TWI285298B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
TWI285298B
TWI285298B TW092133008A TW92133008A TWI285298B TW I285298 B TWI285298 B TW I285298B TW 092133008 A TW092133008 A TW 092133008A TW 92133008 A TW92133008 A TW 92133008A TW I285298 B TWI285298 B TW I285298B
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TW
Taiwan
Prior art keywords
resin composition
photosensitive resin
acid
meth
mass
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TW092133008A
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Chinese (zh)
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TW200419307A (en
Inventor
Koji Ichikawa
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Sumitomo Chemical Co
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Publication of TWI285298B publication Critical patent/TWI285298B/en

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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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • 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
    • 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
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Architecture (AREA)
  • Mathematical Physics (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

This invention provides a photosensitive resin composition which can be used for making a pixel having an excellent planar characteristic with less residue remaining in the portion of a layer that is removed in a developing process. The photosensitive resin composition contains a binder resin having a construction unit derived from a (metha) acrylic acid and a (metha) acrylic acid, wherein the content of the (metha) acrylic acid in the solid component of the photosensitive resin composition is from 0.010 to 0.16% mass.

Description

1285298 玖、發明說明 【發明所屬之技術領域】 本發明為關於一種光敏性樹脂組成物。 【先前技術】 彩色液晶顯示裝置或攝像元件等中之彩色濾光片之製 成，一般是在玻璃基板或矽晶基板上形成紅、綠、及藍三 原色畫素（pixel)。同時，為了將此等畫素間遮光，一般則 設置黑色矩陣（black matrix)。為形成該各色晝素，須在形 成有黑色矩陣圖案之基板上，以旋鍍法（spin c〇adng)將含 各色所相當之顏料之光敏性樹脂組成物均勻地塗布，之後 再、’二加熱乾燥，忒塗膜再曝光顯像，或再於必要時採取加 ”、、更化方法，彩色濾光片所必要之各色經如此反複操作， 即可得到各色之圖像。 用於此用途之光敏性樹脂組成物已知之例可舉如顏 料、甲基丙烯酸苯甲醋/甲基丙稀酸/苯乙烯共聚物、感放 射線化合物、及含有機㈣之組成物（參考專利文獻υ。但 在使用該組成物時，在形成各色畫素或黑色矩陣時，會有 『顯像部份中餘留殘留物，造成畫素之平坦性不足之問 題。 專利文獻1特開平第5-343631號公報 【發明内容】 本：明之目的在提供一種光敏性樹脂組成物，其不顯 像^中之殘留物餘留少，可製成平坦性優良之書素。 本發明人等為發現可解決上述問題之光敏性樹脂組成 315272 5 1285298 :成及重複之結果，發現含(甲基)丙稀酸所 早位之黏著樹脂（binder resin)與特定量之（甲 =稀-夂單體之光敏性樹脂組成物，可減少不顯像部份中 :留物之殘留’因此可製成平坦性優良之畫素，而完成本 毛明。 亦即本發明提供一種光敏性樹脂組成物，其特徵為光 ㈣樹脂組成物中含構成單位製自（甲基）丙烯酸之黏著樹 月曰與（甲基）丙烯酸’該光敏性樹脂組成物固形物中（甲基） 丙烯酸之含量為0.010至0.16質量％。 【實施方式】 以下詳細說明本發明。 本發明之光敏性樹脂組成物為含構成單位製自（甲基） 丙稀酸之黏著樹脂與（甲基）㈣酸之組成物，該組成物為 固形物中（甲基）丙烯酸之含量為0 010至016質量％之組 成物。 黏著樹脂之例可舉如含構成單位製自（甲基）丙烯酸之 (甲基）丙烯酸系聚合物。其中（甲基）丙烯酸指丙烯酸或甲基 丙烯酸者。 在（甲基）丙烯酸中，可例舉如：不飽和單羧酸或不飽 和二羧酸等不飽和多元羧酸等之分子中，亦可包含構成單 位為來自於分子中至少含丨個具羧基之不飽和羧酸等之含 羧基之單體者。 其中之不飽和單羧酸可例舉如丁烯酸、^^氣丙烯酸、 肉桂酸等。 6 315272 1285298 不飽和二羧酸之例可舉如順丁烯二酸、反丁烯二酸、 衣康酸、順式甲基丁烯二酸、甲基富馬酸等。 不飽和多元羧酸亦可例舉如其酸酐，其具體例可舉如 順丁稀二酸sf、衣康酸軒、順式甲基τ烯二酸肝等。不飽 和多元羧酸亦可例舉如其單（2_甲基丙烯醯氧基烷基）酯， 例如琥抬酸單（2_丙烯醯氧基乙酯）、琥站酸單（2_甲基丙烯 醯氧基乙酯）、苯二酸單（2_丙烯醯氧基乙酯）、苯二酸單（2· 甲基丙烯醯氧基乙酯）等。不飽和多元羧酸亦可例舉如其兩 端含二羧基之聚合物之單（甲基）丙烯酸酯，其例可舉如 竣基聚己内s旨單丙烯酸s旨、ω，基聚己㈣單甲基丙稀酸 醋等。此等含叛基之單體可單獨或以其2種以上混合使 用。 稀苯甲基甲H、p_乙稀苯f基甲㈣、p乙稀苯甲基環氧丙 醚、m-乙烯苯甲基環氧丙醚、〇_乙烯苯甲基環氧丙醚、茚 等芳族乙浠化合物； 構成單位為製自（甲基）丙烯酸之（甲基）丙稀酸系聚合 物中，亦可含製自其他可共聚之單體之構成單位，該單體 之::可舉如苯乙烯、曱基苯乙烯、。_乙烯甲笨、爪乙烯 甲苯P乙烯甲苯、P-氣苯乙烯、。-甲氧基苯乙烯、m_曱 氧基苯乙烯、P-甲氧基苯乙烯、〇_乙烯苯曱基甲醚、…乙 丙烯酸曱酯、甲基丙烯酸"旨、丙烯酸乙酯、甲基丙烯酸 乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、 甲基丙稀酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酿、 丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸第二_ 丁酯、曱 315272 7 1285298 基丙烯酸第二-丁酯、丙烯酸第三-丁酯、曱基丙烯酸第三-丁酯、丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯 酸-2 -經基丙S旨、甲基丙稀酸β 2 - 基丙醋、丙稀酸-3 -輕基 丙酯、甲基丙烯酸-3-羥基丙酯、丙烯酸-2-羥基丁酯、甲基 丙烯酸-2-羥基丁酯、丙烯酸-3-羥基丁酯、甲基丙烯酸-3-羥基丁酯、丙烯酸-4-羥基丁酯、甲基丙烯酸-4-羥基丁酯、 丙烯酸稀丙酯、甲基丙烯酸烯丙酯、丙烯酸苯甲酯、甲基 丙烯酸苯甲酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯 酸苯酯、甲基丙烯酸苯酯、丙烯酸-2-甲氧基乙酯、曱基丙 烯酸-2-甲氧基乙酯、丙烯酸-2-苯氧基乙酯、甲基丙烯酸-2-苯氧基乙酯、丙烯酸甲氧基二乙二醇酯、甲基丙烯酸甲 氧基二乙二醇酯、丙稀酸甲氧基三乙二醇酯、甲基丙烯酸 甲氧基三乙二醇酯、丙稀酸甲氧基丙二醇酯、甲基丙烯酸 甲氧基丙二醇酯、丙烯酸曱氧基二丙二醇酯、甲基丙烯酸 甲氧基二丙二醇酯、丙烯酸異冰片酯、甲基丙稀酸異冰片 酯、丙烯酸二環戊二烯酯、甲基丙烯酸二環戊二烯酯、丙 烯酸-2-羥基-3-苯氧基丙酯、甲基丙烯酸_2_羥基-3-苯氧基 丙酯、單丙烯酸丙三醇酯、單甲基丙烯酸丙三醇酯等不飽 和羧酸酯類； 丙烯酸_2_胺基乙酯、甲基丙烯酸_2_胺基乙酯、丙烯酸_2_ 二甲基胺基乙S旨、甲基丙烯酸-2-二甲基胺基乙酯、丙烯酸 -2-胺基丙酯、甲基丙烯酸_2_胺基丙酯、丙烯酸-2-二甲基 胺基丙酯、甲基丙烯酸_2_二甲基胺基丙酯、丙烯酸胺基 丙酯、曱基丙烯酸-3-胺基丙酯、丙烯酸_3_二甲基胺基丙 8 315272 1285298 醋、甲基丙烯酸-3-二甲基胺基丙醋等不飽和敌酸胺基烷基 酯類； 丙烯酸環氧丙冑、甲基㈣酸環氧丙s旨等不飽和㈣環氧 丙酯類； 乙&L乙烯S曰、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等 羧酸乙稀酯類； 乙烯甲醚、乙烯乙醚、烯丙基環氧丙醚等不飽和醚類； 丙烯腈、甲基丙烯腈、α'氣化丙烯腈、氰化伸乙烯等氰乙 稀化合物； 丙烯醯胺、甲基丙烯醯胺、氯化丙烯醯胺、Ν_2_羥基乙 基丙..烯醯胺、Ν-2-羥基乙基甲基丙烯醯胺等不飽和醯胺 類； 馬來酸酐縮亞胺、Ν-苯基馬來酸酐縮亞胺、環己基馬來 酸酐縮亞胺等不飽和亞胺類； 1，3-丁二烯、異戊二烯、氣戊二烯等不飽和脂族共軛二烯 類； 聚苯乙烯、聚丙烯酸甲酯、聚甲基丙稀酸甲酯、聚丙烯酸 正丁酯、聚甲基丙烯酸正丁酯、聚矽氧烷之聚合物分子鏈 之末端上含單丙烯醯基或單甲基丙烯醯基之巨聚單體類 等。 此等單體可以各自單獨或以其2種以上組合使用。 前述（曱基）丙烯酸系聚合物中含有來自含羧基之單體之構 成單位時，其含量一般以10至50質量％為宜，μ至40 質量％更佳，25至40質量％又更佳。其含量在1〇至5〇質 9 315272 1285298 里/〇時，其對顯像液之溶解性佳，顯像時可形成正確之圖 像’因此較佳。 前述（甲基）丙烯酸系聚合物之例可舉如（甲基）丙烯酸/ 甲基（甲基）丙烯酸酯共聚物、（甲基）丙烯酸/苯甲基（甲基） 丙烯酸酿共聚物、（甲基）丙烯酸/2_羥乙基（甲基）丙烯酸醋/ 苯甲基（甲基）丙稀酸酯共聚物、（曱基）丙烯酸/甲基（甲基） 丙烯酸酯/聚苯乙烯巨聚單體共聚物、（甲基）丙烯酸/甲基 (甲基）丙浠酸酯/聚甲基（甲基）丙烯酸酯巨單體共聚物、（甲 基）丙烯酸/苯甲基（甲基）丙烯酸酯/聚苯乙烯巨單體共聚 物、（甲基）丙烯酸/苯甲基（甲基）丙烯酸酯/聚甲基（甲基）丙 稀酸酯巨單體共聚物、（甲基）丙烯酸/2_羥乙基（甲基）丙烯 酸酯/苯甲基（甲基）丙烯酸酯/聚苯乙烯巨單體共聚物、（甲 基）丙烯酸/2-羥乙基（甲基）丙烯酸酯/苯甲基（甲基）丙烯酸 酯/聚甲基（甲基）丙烯酸酯巨單體共聚物、（甲基）丙烯酸/苯 乙烯/苯甲基（甲基）丙烯酸酯/N-苯基馬來酸酐縮亞胺共聚 物、（甲基）丙烯酸/琥珀酸單（2-丙烯醯氧基乙基）/苯乙烯/ 苯曱基（甲基）丙烯酸酯/N-苯基馬來酸酐縮亞胺共聚物、（甲 基）丙烯酸/琥珀酸單（2-丙烯醯氧基乙基）/苯乙烯/烯丙基 (甲基）丙烯酸酯/N-苯基馬來酸酐縮亞胺共聚物（甲基）丙烯 酸/苯甲基（甲基）丙烯酸酯/N-苯基馬來酸酐縮亞胺/苯乙烯 /甘油醇單（甲基）丙烯酸酯共聚物等。其中之（甲基）丙烯酸 酯指丙烯酸酯或甲基丙烯酸酯。 其中以（甲基）丙烯酸/苯甲基（甲基）丙烯酸酯共聚物、 (甲基）丙稀酸/苯甲基（甲基）丙烯酸g旨/苯乙稀共聚物、（甲 10 315272 1285298 基）丙烯酸/甲基（甲基）丙烯酸酯共聚物、（甲基）丙烯酸/甲 基（甲基）丙烯酸酯/苯乙烯共聚物等為佳。 前述（甲基）丙烯酸系聚合物可以以構成成份（甲基）丙 烯酸系聚合物溶解於丙二醇單丙醚乙酸酯等溶劑中，加入 偶氮雙異丁腈等聚合起始劑，在70至90°C、空氣下保溫2 至5小時，再降溫至室溫（15至35°C )下終止反應之方法等 而製成。 前述（甲基）丙烯酸系聚合物之製造方法記載在 第2000-98606號公報、特開第2000 - 1 94 1 32號公報中 前述（甲基）丙烯酸系聚合物換算聚苯乙烯之重量平均 分子ϊ 一般以5,000至50,〇〇〇者為佳，或8 〇〇〇至4〇 〇〇〇 更佳，10,000至35,000又更佳。分子量為5 〇〇〇至5〇 〇〇〇 時，可增加其塗膜之硬度、臈餘留率提高、未曝光部份對 顯像液之溶解性佳，可提高其像解析度，因此較佳。 前述（甲基）丙烯酸系聚合物之酸值，一般以5〇至15〇 者為且60至140更佳’ 80至135又更佳。前述酸值為 5〇至150時’可增加其對顯像液之溶解性，使未曝光部份 易於溶解，且其感度高在顯像時透光部份之圖像會餘留增 加膜餘留率，因此較佳。 此處所指之酸值為測定复由$ ,, .其中和4(甲基）丙烯酸系聚合 物所必須之氫氧化鉀之量（m 一 一 h ffl ^ ^ 般可以求其滴定時所使 用之虱乳化鉀水溶液量。 感光性樹脂組成物之總固 般以 〜U形物中前述黏著樹脂之含量 υ ς至90質量％者為宜 里 10至70質量％更佳。黏著 315272 11 1285298 、十月曰之έ里為5至90質量％時，其對顯像液之溶解性完 全，無晝素部份之基板上顯像時不易產生殘留物，且其顯 夺+光邛伤之晝素部份膜不易減損，無畫素部份之脫除 ^生好，因此較佳。 本發明之感光性樹脂組成物中含有前述黏著樹脂及 (甲基）丙烯酉文，其感光性樹脂組成物中（甲基）丙烯酸之含量 /頁在0.G1質1 %以上G 16質量％以下，在G㈣質量％以 上〇·ΐ5質量％以下更佳，或〇〇2質量％以上〇12質量％以 下又更锃。（甲基）丙烯酸之含量在〇〇1〇質量❶/❶以上 :里％以下時’可減少塗膜熱處理步驟時加熱爐内之污 :且可減少不顯像部之殘留物，因此可製成平坦性佳之 旦素另方面’（甲基）丙烯酸之含量在不足0010質量％ 時，顯像時會有殘留物附著，超過〇16質量％時，畫素之 平坦性會變差。 該感光性樹脂組成物中（甲基）丙烯酸之含量可以以以 下（1)或（2)中所示之方法加以調整。 ⑴將以前述方法等所得到具有來自（甲基）丙烯酸之構成單 位之黏著Μ月日溶於庚院等溶劑中，以調整溶劑之量或洗淨 次數調節感光性樹脂組成物中（曱基）丙稀酸含量成〇 〇1質 量°/❻以上0.16質量％以下之方法。 (2)在製成以前述方法蓉讲彡曰 寺所付到具有來自（曱基）丙烯酸之構 成單位之黏著樹脂後’再以溶劑洗淨餘留黏著樹脂中未反 應之黏著樹脂構成成份(其中含(甲基)丙烯酸)，或必要時再 沉殿等而精製黏著樹脂’-度大致去除其全部未反應之原 12 315272 1285298 :二：ΐ精製之接著樹脂後，再在使用其調製光敏性樹脂 、，且成物時重新加入（甲基）丙烯酸之方法。 方法（1)或（2)中’洗淨所使用溶劑之種類只要為可溶解 #者樹脂中餘留之（甲基）丙稀酸者即可，並無特別限定， ，、例可舉如甲醇、己烷、庚烷等碳原子數4 1〇之脂族羥， %己烷、環庚烷等碳原子數4 1〇之脂環經等，其中以使 用己院、庚烧較佳，使用庚烧更佳。溶劑之❹量，一般 :對：著樹脂質量之2至2〇倍程度為宜，3至1〇倍更佳， / :二人數’ -般以次為宜，2至4次更佳。洗淨溫 又、要未達/合劑之彿點者即可’並無特別限定，但在經濟 性、洗淨效果之觀點等上，一般以4〇 3〇°C更佳。 