（A)-2之外，其他以與實施例3 相同的條件製造晝素圖案並進行評估，確認於90秒顯像 下，線寬變細10%以上，因此線寬判定為不良（X)。此外， 圖案直線性及密著性判定亦為不良(X)。 比較例3 除將（C)成份變更為2.0重量份之(C)-3之外，其他以 與實施例4相同的條件製造晝素圖案，評估之後，觀察到 圖案直線性不良（X)，此外，被認為是（C)-3的不溶物之異 31 316123D01 201142502 物，以點狀存在於塗膜表面上。 比較例4 除了將(A)成份變更為（A)-2之外，其他以與實施例5 相同的條件製造成晝素圖案，評估之後，確認於80秒顯像 下，由於感度不足而使圖案產生缺陷，因而判定為不良（X)。 比較例5 除了將（C)成份變更為18重量份之(C)-6之外，其他以 與實施例5相同的條件製造晝素圖案，評估之後，確認於 90秒顯像下，線寬變細10%以上，因此線寬判定為不良 (X)。此外，圖案直線性亦不良(X)。 比較例6 除了將（C)成份的添加量變更為0.1重量份之外，其他 以與實施例5相同的條件製造晝素圖案，評估之後，確認 於50秒顯像下，線寬變細10%以上，因此線寬判定為不 良(X)。此外，圖案直線性及密著性判定亦為不良(X)，表面 粗糙:度為250 A，亦為不良(X)。 比較例7 除將(A)成份的種類變更為(A)-3之外，其他以與實施例8 相同的條件製造晝素圖案，評估之後，圖案直線性及密著 性均判定為不良(X)。 【圖式簡單說明】 【主要元件符號說明】 «、《、 32 316123D01316123D01 S 27 201142502 Weight). [Table 1] Example (addition amount) 1 2 3 4 5 6 7 8 (A) Ingredient (A)-l 107 107 107 107 124 124 124 124 (B) Ingredient (B) 40 40 40 40 30 30 30 30 (C)-l 0.40 0.40 1.10 0.60 0.70 0.70 1.20 1.20 (C)-2 0.10 0.10 (C) Composition (C)-3 0.10 (C)-4 0.30 (C)-5 0.20 (D)-l 626 ( D)-2 107.7 107.7 (D) Ingredient (D)-3 183.3 (D)-4 5.1 5.1 (D)-5 84.5 84.5 84.5 84.5 (E) Ingredient (E)-l 400 400 300 400 400 400 400 400 ( E)-2 __------ ' (F) Component (F) 1.0 1.0 1.0 1.0 (G) Composition (〇) 0.30 0.30 0.30 0.30 0.25 0.25 0.25 0.25 (H) Composition (H) 0.42 0.42 0.40 0.40 0.25 0.25 0.25 0.25 ~ solid content (%) 20.6 20.6 20.7 20.3 20.7 20.8 21.0 21.1 P/B 1.55 1.55 2.50 0.78 1.70 1.70 1.70 1.70 28 316123D01 201142502 Using a spin coater, the color filter obtained by mixing these compositions is used. The photosensitive resin composition was applied to a glass substrate of i25 mm x 25 mm by a film thickness of 10 Vm or 前 before baking, and baked at 90 ° C for 2 minutes. Adjust the exposure interval to 80/zm'. The line/space is 2 ()/zin/20/zm above the dry film, and the negative mask of 100em/100#m is 3 lines of lightness of 3〇mw/cm2. The ultrahigh pressure mercury lamp irradiates ultraviolet rays of l〇〇mj/cm2 to perform photohardening reaction of the photosensitive portion. Next, the exposed coated film was irradiated with a 0.04% potassium hydroxide aqueous solution at 23 C at a pressure of 1 kgf/cm for .00 sec or § 〇 second to visualize and perform lkgf/cm2 pressure. After spraying with water to remove the unexposed portion of the coating film, a halogen pattern was formed on the glass substrate, and then a hot drying machine was used, and after performing hot post-baking at 230 ° C for 30 minutes, the pattern line width and the pattern straight line were evaluated. Sex and coating surface roughness. Further, under the conditions of 121 ° C, 100% RH, 2 atm, and 24 hours, a PCT (Pressure Cooker Test 'High Pressure Water Gas Test') and a pattern of 20 em were applied to the substrate after patterning after baking. A cellophane tape (Cellophane Tape) was attached to the top, and the pattern adhesion was evaluated by performing a peeling test. The pattern evaluation items and methods of the pattern element in the examples and the comparative examples are as follows. Film thickness: measured by a stylus type height difference shape measuring instrument (manufactured by KLA_Tencor, trade name: P-10). Pattern line width: length measuring microscope (manufactured by Nikon, Japan, trade name: XD-20), red, green, yellow photosensitive tree 29 316123D01 201142502 Fat composition 'mask width is 1〇〇' m For the object, the mask width is 20/m, and if the line is black photosensitive resin composition (good), when it exceeds ±10%, it is χ (when the rate is not more than ±10%, the pattern is linear: Microscopic observation revealed that the ruthenium pattern peeled off from the substrate and the outline of the pattern was eight, if not good, if it was observed to peel off from the substrate and the macro was: jagged, it was 〇 (good x (bad). (b) edge of the case Part of the mineral tooth shape is the surface roughness of the coating film: the value of the image and the degree of (Ra). If it is less than 150 A, the surface of the coating film is thick after the chain is x (bad U 〇 (good), if it exceeds 150, the result is shown in the second table. In the example where the first block is the imaging time of 5G