L至 在此可舉例如將在丙二醇單甲醚乙酸酯（PGMA)中反 應所得到之黏著樹脂PGMA溶液，以歧之溶劑洗淨時 :烷之使用量一般以以對黏著樹脂質量21 2〇倍程度為 宜’ 3至1G倍更佳，洗淨溫度__般以室溫（抓至3 為佳。 在PGMA中反應所得到之黏著樹脂，以在庚院中再沉 殿者為佳，再沉殿後過濾並經庚院清洗3 :欠，即大致可將 黏著樹脂中餘留未反應之原料完全去除。 “本發明之光敏性樹脂組成物中亦可含著色劑，在不含 者色劑時’可使用以形成保護膜、隔層膜等，含著色劑時， 可使用以形成濾色膜等。 者色劑以顏料者為佳，顏料之例可舉如有機 1 1 Λ、、、 315272 13 1285298 機顏料。 無機顏料可例舉如金屬氧化物或金屬配位化合物之金 屬化合物，其具體例可舉如鐵、鈷、鋁、鎘、鉛、銅、鈦、 鎮、鉻、辞、銻等金屬之氧化物或複合金屬氧化物。 有機顏料之具體例可舉如色料分類表（Color Index，The Society of Dyers and Colourists 出版）中分類為 顏料（Pigment)之化合物。其更具體之例可舉如以丁色料分 類（C.I.)編號之化合物，但並不限定於此。 色料分類（The Society of Dyers and Colourists 出版） 中分類為顏料（Pigment)之化合物，具體之例可舉如c.ι·黃 色顏料-1、C.I.黃色顏料-3、C.I·黃色顏料-12、C.I.黃色顏 料_13、C.I·黃色顏料_14、C.I·黃色顏料_15、C.I.黃色顏料 _16、C.I·黃色顏料_17、€.1·黃色顏料_20、C.I·黃色顏料_24、 C.I·黃色顏料-3 1、C.I·黃色顏料-53、C.I·黃色顏料-83、C.I. 黃色顏料-86、C.I·黃色顏料-93、C.I.黃色顏料-94、C.I.黃 色顏料-109、C.I.黃色顏料-no、c.I.黃色顏料_117、c丄 黃色顏料-125、C.I·黃色顏料-128、C.I·黃色顏料_137、C I· 貝色顏料_138、C.I·黃色顏料_139、C.I.黃色顏料·147、C.I. 黃色顏料-148、C.I.黃色顏料-150、αι•黃色顏料-153、c丄 汽色顏料-154、C.I.黃色顏料-166、C.I.黃色顏料-173、C.I. 頁色顏料_194、C.I·黃色顏料-214等黃色顏料；c·][•橙色顏 料-13、C.I·橙色顏料_31、C I•橙色顏料_36、C I•橙色顏料 •3 8、C.I·橙色顏料·4〇、C.I·橙色顏料_42、C ][•橙色顏料_43、 C.I·橙色顏料-5：l、C·;[•撥色顏料_55、C I•橙色顏料_59、c丄 315272 14 1285298 撥色顏料-61、C.I·橙色顏料-64、C.I·橙色顏料_65、c·;[•橙 色顏料-7卜C.I.橙色顏料-73等橙色顏料；C.I·紅色顏料-9、 C.I.紅色顏料·97、C.I·紅色顏料-105、C.I·紅色顏料_122、 C.I.紅色顏料-123、C.I·紅色顏料-144、C.I.紅色顏料_149、 C.I·紅色顏料-166、C.I·紅色顏料_168、C.I.紅色顏料_176、 C.I·紅色顏料-177、C.I·紅色顏料_180、c_I·紅色顏料_192、 C.I·紅色顏料-209、C.I·紅色顏料_215、C.I·紅色顏料_216、 C.I.紅色顏料-224、C.I·紅色顏料_242、c.I.紅色顏料_254、 C.I·紅色顏料-264、C.I·紅色顏料_265等紅色顏料；C I•藍 色顏料-15、C.I·藍色顏料_15:3、C.I·藍色顏料_15:4、C I. I色顏料-15.6、C.I.藍色顏料_6〇等藍色顏料；ci·紫色顏 料-1、C.I.紫色顏料-19、C.I·紫色顏料_23、c.I.紫色顏料_ 29、C.I·紫色顏料-32、C.I.紫色顏料_36、C I•紫色顏料_38 等紫色顏料；C.I·綠色顏料_7、C I•綠色顏料_36等綠色顏 料；C.I·棕色顏料-23、C.I·棕色顏料_25等棕色顏料；c丄 黑色顏料-1、C.I·黑色顏料-7等黑色顏料等；其中以含C I· 黃色顏料·138、C.I.黃色顏料_139、αι•黃色顏料·15〇、c丄 紅色顏料_177、C.I·紅色顏料_2〇9、C.I·紅色顏料_254、C.I. 紫色顏料-23、C.I.藍色顏料_15:6、c丄綠色顏料_36中選擇 之至少1種顏料者為佳。 此等著色劑可以各自單獨或以其2種以上混合使用。 光敏性樹脂組成物總固形物中著色劑之含量一般以〇至6〇 質量％為宜，或1〇至55質量％更佳。著色劑之含量在〇 至60質量。/。時，製成薄膜之畫素色彩濃度充份，且不會降 15 315272 1285298 低顯像時非畫素部份之脫除性，不易產生殘留物，因此 佳。 又 本發明之光敏性樹脂組成物中亦可含光聚合性化合 物。光聚合性化合物為可經光及後述之光聚合起始劑聚合 之化合物，其例如單官能單體、2官能單體、或其他多官 能單體。 單官能單體之具體例可舉如壬基苯基卡必醇丙烯酸 酉曰、2-羥基-3-苯氧基丙基丙烯酸酯、2_乙基己基卡必醇丙 烯酸酯、2-羥基乙基丙烯酸酯、N_乙烯吡咯烷酮等。 2官能單體之具體例可舉如^-己烷二醇二（甲基）丙 =酸酯、乙二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯 酸酯、三乙二醇二（甲基）丙烯酸酯、聯酚a之雙（丙稀醯氧 基乙基）醚、3-甲基戊二醇二（甲基）丙烯酸酯等。 其他夕S能單體之具體例可舉如三羥甲基丙烷三（甲 基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲 基）丙烯酸_、二季戊四醇五（甲基）丙烯酸醋、二季戊四醇 八（甲基）丙稀酸酉旨等。盆中以推用， f ，、甲以便用2官能以上之多官能單 體為佳。 前述之光聚合性化合物，以對黏著樹脂與光聚合性化 合物總量⑽份’以質量！至6〇份質量者為宜，以5至 5〇份質量為更佳。光聚合性化合物含量為i至6()份質量 時，其畫素部份之強度或平滑性有變好傾向，因此較佳。 本發明之光敏性樹脂組成物中亦可含光聚合起始劑。 先聚合起始劑以其中至少含i種選自三吖嗪化合物、乙醯 315272 16 1285298 苯化合物、及雙咪唑化合物之群中之化合物及多官能硫醇 化合物者為宜’含二㈣化合物及多官能硫醇化合物者更 佳。含前述光聚合起始劑之光敏性樹脂組成物，可增加其 靈敏度’使用此等所形成之膜，其晝素部份之強度或表面 平滑性會更佳。更且’冑用光聚合起始輔劑所得到之光敏 性樹脂組成物，因可更增加其靈敏度，使用其形成濾色膜 時亦可提高其生產性，因此較佳。 其中之三吖嗪化合物可例舉如2,4_雙（三氣甲基）_6_ (4-甲氧基苯基）-1，3,5-三吖嗪、2,4-雙（三氯甲基）-6-(4_甲氧 基萘基）-1，3,5·三吖嗪、2,4-雙（三氯甲基）_6_胡椒基 二吖嗪、2,4-雙（三氣甲基）_6_(4_甲氧基苯乙烯基）—ns•三 吖嗪、2,4_雙（三氣甲基）_6_〔2_(5_甲基呋喃_2_基）乙烯基〕 _1，3,5_三吖嗪、2,4-雙（三氣甲基）_6_〔 2-(呋喃_2_基）乙烯基〕 •1，3,5-三吖嗪、2,4-雙（三氣甲基）_6_〔 2_(4_二乙基胺基_2_ 甲基苯基）乙烯基〕_1，3,5-三吖嗪、2,4-雙（三氣甲基）_6_ 〔2-(3,4-二甲氧基苯基）乙烯基〕-1，3,5_三。丫嗓等。 乙醯苯化合物可例舉如二乙氧基乙醯苯、2_經基_2_甲 基-1-苯基丙烷-1-酮、苯甲基二甲縮酮、2-羥基_ι_〔4-(2_ 經基乙氧基）苯基〕-2 -甲基丙院- Ι- g同、1_經基環己基苯基 酮、2 -甲基-1-(4 -甲基硫代苯基）-2-嗎琳丙烧-1-酮、2-苯甲 基-2-二甲基胺基-1-(4-嗎啉代苯基）丁烷-丨_酮、2_羥基_2_ 甲基- l-〔 4-(1-甲基乙稀基）苯基〕丙烧-1_酮之低聚物等。 雙咪唑化合物可例舉如2,2’-雙（2-氣苯基）-4,4，，5,5，-四 苯基雙咪唑、2,2f-雙（2,3-二氯苯基）-4,4，，5,5，-四苯基雙味 315272 17 1285298 6-75372號公報及特開平第1285298 发明, DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. [Prior Art] The color filter in a color liquid crystal display device or an image pickup device or the like is generally formed by forming red, green, and blue primary color pixels on a glass substrate or a twin crystal substrate. At the same time, in order to shield the pixels from each other, a black matrix is generally set. In order to form the respective color halogens, the photosensitive resin composition containing the pigments corresponding to the respective colors must be uniformly coated on the substrate on which the black matrix pattern is formed by spin plating, and then After heating and drying, the enamel coating film is re-exposure-developed, or if necessary, the addition, and the refining method are adopted, and the colors necessary for the color filter are repeatedly manipulated to obtain images of the respective colors. The known photosensitive resin composition is exemplified by a pigment, a benzyl methacrylate/methacrylic acid/styrene copolymer, a radiation sensitive compound, and a composition containing the organic compound (refer to the patent document υ. When the composition is used, when the respective color pixels or the black matrix are formed, there is a problem that the residue remains in the developing portion, which causes a problem that the flatness of the pixel is insufficient. Patent Document 1 Japanese Patent Laid-Open No. 5-343631 [Brief Description of the Invention] The purpose of the present invention is to provide a photosensitive resin composition which can be used as a book having excellent flatness without being left in the image. ask Photosensitive resin composition 315272 5 1285298 : As a result of the formation and repetition, it was found that a binder resin containing a (meth)acrylic acid in the early position and a specific amount of the photosensitive resin of the methyl group The composition can reduce the residue in the unimaged portion: the residue of the residue can be made into a fineness flatness, and the present invention can be completed. That is, the present invention provides a photosensitive resin composition characterized by light. (4) The resin composition contains a constituent unit of (meth)acrylic acid and a (meth)acrylic acid. The content of the (meth)acrylic acid in the photosensitive resin composition is 0.010 to 0.16 mass%. [Embodiment] The present invention will be described in detail below. The photosensitive resin composition of the present invention is a composition comprising an adhesive resin of a (meth)acrylic acid and a (meth)(tetra) acid, which is a solid form. The composition of the (meth)acrylic acid is from 0 010 to 016% by mass. Examples of the adhesive resin include a (meth)acrylic polymer containing a constituent unit derived from (meth)acrylic acid. Base) The acid refers to acrylic acid or methacrylic acid. The (meth)acrylic acid may, for example, be a molecule such as an unsaturated polycarboxylic acid such as an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid, or may comprise a constituent unit. The monomer derived from a carboxyl group containing at least one carboxyl group-containing unsaturated carboxylic acid in the molecule, and the unsaturated monocarboxylic acid may, for example, be crotonic acid, methacrylic acid, cinnamic acid, etc. 6 315272 1285298 Examples of the unsaturated dicarboxylic acid may, for example, be maleic acid, fumaric acid, itaconic acid, cis-methylbutenedioic acid, methyl fumaric acid, etc. Unsaturated polycarboxylic acid may also be used. For example, an acid anhydride thereof may, for example, be succinic acid sf, itaconic acid, cis-methyl taudiol liver, etc. The unsaturated polycarboxylic acid may also be exemplified by a single (2-methyl group). Propylene methoxyalkyl) esters, such as succinic acid mono(2-propenyloxyethyl ester), succinic acid mono(2-methylpropenyloxyethyl ester), phthalic acid mono(2-propylene)醯 methoxyethyl ester), phthalic acid mono (2· methacryloxyethyl ester), and the like. The unsaturated polycarboxylic acid may, for example, be a mono(meth)acrylate such as a polymer having a dicarboxy group at both ends thereof, and examples thereof include a mercapto group, a monoacrylic acid, a ω, a poly(tetra) group. Monomethyl acrylate vinegar and the like. These excimer-containing monomers may be used singly or in combination of two or more kinds thereof. Dilute benzyl methyl H, p_ethyl benzene f-methyl (tetra), p-ethyl benzyl methacrylate, m-vinyl benzyl epoxypropyl ether, 〇 _ vinyl benzyl methacrylate An aromatic acetamidine compound; the constituent unit is a (meth)acrylic acid-based (meth)acrylic acid-based polymer, and may also comprise a constituent unit derived from another copolymerizable monomer. :: styrene, mercapto styrene, for example. _ ethylene methyl stupid, claw ethylene toluene P vinyl toluene, P-gas styrene. -Methoxystyrene, m_methoxy styrene, P-methoxystyrene, 〇_vinyl benzoyl methyl ether, ... decyl methacrylate, methacrylic acid " Ethyl acrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, methyl Isobutyl acrylate, second-butyl acrylate, 曱315272 7 1285298 second-butyl acrylate, third-butyl acrylate, third-butyl methacrylate, 2-hydroxyethyl acrylate, methyl 2-hydroxyethyl acrylate, 2-(acrylic acid)-2-methyl propyl acrylate, methyl 3-propyl propyl acrylate, 3-propyl propyl methacrylate, 3-hydroxypropyl methacrylate , 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, methacrylic acid-4 -hydroxybutyl ester, propyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate , cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxy triethylene glycol acrylate, methacrylic acid Oxytriethylene glycol ester, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, decyloxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, A Isobornyl acrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, _2-hydroxy-3-methacrylate Unsaturated carboxylic acid esters such as phenoxypropyl ester, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, acrylic acid _2_ Dimethylaminoethyl S, -2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-amino methacrylate Propyl ester, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, aminopropyl acrylate, 3-aminopropyl methacrylate, acrylic acid _3_ Dimethylaminopropyl 8 315272 1285298 hydroxyacetic acid, dimethyl dimethyl acrylate acrylate and other unsaturated alkylamine alkyl esters; acrylonitrile acrylate, methyl (tetra) acid propylene s Unsaturated (tetra)glycidyl esters; ethyl carboxylic acid esters such as ethyl bromide, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ether, allylic Unsaturated ethers such as propylene glycol, acrylonitrile, methacrylonitrile, α' gasified acrylonitrile, cyanide ethylene and other cyanoethylene compounds; acrylamide, methacrylamide, propylene chloride Amine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine Unsaturated imines such as cyclohexylmaleic acid imide; unsaturated aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and gas pentadiene; polystyrene, poly Methyl enoate, polymethyl methacrylate, polybutyl acrylate, n-butyl methacrylate, polyoxymethane, polymer polymer chains containing monopropenyl sulfhydryl or monomethacrylic acid at the end The macromonomers of the sulfhydryl group and the like. These monomers may be used singly or in combination of two or more kinds thereof. When the (mercapto)acrylic polymer contains a constituent unit derived from a carboxyl group-containing monomer, the content thereof is usually 10 to 50% by mass, more preferably μ to 40% by mass, and still more preferably 25 to 40% by mass. . When the content is from 1 〇 to 5 〇 9 315272 1285298 〇 / ,, it has good solubility to the developing liquid, and a correct image can be formed when developing. Examples of the (meth)acrylic polymer include a (meth)acrylic acid/methyl(meth)acrylate copolymer, a (meth)acrylic acid/benzyl(meth)acrylic acid graft copolymer, ( Methyl)acrylic acid/2-hydroxyethyl (meth)acrylic acid vinegar / benzyl (meth) acrylate copolymer, (mercapto) acrylic acid / methyl (meth) acrylate / polystyrene Polymonomer copolymer, (meth)acrylic acid/methyl(meth)propionate/polymethyl(meth)acrylate macromonomer copolymer, (meth)acrylic acid/benzyl (methyl) Acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, (methyl) Acrylic acid/2_hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate /Benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylate / styrene / benzene (meth) acrylate / N-phenyl maleic acid imide copolymer, (meth) acrylic acid / succinic acid mono (2-propenyloxyethyl) / styrene / phenyl fluorenyl (methyl Acrylate/N-phenylmaleic acid imide copolymer, (meth)acrylic acid/succinic acid mono(2-propenyloxyethyl)/styrene/allyl (meth)acrylate/ N-phenylmaleic acid imide copolymer (meth)acrylic acid / benzyl (meth) acrylate / N-phenyl maleic anhydride imine / styrene / glycerol mono (meth) acrylate Ester copolymers and the like. Among them, (meth) acrylate means acrylate or methacrylate. Among them, (meth)acrylic acid/benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate g / styrene copolymer, (A 10 315272 1285298 Acrylic acid/methyl (meth) acrylate copolymer, (meth) acrylate / methyl (meth) acrylate / styrene copolymer, etc. are preferred. The (meth)acrylic polymer may be dissolved in a solvent such as propylene glycol monopropyl ether acetate as a component (meth)acrylic polymer, and a polymerization initiator such as azobisisobutyronitrile may be added at 70 to It is prepared by incubating at 90 ° C for 2 to 5 hours in air, and then cooling to room temperature (15 to 35 ° C) to terminate the reaction. The method for producing a (meth)acrylic polymer is described in JP-A No. 2000-98606 ϊ Generally it is 5,000 to 50, which is better, or 8 to 4 is better, and 10,000 to 35,000 is better. When the molecular weight is 5 〇〇〇 to 5 ,, the hardness of the coating film can be increased, the residual ratio of ruthenium can be increased, and the solubility of the unexposed portion to the developing solution can be improved, and the image resolution can be improved, so good. The acid value of the aforementioned (meth)acrylic polymer is generally from 5 Å to 15 Å and more preferably from 60 to 140 Å to 80 135. When the acid value is 5 〇 to 150 Å, the solubility in the developing solution can be increased, the unexposed portion is easily dissolved, and the sensitivity is high. When the image is developed, the image of the light-transmitting portion remains. Retention rate is therefore preferred. The acid value referred to herein is determined by the amount of potassium hydroxide necessary for the 4 (meth)acrylic polymer (m-hffl ^ ^ can be used for