seconds, the left result of each of the embodiments is as shown in the second table (four). Example of development time_, [Table 2] Example 1 Film thickness (/zm) 1.5 Line width (μm) Line roughness (%) Determination chart Linear surface roughness R(A) Adhesion 106.4 106.8 6.02 5.48 〇〇〇(6〇)〇〇〇〇(76)〇108.3 7.66 〇〇〇(75) 〇Η 2 ----- Example 3 ---——_ Example 4 1.5 1.5 107.4 102.3 98.6 105.3 103.2 6.89 2.25 -1.42 5.03 3.10 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇(83) (106) (110) (80) ( 92) 〇〇〇〇〇 316123D01 30 201142502 Example 5 Example 6 Example 7 Example 8 Film thickness (//m) 1.0 1.0 1.0 1.0 Line width (//m) 20.32 18.98 20.89 19.50 21.67 19.67 21.80 20.78 Line roughness (%) 1.57 - 5.88 4.26 -2.56 7.71 -1.68 8.26 3.75 Determining the 直线 pattern linearity 〇〇〇〇〇〇〇〇 surface 〇〇〇〇〇〇〇〇 Ra(A) (94 ) (110) (93) (100) (86) (93) (83) (80) Adhesion 〇〇〇〇〇〇〇〇 Comparative Example 1 Regarding (C) component, except (C)-4 was changed to The moiré pattern was formed under the same conditions as in Example 1 except that 0.3 parts by weight and (C)-6 were changed to 1.5 parts by weight, and after evaluation, a graph was observed. Serrated contour, linear pattern so as bad (X). Comparative Example 2 A halogen pattern was produced and evaluated under the same conditions as in Example 3 except that the component (A) was changed to (A)-2, and it was confirmed that the line width was reduced by 10% under 90 seconds of development. As described above, the line width is judged to be defective (X). In addition, the pattern linearity and adhesion determination are also poor (X). Comparative Example 3 A halogen pattern was produced under the same conditions as in Example 4 except that the component (C) was changed to 2.0 parts by weight of (C)-3, and after evaluation, a pattern linearity defect (X) was observed. Further, it is considered to be the insoluble matter of (C)-3, 31 316123D01 201142502, which is present in the form of dots on the surface of the coating film. Comparative Example 4 A halogen pattern was produced under the same conditions as in Example 5 except that the component (A) was changed to (A)-2. After the evaluation, it was confirmed that the image was insufficient in sensitivity after 80 seconds of development. The pattern is defective and thus judged to be defective (X). Comparative Example 5 A halogen pattern was produced under the same conditions as in Example 5 except that the component (C) was changed to 18 parts by weight of (C)-6, and after evaluation, it was confirmed that the line width was 90 seconds. When the thickness is 10% or more, the line width is judged to be defective (X). In addition, the linearity of the pattern is also poor (X). Comparative Example 6 A halogen pattern was produced under the same conditions as in Example 5 except that the amount of the component (C) was changed to 0.1 part by weight. After the evaluation, it was confirmed that the line width became thinner under 50 seconds of development. Above %, the line width is judged to be bad (X). In addition, the linearity and adhesion of the pattern were also judged to be poor (X), and the surface was rough: the degree was 250 A, which was also bad (X). Comparative Example 7 A halogen pattern was produced under the same conditions as in Example 8 except that the type of the component (A) was changed to (A)-3, and the pattern linearity and adhesion were judged to be bad after evaluation ( X). [Simple diagram description] [Main component symbol description] «, ", 32 316123D01
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| JP2003304248A JP4437651B2 (en) | 2003-08-28 | 2003-08-28 | Photosensitive resin composition and color filter using the same |
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- 2003-08-28 JP JP2003304248A patent/JP4437651B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI351581B (en) | 2011-11-01 |
| JP4437651B2 (en) | 2010-03-24 |
| JP2005077451A (en) | 2005-03-24 |
| TW200508799A (en) | 2005-03-01 |
| KR20050021902A (en) | 2005-03-07 |
| TWI447523B (en) | 2014-08-01 |
| KR101077077B1 (en) | 2011-10-26 |
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