titration) The amount of the emulsified potassium aqueous solution is as follows: The total solid content of the photosensitive resin composition is preferably from 10 to 70% by mass in the amount of the above-mentioned adhesive resin in the U-shaped form, preferably from 10 to 70% by mass. Adhesive 315272 11 1285298, ten When it is 5 to 90% by mass in the ruthenium, the solubility to the developing solution is complete, and the residue on the substrate without the halogen component is less likely to cause residue, and the sputum which is marked with light damage The photosensitive resin composition of the present invention contains the above-mentioned adhesive resin and (meth)acrylic acid, and the photosensitive resin composition thereof is not easily degraded, and the photosensitive resin composition of the present invention contains the above-mentioned adhesive resin. The content of the medium (meth)acrylic acid/page is 0.1% or more and G 16% by mass or less, more preferably G (four)% by mass or more, more preferably 5% by mass or less, or 2% by mass or more and 〇 12% by mass or less. It is even more ambiguous. The content of (meth)acrylic acid is above 〇1〇〇❶/❶: At the time of 'reducing the stain in the heating furnace during the heat treatment step of the coating film: and reducing the residue of the non-image developing portion, so that the flatness is better, and the content of the (meth)acrylic acid is less than 0010% by mass. When the image is formed, the residue adheres, and when it exceeds 16% by mass, the flatness of the pixel deteriorates. The content of (meth)acrylic acid in the photosensitive resin composition may be (1) or (2) below. The method shown in the above is adjusted. (1) The adhesive having the constituent unit derived from (meth)acrylic acid obtained by the above method or the like is dissolved in a solvent such as Gengyuan, and the amount of the solvent or the number of times of washing is adjusted. In the photosensitive resin composition, the (mercapto) acrylic acid content is 〇〇1 mass ° / ❻ or more and 0.16 mass % or less. (2) In the above-mentioned method, the 彡曰 彡曰 彡曰 所 所 所 所 所After the adhesive resin of the constituent unit of acrylic acid is used, the unreacted adhesive resin component (containing (meth)acrylic acid) in the remaining adhesive resin is washed with a solvent, or the adhesive resin is refined by a sinking chamber if necessary. '- degree roughly goes All of the unreacted original 12 315272 1285298: 2: After the refining of the resin, the method of re-adding the (meth)acrylic acid when the photosensitive resin is prepared and formed, and the method (1) or (2) The type of the solvent used for the "cleaning" is not particularly limited as long as it is a (meth)acrylic acid remaining in the resin which can be dissolved, and examples thereof include methanol, hexane, and heptane. The aliphatic hydroxy group having a carbon number of 4 〇, the alicyclic ring having a carbon number of 4 〇 such as % hexane or cycloheptane is preferably used, and it is preferably used by using a hexagram or a heptane. The amount of bismuth, generally: pair: 2 to 2 times the quality of the resin is appropriate, 3 to 1 times better, /: two people '- generally preferred, 2 to 4 times better. It is not particularly limited, but it is generally 4 〇 3 〇 ° C in terms of economy and washing effect. L to the above, for example, the adhesive resin PGMA solution obtained by reacting in propylene glycol monomethyl ether acetate (PGMA) is washed with a solvent: the amount of the alkane is generally used to be the mass of the adhesive resin 21 2 The degree of 〇 times is preferably '3 to 1G times better, the washing temperature __ is usually room temperature (grasping to 3 is better. The adhesive resin obtained by reaction in PGMA is better for sinking in the Gengyuan.) After the chamber is filtered, it is filtered and cleaned by Gengyuan. 3: Under, that is, the unreacted raw material remaining in the adhesive resin can be completely removed. "The photosensitive resin composition of the present invention may also contain a coloring agent, and When the toner is used, it can be used to form a protective film, a barrier film, etc., and when a coloring agent is contained, it can be used to form a color filter film or the like. The colorant is preferably a pigment, and the pigment is exemplified by an organic one. , 315272 13 1285298 machine pigment. The inorganic pigment may be exemplified by a metal oxide or a metal complex compound, and specific examples thereof may be iron, cobalt, aluminum, cadmium, lead, copper, titanium, town, chromium, An oxide or composite metal oxide of a metal such as rhodium or ruthenium. The compound may be exemplified by a color classification (Color Index, published by The Society of Dyers and Colourists) as a pigment (Pigment), and more specific examples thereof may be a compound numbered by a butyl color (CI). However, it is not limited to this. The colorant classification (published by The Society of Dyers and Colourists) is classified as a pigment (Pigment), and specific examples thereof include c. i. yellow pigment-1 and CI yellow pigment-3. CI·Yellow Pigment-12, CI Yellow Pigment_13, CI·Yellow Pigment _14, CI·Yellow Pigment _15, CI Yellow Pigment _16, CI·Yellow Pigment _17, €.1·Yellow Pigment _20, CI ·Yellow pigment _24, CI·Yellow pigment-3 1, CI·Yellow pigment-53, CI·Yellow pigment-83, CI yellow pigment-86, CI·Yellow pigment-93, CI yellow pigment-94, CI yellow pigment -109, CI yellow pigment-no, cI yellow pigment _117, c 丄 yellow pigment-125, CI·yellow pigment-128, CI·yellow pigment _137, CI·bei pigment _138, CI·yellow pigment _139 , CI yellow pigment · 147, CI yellow pigment - 148, CI yellow pigment - 150, αι Yellow pigment-153, c丄 steam pigment-154, CI yellow pigment-166, CI yellow pigment-173, CI page pigment _194, CI·yellow pigment-214 and other yellow pigments; c·][• orange pigment- 13, CI · orange pigment _31, CI • orange pigment _36, CI • orange pigment • 3 8, CI · orange pigment · 4 〇, CI · orange pigment _42, C ] [• orange pigment _43, CI· Orange pigment-5: l, C ·; [• dial pigment _55, CI • orange pigment _59, c 丄 315272 14 1285298 dial pigment - 61, CI · orange pigment - 64, CI · orange pigment _65, c·;[•Orange Pigment-7 Bu CI Orange Pigment-73 and other orange pigments; CI·Red Pigment-9, CI Red Pigment·97, CI·Red Pigment-105, CI·Red Pigment_122, CI Red Pigment- 123, CI·Red Pigment-144, CI Red Pigment _149, CI·Red Pigment-166, CI·Red Pigment _168, CI Red Pigment _176, CI·Red Pigment-177, CI·Red Pigment _180, c_I ·Red pigment _192, CI·Red pigment-209, CI·Red pigment _215, CI·Red pigment _216, CI red pigment-224, CI·Red pigment _242, cI red Red pigment such as _254, CI·red pigment-264, CI·red pigment _265; CI•blue pigment-15, CI·blue pigment _15:3, CI·blue pigment _15:4, C I. I color pigment -15.6, CI blue pigment _6 〇 and other blue pigment; ci · purple pigment-1, CI purple pigment -19, CI · purple pigment _23, cI purple pigment _ 29, CI · purple pigment -32, CI purple pigment _36, CI•purple pigment _38 and other purple pigments; CI·green pigment _7, CI•green pigment _36 and other green pigments; CI·brown pigment-23, CI·brown pigment _25, etc. Brown pigment; c丄 black pigment-1, CI·black pigment-7 and other black pigments; among them, CI·yellow pigment·138, CI yellow pigment _139, αι•yellow pigment·15〇, c丄 red pigment_ Preferably, at least one of the pigments selected from the group consisting of 177, CI·red pigment _2〇9, CI·red pigment _254, CI purple pigment-23, CI blue pigment _15:6, and c丄 green pigment _36 is preferred. These coloring agents may be used singly or in combination of two or more kinds thereof. The content of the colorant in the total solid content of the photosensitive resin composition is preferably from 〇 to 6 〇 by mass, or more preferably from 1 55 to 55% by mass. The colorant is present in an amount of from 〇 to 60% by mass. /. When the film is made into a film, the color density is sufficient, and it does not fall. 15 315272 1285298 The non-pixel part of the low-resolution image is removed, and residue is not easily generated, so it is preferable. Further, the photosensitive resin composition of the present invention may contain a photopolymerizable compound. The photopolymerizable compound is a compound which can be polymerized by light and a photopolymerization initiator described later, and is, for example, a monofunctional monomer, a bifunctional monomer, or other polyfunctional monomer. Specific examples of the monofunctional monomer include mercaptophenyl carbitol ruthenium acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy ethane Acrylate, N_vinylpyrrolidone, and the like. Specific examples of the bifunctional monomer include ^-hexanediol di(methyl)propane=ester, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and three. Ethylene glycol di(meth)acrylate, bisphenol bis(acryloxyethyl)ether, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of the other S-energy monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid, and dipentaerythritol penta(methyl). Acrylic vinegar, dipentaerythritol octa(methyl) acrylate, and the like. It is preferred to use a polyfunctional monomer having two or more functional groups in the pot. The above photopolymerizable compound is in a mass of 10% by weight of the total amount of the adhesive resin and the photopolymerizable compound! It is better to use 6 tones of quality, preferably 5 to 5 parts by mass. When the content of the photopolymerizable compound is from i to 6 parts by mass, the strength or smoothness of the pixel portion tends to be good, which is preferable. The photosensitive resin composition of the present invention may further contain a photopolymerization initiator. The first polymerization initiator is preferably a compound containing a compound selected from the group consisting of a triazine compound, an acetamidine 315272 16 1285298 benzene compound, and a bisimidazole compound, and a polyfunctional thiol compound. More preferred are polyfunctional thiol compounds. The photosensitive resin composition containing the photopolymerization initiator can increase the sensitivity. The film formed using these can have a higher strength or surface smoothness of the halogen portion. Further, the photosensitive resin composition obtained by using the photopolymerization starting adjuvant is preferred because it can further increase the sensitivity and can also improve the productivity when the color filter film is formed. Among them, the triazine compound may, for example, be 2,4-bis(trimethylmethyl)_6_(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5·trioxazine, 2,4-bis(trichloromethyl)_6_piperidyl dioxazine, 2,4-double (three gas methyl) _6_(4_methoxystyryl)-ns•triazine, 2,4_bis(trimethylmethyl)_6_[2_(5-methylfuran-2-yl)ethylene _1,3,5_trioxazine, 2,4-bis(trimethylmethyl)_6_[2-(furan-2-yl)vinyl] • 1,3,5-triazine, 2, 4-bis(trimethylmethyl)_6_[2-(4-diethylamino-2-phenylphenyl)vinyl]_1,3,5-triazine, 2,4-bis(trimethyl) )_6_[2-(3,4-Dimethoxyphenyl)vinyl]-1,3,5_tri. Hey. The acetophenone compound may, for example, be diethoxyacetamidine, 2-hydrazino-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy_ι_[ 4-(2-Pentylethoxy)phenyl]-2-methylpropanol - Ι-g, 1_ylcyclohexyl phenyl ketone, 2-methyl-1-(4-methylthio) Phenyl)-2-morphinpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-indole-ketone, 2-hydroxyl An oligomer of _2_methyl-l-[4-(1-methylethenyl)phenyl]propan-1-yl ketone. The biimidazole compound may, for example, be 2,2'-bis(2-phenylphenyl)-4,4,5,5,-tetraphenylbisimidazole, 2,2f-bis(2,3-dichlorobenzene) Base)-4,4,,5,5,-tetraphenyl double flavor 315272 17 1285298 6-75372 and special opening

(參考例如特開平第7- 開平第7-10913號公報等。）等，其中以使用 °坐（參考例如特開平第 號公報等。）、2,2，-雙 2,2’-雙（2_ 氣 1 其、-4 4 2,2’-雙（2-氣苯基M，4，，5,5i_四苯基雙咪唑、厶2，-雙二 氣苯基）-4,4’，5,5’_四苯基雙咪唑較佳。 多官能硫醇化合物為分子中含2個以上硫醇基之化合 物，特別以脂族羥基上含複數硫醇基之脂族烴多官能硫^ 化合物為佳。 脂族烴多官能硫醇化合物可例舉如己烷二硫醇、壬烷 一硫醇、1，4-二甲硫基苯、丁烷二醇雙硫代丙酸酯、丁烷 二醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、三羥甲基 丙烷參硫代乙醇酸酯、丁烷二醇雙硫代丙酸酯、三羥甲基 丙烷參硫代丙酸酯、三羥甲基丙烷參硫代乙醇酸酯、季戊 四醇肆硫代丙酸酯、季戊四醇肆硫代乙醇酸酯、參羥基乙 基參硫代丙酸自旨、多元羥基化合物之硫代乙醇酸酯、硫代 丙酸酯等，其中以使用三羥甲基丙烷參硫代丙酸酯、三羥 甲基丙燒參硫代乙醇酸酯、季戊四醇肆硫代丙酸酯等為 佳，使用季戊四醇肆硫化丙酸酯更佳。 前述之光聚合起始劑中亦可以并用在該範疇中_般所 18 315272 1285298 使用之光聚合起始劑，其例可舉如苯偶因系、二苯甲酮系、 噻噸酮系、蒽系之起始劑等。更具體之例可舉如以下之化 合物’此等可單獨或以其2種以上組合使用。 (i) 苯偶因系可例舉如苯偶因、苯偶因甲醚、笨偶因乙醚、 苯偶因異丙醚、苯偶因異丁喊等， (ii) 二苯甲酮系可例舉如二苯甲酮、〇_苯醯苯甲酸甲酯、4_ 苯基二苯甲酮、硫化_4-苯甲基_4，_甲基二苯基、3,3，，4,4,_ 四（第三丁基過氧化羰基）二苯甲酮、2,4,6•三甲基二苯曱酮 等， (iii) 噻噸酮系可例舉如2_異丙基噻噸酮、4_異丙基噻噸 酮、2,4-二乙基噻噸酮、2,4_二氣噻噸酮、^氯“·丙氧基噻 °頓S同等， (iv) 蒽系可例舉如9，1〇_二甲氧基蒽、2•乙基_9，1〇_二甲氧基 蒽、9，1〇-二乙氧基蒽、2_乙基_9，1〇_二乙氧基蒽等， (v) 其他可例舉如氧化_2,4,6-三甲基苯甲醯二苯基膦、2,2，_ 雙（〇-氣笨基）-4,4，，5,5，_四苯基_丨，2，_雙咪唑、ι〇_ 丁基_2_氣 A#㈣' 2_乙基蒽®昆、苯甲基、9，10-菲酉昆、樟腦醌、苯 基乙醛酸甲酯、二茂鈦化合物等。 光聚合起始劑可單獨或以其複數種組合使用。 光聚合起始劑中亦可再組合使用光聚合起始輔劑。 光聚合起始輔劑可例舉如胺系化合物、烷氧基葱系化合 物、噻噸酮系化合物等。 胺系化合物可例舉如三乙醇胺、甲基二乙醇胺、三異 丙醇胺、4 -二审装4 ro 一 T i 本甲酸曱酯、‘二曱基胺苯甲酸乙酯、 19 315272 1285298 4 一甲基胺笨甲酸異戊酯、苯甲酸-2-二甲基胺基乙酯、4_ 一甲基胺笨甲酸-2 -乙基己酯、Ν,Ν-二曱基對甲苯胺、4,4匕 雙（一甲基胺基）二苯甲酮（通稱為米蚩酮（Michler，s ketone))、4,4’_雙（二乙基胺基）二苯甲酮、4,4，_雙（乙基甲基 胺基）二苯甲酮等，其中以4,4，_雙（二乙基胺基）二苯甲_較 佳。 烧氧基恩系化合物可例舉如9,1 〇-二甲氧基蒽、2-乙基 9，1〇-一甲氧基恩、91〇_二乙氧基蒽、2_乙基_91〇_二乙 基蒽等。 嗟嘲酮系化合物可例舉如2_異丙基噻噸酮、4_異丙基 噻噸酮、2,4-二乙基噻噸酮、2,4_二氯噻噸酮、卜氣丙氧 基°塞σ頓酮等。 光聚合起始輔劑亦可使用市售者，市售之光聚合起始 辅劑可例舉如商品名「EAB-F」（保土谷化學工業（株）製造） 等。 光聚合起始劑及光聚合起始輔劑之組合可例舉如二乙 氧基乙醯苯/4,4’-雙（二乙基胺基）二苯甲酮、甲基_2_嗎琳 代_1-(4-甲基硫苯基）丙烧-1-酮/4,4’-雙（二乙基胺基）二苯 甲酮、2-羥基-2 -甲基-1-苯基丙烷-ΐ_酮/4,4，_雙（二乙基胺基） 二苯曱酮、苯甲基二甲縮酮/4，4，-雙（二乙基胺基）二苯甲 _、2-羥基-2-甲基_1_〔 4-(2-羥基乙氧基）苯基〕丙烷酮 /4,4、雙（二乙基胺基）二苯曱酮、1_羥基環己基苯基酮/4,4，_ 雙（二乙基胺基）二苯曱酮、2-經基-2-曱基-1-〔 4-(1-甲基乙 烯基）苯基〕丙烷-1-酮之低聚物/4,4，-雙（二乙基胺基）二笨 20 315272 1285298 曱酮、2-苯甲基-2-二曱基胺基-嗎啉代苯基）丁烷β1_ 酮/4,4’-雙（二乙基胺基）二苯甲_等，其中以2_甲基_2_嗎啉 代-1-(4-甲基硫苯基）丙烷_1_酮/4,4，_雙（二乙基胺基）二苯 甲酮較佳。 光聚合起始劑一般以對黏著樹脂及光聚合性化合物總 计100負量份為0.1至40質量份為佳，^^至質量份更 佳。光聚合起始輔劑一般以對黏著樹脂及光聚合性化合物 總计10 0質量份為0 · 1至5 0質量份為佳，i至4 〇質量份 更佳。光聚合起始劑含量為〇. 1至4 〇質量份時，會傾向於 增加光敏性樹脂組成物之靈敏度、使用前述光敏性樹脂組 成物形成晝素部份之強度、或增加前述畫素之表面之平滑 性，因而較佳。 此外，光聚合起始輔劑為〇·丨至5〇質量份時，會傾向 於增加光敏性樹脂組成物之靈敏度，提高前述光敏性樹脂 組成物所形成濾色膜之生產性，因此較佳。 本發明之光敏性樹脂組成物中亦可含溶劑。 該溶劑之例可舉如乙二醇單甲鱗、乙二醇單乙喊、乙 二醇單丙鱗、及乙二醇單丁醚之乙二醇單烷基醚類；二乙 二醇二甲酿、二乙二醇二乙鱗、二乙二醇二丙醚、及二乙 一醇一丁醚之一乙二醇二烧基醚類；曱基乙酸纖S旨、及乙 基乙酸纖S曰之乙一醇烧基乙酸醋類；丙二醇單甲喊乙酸 酯、丙二醇單乙_乙酸酯、丙二醇單丙驗乙酸酯、甲氧基 丁基乙酸酯、及甲氧基戊基乙酸酯之烷基二醇烷基醚乙酸 酯類；苯、甲苯、二甲苯、及均三甲苯等芳族烴類；丁酮、 21 315272 1285298 丙’、甲基正戊基曱酮、曱基異丁酮、及環己酮等酮類； 丙肖、丁醇、己醇、環己醇、乙二醇'及丙三醇等 知類’ 3-乙氧基丙酸乙酯、及3_曱氧基丙酸甲酯等 丁内酯等環酯類等。 、 其中以使用丙二醇單甲醚乙酸酯為佳。 此等溶劑可以各自單獨或以其2種以上組合使用。 、光敏性樹脂組成物中溶劑之含量，以6〇至9〇質量％ 為佳，70至85質量％更佳。溶劑之含量為⑼至列質量二 時，傾向於塗布性佳，因此較佳。 节本毛明之光敏性樹脂組成物中，在必要時亦可再含填 劑、其他之高分子化合物、顏料分散劑、密著促進劑、抗 氧化劑、紫外線吸收劑、抗凝結劑等添加劑。 填劑之具體例可舉如玻璃、石夕膠、氧化銘等；其他之 高分子化合物之具體例可舉如聚乙烯醇、聚丙烯酸、聚乙 二醇單烧基醚、聚氟烷基丙烯酸酯等。 顏料^散劑可使用一般市售之顏料分散劑，其例可舉 士夕系t系、酉旨系、陽離子系、陰離子系、非離子系、 兩性等界面活性劑等，&等可單獨或以其2種以上組合使 6 一亞月女類等’及其他商品名KP (信越化學工業（株）製 过）I福樂（共榮化學（株）製造）、貌多普（丁⑽舰Η。—。 上述界面活性劑之例可 %乳乙烧燒基苯基喊類、聚 肪酸S曰類、脂肪酸變性聚酉旨 舉如聚環氧乙烷烷基醚類、聚 乙二醇二酯類、山梨糖醇酐脂 類、3級胺變性聚胺旨類、聚 22 315272 1285298 公司製造）、吴加福斯（大日本油墨化學工業（株）製造）、福 樂多（住友3M(株）製造）、旭加德、撒佛隆（以上為旭玻璃（株） 製造）、沙巴思（Astra Zeneca(株）製造）、efka(efka CHEMICALS公司製造）、PB821(味之素（株）製造）等。 密著促進劑之具體例可舉如乙稀三甲氧基石夕烧、乙稀 三乙氧基石夕烧、乙烯三（2_甲氧基乙氧基）石夕烧、n_(2_胺基 乙基)-3-胺基丙基曱基二甲氧基矽烷、N_(2_胺基乙基)_3_ 胺基丙基三曱氧基石夕烧、3_胺基丙基三乙氧基石夕烧、3_環 氧丙氧基丙基三甲氧基錢、3_環氧丙氧基丙基甲基二甲 氧基石夕烧、2-(3,4-環氧基環己基）乙基三甲氧基石夕烧、3_氯 丙基甲基一甲氧基石夕烧、3 -氯丙基三甲氧基石夕炫、3_甲基 丙稀酿氧基丙基三甲氧基钱、3_氫硫基丙基三甲氧基石夕 烷等。 抗氧化劑之具體例可舉如2,2，_硫代雙（4_甲基_6_第三_ 丁基酚）、2,6-二-第三-丁基_4_甲基酚等。 紫外線吸收劑之具體例可舉如、2_(3_第三-丁基·2_羥 基-5-甲基苯基)-5_氣化苯并三唑、烷氧基二苯甲酮土等。 抗凝結劑之具體例可舉如聚丙烯酸納等。 本發明之光敏性樹脂組成物可以例如如下調製。即先 將著色劑與溶劑混合，再以球磨機分散使著 下程度。此時，依其須要亦可再;吏成用= 分散劑，含（甲基）丙烯酸之黏著樹脂可全部或部份配合。 再於得到之分散液（以下亦可稱之為磨散主劑。）中加入其 餘之含（甲基）丙烯酸之黏著樹脂、光聚合性化合物及光聚 315272 23 1285298 合起始劑，或再於必要時加入添加劑，再必要時再追加溶 劑添加至達所要之濃度，即可得到光敏性樹脂組成物。 如此調製成之光敏性樹脂組成物再塗布於基板上，去 除溶劑等揮發性成份即形成層，前述層再隔光罩曝光、顯 像’即形成圖案（pattern)。 其中之基板可例舉如玻璃基板、矽基板、聚碳酸酯基 板、聚酯基板、芳族聚醯胺基板、聚醯胺亞胺基板、聚亞 胺基板、A1基板、GaAs基板等表面平坦之基板等。 此等基板亦可再經矽烷偶合劑等藥品之藥品處理、電 漿處理、離子塗層處理、濺鍍處理、氣相反應處理、真空 蒸鍍（沈積）處理等前處理。 此等基板上亦可再形成其他之著色圖像。 基板在使用矽基板之情形時，矽基板之表面亦可再形 成電荷耦合元件（CCD)、薄膜電晶體（TFT)等。 將光敏性樹脂組成物塗布於前述基板（包含已形成其 他著色圖案之基板）上，最好以一般之旋鍍機或省液鍍機或 無轴式鍍機塗布於前述基板等上，其次再將溶劑等揮發成 分經加熱乾燥（預加熱）。加熱操作一般為在約40°C至120 °C下進行1至5分鐘左右。 經如此操作後，光敏性樹脂組成物固形物即可在基板 或已形成其他著色圖案之基板上形成平坦性良好之層。 該形成之層再隔光罩曝光、顯像。 曝光可使用i光（波長365nm)、h光、g光等，以使用 i光（波長3 65nm)為佳。i光（波長365nm)使用之光源以超 24 315272 1285298 T%壓水銀燈（Ushio電機（株）製造；ΗΒ_751〇5ΑΑ 0P1)等為 <土 ’曝光I 一般為50至400mJ/cm2程度。 顯像一般使用後述含鹼性化合物及界面活性劑之顯像 液。 曝光、顯像後必要時亦可再在150°C至230°C下進行 1 〇至60分鐘程度之加熱硬化（後加熱）。 具體地’即將光敏性樹脂組成物如下塗布在基材上， 再經曝光（光硬化）及顯像，即可形成黑色矩陣或著色畫素 等。 旦’、 即先將光敏性樹脂組成物旋鍍在基板（一般為玻璃） 上’再經預加熱去除溶劑，即得平滑之塗膜。此時，塗膜 厚約為1至3/zm程度。 如此操作得到之塗膜，為得到其目的之黑色矩陣或畫 素’須再隔遮蓋光罩照射紫外線。此時，為使曝光部份整 體能均勻地照到平行光，且使光罩與基板能在正確之位置 上，最好使用光罩定位器等裝置。 之後，再使硬化完成之塗膜接觸稀鹼溶液溶解未曝光 部份，再經顯像，即可得到目的之黑色矩陣或畫素。顯像 後即可再依其必要，在150它至23(rCT 1〇至6〇分鐘程度 之加熱硬化（後加熱）。 曝光後顯像使用之顯像液一般使用含鹼性化合物與界 面活性劑之水溶液。鹼性化合物無機或有機之鹼性化合物 均可。 無機鹼性化合物之具體例可舉如氫氧化鈉、氫氧化 315272 25 1285298 鉀、磷酸氫二鈉、磷酸二* ^^ , 虱鈉、石夕年酉夂氫二銨、石粦酸二氫銨、 填酸二氫卸、石夕酸鈉、 ^ r酉文鉀、石反酸鈉、碳酸鉀、碳酸氫 鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、氨水等。 有機驗性化合物之呈獅彳丨血 具體例可舉如氫氧化四甲基銨、氫 二曱基胺、三甲基 乙基胺、單異丙基胺、二異 氧化_2-羥基乙基三甲基銨、單甲基胺 胺、單乙基胺、二乙基胺、 丙基胺、乙醇胺等。 此等無機及有機驗性介人必 留 双庇化合物可早獨或以其2種以上组 合使用。 顯像液中鹼性化合物 佳，0.03至5質量％更佳 之濃度以0.01至10質量。/〇為 驗性顯像液中之界面活性劑可任意為非離子界面活性 劑、陰離子界面活性劑、陽離子界面活性劑均可。 非離子界面活性劑之具體例可舉如聚環氧乙烧烧基 喊、聚環氧乙烷芳基醚、聚環氧乙烷烷基芳基醚、其他之 聚環氧乙烧衍生物、環氧乙烧/環氧丙烧聚絮聚合物、山梨 糠醇酐月日肪1 g日、聚壤氧乙烧山梨糖醇酐脂肪酸醋、聚環 氧乙烷山梨糖醇脂肪酸酯、丙三醇脂肪酸酯、聚環氧乙烷 脂肪酸酯、聚環氧乙统燒基胺等。 陰離子界面活性劑之具體例可舉如月桂醇硫酸酯鈉或 油醇硫酸酯鈉之高級醇硫酸鹽類，月桂基硫酸鈉或月桂基 硫酸銨之烷基硫酸鹽類，十二烷基苯磺酸鈉或十二烷基萘 磺酸鈉之烷基芳基磺酸鹽類等。 陽離子界面活性劑之具體例可舉如硬脂醯胺鹽酸鹽或 315272 26 1285298 月桂基三甲基氣化銨之胺鹽或4級銨鹽等。 此等界面活性劑可單獨或以其2種以上組合使用。 顯像液中界面活性劑之濃度一般以〇〇1至ι〇質量。/ 為宜，或0·05至8質量％更佳，〇」至5質量％又更佳里。❶ 如上光敏性樹脂組成物經塗布、乾燥，所得到之乾把 塗膜（圖像形成）經曝光以顯像之各操作，即可形成畫^ 黑色矩陣，再反複㈣色片所必須之顏色數之操作 成濾色片。 ^ 濾色膜-般是由黑色矩陣及紅、綠及藍之三原色晝素 配置在基板上所形成’因此以本發明之光敏性樹脂組成物 含-顏色所相當之著色材料經如上之操作，即可形成該色 之黑色矩陣或晝素’其他所要之顏色再財發明之光敏性 樹脂組成物含其所相當之著色材料同樣操作，即可將黑色 矩陣或三原色晝素配置在基板上。#然，本發明之光敏性 樹脂組成物亦適用於只含黑色矩陣或三原色中任一色、二 色、或三色者。遮光層之黑色矩陣亦可例如在鉻層等形成。 以本毛明之光敏性樹脂組成物製成之濾色片，可縮小 面内之膜厚差’例如在1至厚之膜中，面内膜厚之 差在〇.15^m以下，甚至可達〇〇5^m以下。因此，所得 到之滤色膜有優良之平滑性及透明性，且以其裝置於彩色 液明顯不裝置中，可以以高製成率製成品質優良之液晶顯 示面板。 本發明之光敏性樹脂組成物，可廣泛利用紫外線硬化 型油墨或光阻劑等，因此適於使用於彩色液晶顯示裝置或 27 315272 1285298 影像元件中形成晝素（著色圖像）。 實施例： 上述中已說明本發明之實施形態，但上述中所揭示本 發明之實施形態亦僅為例示，本發明之範圍並不限定於此 等實施形態。本發明之範圍如在申請專利範圍中所示，同 時亦包含與申請專利範圍意義及範圍内相等之所有變更。 以下再以實施例詳細說明本發明，但本發明並不限定於此 等實施例。以下之含量及使用量中所指之％及份，未特別 指明時均為質量基準。 本實施例中所使用之成份如下，以下亦有簡略表示 者。 (a_l)C.I·紅色顏料-254 (a-2)C.I.黃色顏料-139 (a-3)C.I·綠色顏料_36 (a_4)C.I·黃色顏料-150 (b-Ι)黏著樹脂：甲基丙烯酸與苯甲基甲基丙烯酸酯之共聚 物〔甲基丙烯酸單位與苯甲基甲基丙烯酸酯單位之比例為 質篁比（莫爾比）〕30:70，酸值為113,換算聚苯乙稀之重 里平均分子量為25,000 ’黏著樹脂中所含甲基丙稀酸之 里，對黏著樹脂之質量分率為〇 · 〇 8 %。） (b-2)黏著樹脂:曱基丙烯酸與苯曱基甲基丙烯酸酯之共聚 :〔甲基丙稀酸單位與苯甲基甲基丙烯酸料位之比例為 =量比（莫爾比）〕30:70,酸值為113，換算聚苯乙稀之重 里平均刀子篁為25’000 ’黏著樹脂中所含甲基丙婦酸之 315272 28 1285298 量’對黏著樹脂之質量分率為〇28%。） (b-3)點著樹脂：甲基丙 物〔甲基丙浠酸單…甲、二 = 丙稀酸…聚 ^ θ L 〃、本甲基甲基丙烯酸酯單位之比例另 i 莫爾比）〕3㈣，酸值為⑴，換算聚苯乙稀之重 ^均分子量為25，_’黏著樹脂中所含甲基丙稀酸之 里，對黏著樹脂之質量分率為〇 45%。） (::)=樹脂:甲基丙浠酸與苯甲基甲基丙烯酸酷之共聚 基㈣酸單位與苯甲基甲基丙賴料位之比例為 :里t (莫爾比）〕π，，酸值為ιΐ3，換算聚苯乙稀之重 Γ均分子量為25’000’黏著樹脂中所含甲基丙稀酸之 里，對黏著樹脂之質量分率為q.68%。） (b_M著m基丙_與苯甲基甲基丙烯酸醋之共聚 j甲基丙浠酸單位與苯甲基甲基丙烯酸醋單位之比例為 :里比（莫爾比）〕30:70，酸值為113，換算聚苯乙稀之重 里平均刀子里為25，〇〇〇’黏著樹脂中不含甲基丙烯酸。 ㈣黏著樹脂：甲基丙稀酸與苯甲基甲基丙烯酸醋之共聚 ^甲基丙烯酸單位與苯甲基甲基丙稀酸®旨單位之比例為 =里比（莫爾比）〕30:70，酸值為113，換算聚苯乙稀之重 里平均刀子里為35,〇〇〇 ’黏著樹脂中不含甲基丙烯酸。） (b_7)黏著樹脂:甲基丙烯酸與苯甲基甲基丙烯酸醋之共聚 =甲基丙烯酸單位與苯甲基甲基丙烯酸_單位之比例為 :里比（莫爾比）〕30:70’酸值為113，換算聚苯乙稀之重 =平均刀子里為35,〇〇〇，黏著樹脂中所含甲基丙烯酸之 量，對黏著樹脂之質量分率為〇 39%。） 29 315272 1285298 (b_8)黏著樹脂··甲基丙烯酸與苯甲基甲基丙烯酸酯之共聚 物〔甲基丙烯酸單位與苯甲基甲基丙烯酸酯單位之比例為 質量比（莫爾比）〕27:73，酸值為83，換算聚苯乙烯之重量 平均分子量為25,000，黏著樹脂中不含甲基丙烯酸。） (b_9)黏著樹脂：甲基丙烯酸與苯甲基甲基丙烯酸酯之共聚 物〔甲基丙烯酸單位與笨甲基甲基丙烯酸酯單位之比例為 質量比（莫爾比）〕27:73，酸值為83,換算聚苯乙烯之重量 平均分子量為25,000,黏著樹脂中所含甲基丙烯酸之量， 對黏著樹脂之質量分率為〇·4ΐ%。） (b-10)黏著聚合物：甲基丙烯酸與苯甲基甲基丙烯酸酯之共 聚物〔甲基丙烯酸單位與苯曱基甲基丙烯酸酯單位之比例 為質量比（莫爾比）〕35:65，酸值為135，換算聚苯乙烯之 重量平均分子量為28，000，黏著樹脂中所含甲基丙浠酸之 量，對黏著樹脂之質量分率為〇· 1 〇%。） (b-11)黏著樹脂：甲基丙烯酸與苯甲基甲基丙烯酸酯之共聚 物〔曱基丙稀酸單位與苯甲基甲基丙烯酸酯單位之比例為 質量比（莫爾比）〕30:70，酸值為113，換算聚苯乙烯之重 量平均分子量為25，000,黏著樹脂中所含甲基丙烯酸之 量，對黏著樹脂之質量分率為0.02%。） (e-1)光聚合性化合物：二季戊四醇六丙烯酸酯（日本化藥 (株）製造，KAYARAD DPHA) (d-1)光聚合起始劑：2-曱基-2-嗎啉代4-(4-甲基硫代苯基） 丙烧· 1 -酮 (4-2)光聚合起始劑.2,4-雙（二氣甲基）>><6-胡椒基_1，3,5-三。丫 30 315272 1285298 嗪 (d-3)光聚合起始劑：2-苯甲基-2-二曱基胺基-；ι_(4_嗎琳代 苯基）丁烷-1-酮 (e-Ι)光聚合起始輔劑：2,4-二乙基噻噸酮 (e-2)光聚合起始輔劑雙（二乙基胺基）二苯甲酉同 (f)溶劑：丙二醇單甲醚乙酸酯 (g)環氧化合物〔鄰甲酚酚醛清漆型環氧樹脂，「81；]^1-EPOXY ESCN-195XL-80」（住友化學工業（株）製造）〕 實施例1 〔光敏性樹脂組成物1及樹脂溶液1之調製〕 (a_l) (a-2) 聚醋系顏料分散劑 (b-1) (c-1) (d_l) (d-2) (e-1) (f) (g) 混合後即得光敏性樹脂組成物1 5·36質量份 L34質量份 2.54質量份 5·〇4質量份 3 · 3 6質量份 〇 · 5 0質量份 0 · 5 0質量份 0 · 5 0質量份 79·91質量份 0·84質量份 。光敏性樹脂組成物1中 甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比為 0.02% 〇 以及 315272 31 1285298 (b-l) 5.00質量份 (f) 45.00質量份 混合後即得樹脂溶液1。 取康寧公司製造之5英吋方形#173 7玻璃基板，依序 以中性洗劑、水及醇洗淨後乾燥。再將上述光敏性樹脂組 成物1旋鍵在該玻璃基板上，其次在加熱箱中於1 〇 〇 t下 預加熱3分鐘去除揮發成份。再經冷卻後，再於在大氣條 件下經Ushio電機（株）製造之超高壓水銀燈以15〇mJ/cm2 曝光量照射，即得塗膜A。 另外，以樹脂溶液1取代光敏性樹脂組成物1，如同 上述操作，即得塗膜B。 再另外取在中段階段預加熱後所得到塗膜A之基板，不經 曝光而浸潰於含0.12%之非離子界面活性劑與〇 〇4%之氫 氧化鉀之水性顯像液中，在23 I下顯像8〇秒，再經水洗、 乾燥後即得基板C。 (評定） 上述塗膜A在大氣條件下經22(rc加熱6〇分鐘，塗膜 A :失重比例為8.5%。其減少部份並未完全去除而污染加 熱箱，但該加熱箱内之污染物再自内壁落下附著於塗膜上 因此改善其製成率。 、 塗膜B經上述相同之處理，其失重比例為15 3%。 上述基板C之透光率為100%’殘留物中無光_ 脂組成物。以膜厚計（DEKTAK 3 ((株肌心製 内膜厚之差為18A。 315272 32 1285298 實施例2 〔光敏性樹脂組成物G之調製〕 4·574質量份 1 · 9 6 0質量份 1 ·502質量份 4 · 7 2 2質量份 3 · 8 6 3質量份 1 · 0 3 0質量份 〇·343質量份 81·960質量份 (a-3) (a-4) 聚酯系顏料分散劑 (b_l〇) (c_l) (d-3) (e-2) (Ο 混合後即得光敏性樹脂組成物G。 取玻璃基板〔康寧公司製造，#1737〕，以旋艘法塗布光 敏性樹脂組成物G，再於1 〇〇°C預加熱3分鐘乾燥去除揮 發成份，即得光敏性樹脂組成物層。 該光敏性樹脂組成物層經冷卻後，不隔光罩以丨光〔波 長365nm〕照射。i光之光源使用超高壓水銀燈，曝光量 為150mJ/cm2。其次再將曝光後之玻璃基板（其表面上已形 成著色光敏性樹脂組成物層）浸於顯像液（即含質量分率各 為氫氧化鉀0.05%、丁基萘磺酸鈉〇 2%之水溶液）中顯像， 以純水洗淨。再於大氣條件下經22〇t加熱2〇分鐘，即形 成透明圖像。得到之該圖像上並無殘留物。 再於4述已形成綠晝素之基板上，以旋鍍法塗布光敏 性樹脂組成物丨，再於1〇〇。(：下乾燥3分鐘去除揮發成份， 即形成光敏性樹脂組成物層。其次再將玻璃基板浸於顯像 315272 33 1285298 液（即含質量分率各為氫氧化鉀0 05%、丁基萘磺酸鈉〇 ·2% 之水溶液）中顯像，以純水洗淨。再於大氣條件下經22(rc 加熱20分鐘，即形成透明圖像。測定在塗布光敏性樹脂組 成物1形成塗膜前後綠晝素部份明度值之變化（以〇SP-SP2〇0(〇lymPus光學（株）製造）測定。）為〇 99。 實施例3 〔光敏性樹脂組成物2及樹脂溶液2之調製〕 除變更（b-i)為（b-2)外，以實施例丨同樣操作，即得光 敏性樹脂組成物2及樹脂溶液2。光敏性樹脂組成物2中 甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比為 0.07%。 (評定） 除使用光敏性樹脂組成物2及樹脂溶液2外，相同於 實施例1在大氣條件下經22(TC加熱6〇分鐘，測定其失重 比例，光敏性樹脂組成物2為9· 1 %、樹脂溶液2為2丨·4%。 其減少部伤並未完全去除而污染加熱箱，但加熱箱内之污 染物再自内壁落下附著於塗膜上因此改善其製成率。基板 之透光率為100%，殘留物中無光敏性樹脂組成物。面内 膜厚之差為22Α。 除變更光敏性樹脂組成物丨為光敏性樹脂組成物2 外，相同於實施例1之操作，測定其綠畫素部份明度值之 變化為1.22。 實施例4 〔光敏性樹脂組成物之調製〕 315272 34 1285298 除變更（b-l)為（b_3)外，相同於實施例1之操作，即得 光敏性樹脂組成物3及樹脂溶液3。光敏性樹脂組成物3 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為 0.11 %。 (評定） 除使用光敏性樹脂組成物3及樹脂溶液3外，相同於 實施例1之操作，在大氣條件下經220°C加熱60分鐘測定 其失重比例，光敏性樹脂組成物3為9·6%、樹脂溶液3為 2 6 · 4 。其減少部份並未完全去除而污染加熱箱内，但加 熱箱内之污染物再自内壁落下附著於塗膜上因此改善其製 成率。基板之透光率為100%，殘留物中無光敏性樹脂組 成物。面内膜厚之差為24Α。 在實施例2中除了變更光敏性樹脂組成物1為光敏性 樹脂組成物3以外，其他相同於實施例2之操作，測定綠 畫素部份明度值之變化為0.87。 實施例5 〔光敏性樹脂組成物之調製〕 除變更（b-Ι)為（b-7)外，相同於實施例丨之操作，即得 光敏性樹脂組成物4及樹脂溶液4。光敏性樹脂組成物4 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為 0.10〇/〇 〇 (評定） 除使用光敏性樹脂組成物4及樹脂溶液4外，相同於 實施例1之操作，在大氣條件下經22(rc加熱6〇分鐘測定 315272 35 1285298 其失重比例’光敏性樹脂組成物4為8.6%、樹脂溶液4為 24.2°/。。其減少部份並未完全去除而污染加熱箱，但加熱 箱内之污染物再自内壁落下附著於塗膜上因此改善其製成 率。基板之透光率為100%，殘留物中無光敏性樹脂組成 物。面内膜厚之差為23A。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 月曰組成物4外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為1.1 9。 實施例6 〔光敏性樹脂組成物5及樹脂溶液5之調製〕 除變更（b-Ι)為（b-9)外，相同於實施例丨之操作，即得 光敏性樹脂組成物5及樹脂溶液5。光敏性樹脂組成物5 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為 0.10% 〇 (評定） 除使用光敏性樹脂組成物5及樹脂溶液5外，相同於 實施例1在大氣條件下經22(rc加熱6〇分鐘，測定其失重 比例，光敏性樹脂組成物5為9_5%、樹脂溶液5為27 9%。 其減少部份並未完全去除而污染加熱箱，但加熱箱内之污 染物再自内壁落下附著於塗膜上因此改善其製成率。基板 之透光率為1 00%，殘留物中無光敏性樹脂組成物。面内 膜厚之差為19A。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 脂組成物5外，相同於實施例2之操作，測定綠畫素部份 315272 36 1285298 明度值之變化為1.42。 比較例1 〔光敏性樹脂組成物6及樹脂溶液6之調製〕 除變更（b-Ι)為（b-4)外，相同於實施例丨之操作，即得 光敏性樹脂組成物6及樹脂溶液6。光敏性樹脂組成物6 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為 0.17%。 (評定） 除使用光敏性樹脂組成物6及樹脂溶液6外，相同於 實施例1在大氣條件下經22(rc加熱6〇分鐘，測定其失重 比例，光敏性樹脂組成物6為1〇·6%、樹脂溶液6為371%。 其減少部份並未完全去除而污染加熱箱，加熱箱内之污染 物再自内壁落下附著於塗膜上減低其製成率。基板之透光 率為100%，殘留物中無光敏性樹脂組成物。面内膜厚之 差為28Α 。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 月曰組成物6外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為1.72。 比較例2 〔光敏性樹脂組成物7及樹脂溶液7之調製〕 ^除變更（b-Ι)為（b-5)外，相同於實施例1之操作，即得 光敏性樹脂組成物7及樹脂溶液7。光敏性樹脂組成物7 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為0 % 〇 315272 37 1285298 (評定） 除使用光敏性樹脂組成物7及樹脂溶液7外，相同於 實施例1之操作，基板之透光率為97%，基板上餘留光敏 性樹脂組成物之殘留物。面内膜厚之差為32A。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 月曰組成物7外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為3.02。 比較例3 〔光敏性樹脂組成物8及樹脂溶液8之調製〕 除變更（b-Ι)為（b-6)外，相同於實施例1之操作，即得 光敏性樹脂組成物8及樹脂溶液8。光敏性樹脂組成物8 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為0%。 (評定） 除使用光敏性樹脂組成物8及樹脂溶液8外，相同於 實施例1之操作，基板之透光率為96%，基板上餘留光敏 性樹脂組成物之殘留物。面内膜厚之差為22A。 在實施例2中除變更光敏性樹脂組成物1為光敏性樹 脂組成物8外，相同於實施例2之操作，測定綠晝素部份 明度值之變化為2.89。 比較例4 〔光敏性樹脂組成物9及樹脂溶液9之調製〕 除變更（b-Ι)為（b-8)外，相同於實施例1之操作，即得 光敏性樹脂組成物9及樹脂溶液9。光敏性樹脂組成物9 315272 38 1285298 中甲基丙烯酸之含量對光敏性樹脂組成物固形物之質量比 為0% 〇 (評定） 除使用光敏性樹脂組成物9及樹脂溶液9外，相同於 實施例1之操作，基板之透光率為95%，基板上餘留光敏 性樹脂組成物之殘留物。面内膜厚之差為3 2 A。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 脂組成物”卜，相同於實施例2之操作，測定綠畫素部份 明度值之變化為5.89，因此不佳。 比較例5 〔光敏性樹脂組成物1 〇之調製〕 變更（b-l)為（b_5)並加人0.2 f量份之丙二酸，其他則 相同於實施例1之操作，即得光敏性樹脂組成物ι〇。光敏 性樹脂組成物1〇中甲基丙烯酸之含量對光敏性樹脂組成 物固形物之質量比為0%’纟中丙二酸之含量對光敏性樹 脂組成物固形物之質量比為1 · 〇0/〇。 (評定） 除使用光敏性樹脂組成物1〇外，相同於實施例丨之操 作’基板之透光率為100%，基板上未餘留光敏性樹脂組 成物之殘留物。面内膜厚之差為88A，因此不佳。 在實施例2中除變更光敏性樹脂組成物i為光敏性樹 脂組成物i"卜，相同於實施食"之操作，測定綠畫素部份 明度值之變化為6.42，因此不佳。 比較例6 315272 39 1285298 〔光敏性樹脂組成物1 1之調製〕 變更（b-l)為（b-5)並加入0.2質量份之丙二酸，其他則 相同於實施例1之操作，即得光敏性樹脂組成物u。光敏 性樹脂組成物11中甲基丙烯酸之含量對光敏性樹脂組成 物固形物之質量比為0%，其中丙二酸之含量對光敏性樹 脂組成物固形物之質量比為1〇%。 (評定） 除使用光敏性樹脂組成物丨丨外，相同於實施例丨之操 作，基板之透光率為100%，基板上未餘留光敏性樹脂組 成物之殘留物。面内膜厚之差為82A，因此不佳。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 脂組成物1 0外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為6.44，因此不佳。 比較例7 〔光敏性樹脂組成物12之調製〕 變更（b-Ι)為（b-11)外其他相同於實施例丨之操作，即 知光敏性樹脂組成物12。光敏性樹脂組成物丨2中甲基丙 烯酸之含量對光敏性樹脂組成物固形物之質量比為 0.005% 〇 (評定） 除了使用光敏性樹脂組成物丨2，樹脂溶液12以外， 相同於實施例1之操作，基板之透光率為98%，基板上餘 留光敏性樹脂組成物之殘留物。面内膜厚之差為3 〇 A。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 40 315272 1285298 脂組成物12外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為3.00。 比較例8 〔光敏性樹脂組成物1 3之調製〕 變更（b-Ι)為（b-5)並加入〇·〇2質量份之丙二酸，其他 相同於實施例1之操作，即得光敏性樹脂組成物13。光敏 性樹脂組成物中甲基丙烯酸之含量對光敏性樹脂組成物固 形物之質量比為0%，其中丙二酸之含量對光敏性樹脂組 成物固形物之質量比為〇· 1 %。 (評定） 除使用光敏性樹脂組成物13外，相同於實施例1之操 作，基板之透光率為98%，基板上餘留光敏性樹脂組成物 之殘留物。面内膜厚之差為52人，因此不佳。 在實施例2中除變更光敏性樹脂組成物丨為光敏性樹 脂組成物13外，相同於實施例2之操作，測定綠畫素部份 明度值之變化為4.62，因此不佳。 比較例9 〔光敏性樹脂組成物14之調製〕 變更（b-Ι)為（b-5)並加入0·02質量份之丙二酸，其他 相同於實施例1之操作，即得光敏性樹脂組成物14。光敏 性樹脂組成物1 4中甲基丙烯酸之含量對光敏性樹脂組成 物固形物之質量比為0% ’其中丙二酸之含量對光敏性樹 脂組成物固形物之質量比為〇 ·丨〇/〇。 (評定） 315272 41 1285298 除使用光敏性樹脂組成物14外，相同於實施例1之操 作，基板之透光率為98。/。，基板上餘留光敏性樹脂組成物 之殘留物。面内膜厚之差為54A，因此不佳。 在實施例2中除變更光敏性樹脂組成物1為光敏性樹 脂組成物14外，相同於實施例2之操作，測定綠晝素部份 明度值之變化為4·74，因此不佳。 產業上利用夕 依照本發明可以提供一種光敏性樹脂組成物， 像部份中殘留物之餘留少、，可製成平坦性優良之畫;。 處理二卜加：用/發明光敏性樹脂組成物’其後步驟之熱 物之片二：Γ染之原因造成製成率之降低及顯像殘留 率之降低兩問題可㈣衡地解決 M局生產性製成高品質之濾色膜。 315272 42(Refer to, for example, Japanese Laid-Open Patent Publication No. 7- Kaikai No. 7-10913, etc.), etc., in which a seat is used (refer to, for example, Japanese Patent Laid-Open Publication No. Hei.), 2, 2,-double 2, 2'-double ( 2_ gas 1 which is -4 4 2,2'-bis(2-phenylphenyl M,4,5,5i_tetraphenylbisimidazole, fluorene 2,-bisbiphenyl)-4,4' 5,5'-tetraphenylbisimidazole is preferred. The polyfunctional thiol compound is a compound containing two or more thiol groups in the molecule, particularly an aliphatic hydrocarbon polyfunctional sulfur containing a plurality of thiol groups on the aliphatic hydroxyl group. The compound is preferred. The aliphatic hydrocarbon polyfunctional thiol compound may, for example, be hexanedithiol, decane monothiol, 1,4-dimethylthiobenzene or butanediol dithiopropionate, Butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane thioglycolate, butanediol dithiopropionate, trimethylolpropane Thiopropionate, trimethylolpropane thioglycolate, pentaerythritol thiopropionate, pentaerythritol thioglycolate, hydroxyethyl thiopropionate, multi-hydroxyl compound Thioglycolate, Propionate, etc., wherein trimethylolpropane thiopropionate, trimethylolpropenyl thioglycolate, pentaerythritol thiopropionate, etc. are preferably used, and pentaerythritol bismuth sulfide is used. Further, the photopolymerization initiator may be used in combination with the photopolymerization initiator used in the above-mentioned photopolymerization initiator, and examples thereof include a benzoin system and a benzophenone system. The thioxanthone-based, anthraquinone-based initiator, and the like. More specifically, the following compounds can be used: These may be used singly or in combination of two or more kinds thereof. (i) The benzoin system may be exemplified as a benzophenone. Benzene, methyl benzoate, styrene ether, benzoin isopropyl ether, benzoin, etc., (ii) benzophenone can be exemplified as benzophenone, 〇 benzoquinone Methyl formate, 4_phenylbenzophenone, vulcanized 4-benzyl-3-yl, diphenyl, 4,3,4-diphenyl, 3,3,4,4,4-tetra(t-butylperoxycarbonyl) Benzene ketone, 2,4,6•trimethyldibenzophenone, etc., (iii) thioxanthone can be exemplified by 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2,4_di-thioxanthone, ^ "·propoxy thiophene S is equivalent, (iv) lanthanide can be exemplified by 9,1 〇 _ dimethoxy oxime, 2 ethyl _9, 1 〇 _ dimethoxy oxime, 9, 1 〇-diethoxy hydrazine, 2_ethyl _9, 1 〇 _ diethoxy hydrazine, etc., (v) Other examples may be exemplified by oxidation of 2,4,6-trimethylbenzimidium diphenyl Phosphine, 2, 2, _ bis (〇-gas base)-4,4,,5,5,_tetraphenyl 丨, 2, _bisimidazole, ι〇_ butyl_2_gas A# (four) ' 2_ethyl蒽® quinone, benzyl, 9,10-phenanthrene, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. The photopolymerization initiator can be used alone or in multiples thereof. Used in combination. A photopolymerization starting adjuvant may also be used in combination in the photopolymerization initiator. The photopolymerization starting adjuvant may, for example, be an amine compound, an alkoxy onion compound or a thioxanthone compound. The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, 4-2, 4,4,4,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1,1 Methylamine isoformic acid isoamyl ester, benzoic acid-2-dimethylaminoethyl ester, 4-monomethylamine benzoic acid-2-ethylhexyl ester, hydrazine, hydrazine-dimercapto-p-toluidine, 4, 4匕 bis(monomethylamino)benzophenone (commonly known as Michler, sketone), 4,4'-bis(diethylamino)benzophenone, 4,4, _Bis(ethylmethylamino)benzophenone or the like, wherein 4,4,-bis(diethylamino)benzhydryl is preferred. The alkylene oxide compound may, for example, be 9,1 fluorene-dimethoxy hydrazine, 2-ethyl 9,1 fluorene monomethoxy hydride, 91 〇 diethoxy hydrazine, 2 _ ethyl _ 91 〇 _ diethyl hydrazine and the like. The oxime ketone compound may, for example, be 2 isopropyl thioxanthone, 4 isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, or gas. Propoxyl ° strontonone and the like. For the photopolymerization starting agent, a commercially available photopolymerization starting agent may be used, for example, under the trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.). The combination of the photopolymerization initiator and the photopolymerization starting adjuvant may, for example, be diethoxyethyl benzene/4,4'-bis(diethylamino)benzophenone or methyl-2-? Linde_1-(4-methylthiophenyl)propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1- Phenylpropane-indole-ketone/4,4,_bis(diethylamino)benzophenone, benzyldimethylketal/4,4,-bis(diethylamino)benzol _, 2-hydroxy-2-methyl_1_[4-(2-hydroxyethoxy)phenyl]propanone/4,4, bis(diethylamino)benzophenone, 1-hydroxyl ring Hexyl phenyl ketone / 4,4, bis (diethylamino) dibenzophenone, 2-yl-2-mercapto-1-[4-(1-methylvinyl)phenyl]propane 1-ketone oligomer/4,4,-bis(diethylamino)dilum 20 315272 1285298 anthrone, 2-benzyl-2-oxindoleamino-morpholinophenyl) Butane β1 ketone / 4,4'-bis(diethylamino)benzhydryl- and the like, wherein 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane 1_keto/4,4,_bis(diethylamino)benzophenone is preferred. The photopolymerization initiator is preferably from 0.1 to 40 parts by mass, based on the total of 100 parts by weight of the adhesive resin and the photopolymerizable compound, preferably from 2 parts by mass to parts by mass. The photopolymerization starting adjuvant is preferably from 0. 1 to 50 parts by mass, and more preferably from i to 4 parts by mass, based on 100 parts by mass of the adhesive resin and the photopolymerizable compound. When the photopolymerization initiator content is from 1 to 4 parts by mass, the sensitivity of the photosensitive resin composition tends to increase, the strength of the halogen component is formed using the photosensitive resin composition, or the aforementioned pixel is increased. The smoothness of the surface is therefore preferred. Further, when the photopolymerization starting adjuvant is 〇·丨 to 5 〇 parts by mass, the sensitivity of the photosensitive resin composition tends to increase, and the productivity of the color filter film formed by the photosensitive resin composition is improved, so that it is preferable. . The photosensitive resin composition of the present invention may also contain a solvent. Examples of the solvent include ethylene glycol monomethyl scale, ethylene glycol monoethyl sulfonate, ethylene glycol monopropyl scale, and ethylene glycol monoalkyl ether of ethylene glycol monobutyl ether; diethylene glycol II Alcohol, diethylene glycol diethylene sulphate, diethylene glycol dipropyl ether, and ethylene glycol dialkyl ether, one of diethylene glycol monobutyl ether; thioglycolic acid fiber S, and ethyl acetate fiber S Ethyl alcohol-based acetic acid vinegar; propylene glycol monomethyl acetate, propylene glycol monoethyl acetate, propylene glycol monopropyl acetate, methoxybutyl acetate, and methoxypentyl Alkyl glycol alkyl ether acetates of acid esters; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; butanone, 21 315272 1285298 propyl ', methyl n-amyl fluorenone, fluorenyl Ketones such as isobutyl ketone and cyclohexanone; propyl xiao, butanol, hexanol, cyclohexanol, ethylene glycol 'and glycerol and the like '3-ethoxypropionate ethyl ester, and 3_ a cyclic ester such as butyrolactone such as methyl methoxypropionate. Among them, propylene glycol monomethyl ether acetate is preferred. These solvents may be used singly or in combination of two or more kinds thereof. The content of the solvent in the photosensitive resin composition is preferably 6 Å to 9% by mass, more preferably 70 to 85% by mass. When the content of the solvent is from (9) to the mass of two, it tends to be excellent in coatability, and therefore it is preferred. The photosensitive resin composition of the present invention may further contain additives such as a filler, other polymer compound, a pigment dispersant, a adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-coagulant, if necessary. Specific examples of the filler include glass, shijiao, oxidized, etc., and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylic acid. Ester and the like. As the pigment/powder, a commercially available pigment dispersant can be used, and examples thereof include a surfactant system such as a t-type, a t-type system, a cationic system, an anionic system, a nonionic system, and an amphoteric surfactant. In the case of the combination of the two or more types, the 6th Asian Women's Class and other trade names KP (made by Shin-Etsu Chemical Co., Ltd.) I Fule (manufactured by Kyoei Chemical Co., Ltd.) and Mondo (10) Η — — — — — — — — — — — 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述Diesters, sorbitan esters, grade 3 amine denatured polyamines, poly 22 315272 1285298 company, Wu Jiafusi (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fuledo (Sumitomo 3M) Manufactured by the company), Xujiade, Safron (above), manufactured by Asahi Glass Co., Ltd., Sabbath (manufactured by Astra Zeneca Co., Ltd.), efka (manufactured by efka CHEMICALS), PB821 (Ajinomoto Co., Ltd.) Manufacturing) and so on. Specific examples of the adhesion promoter include, for example, ethylene trimethoxy sulphur, ethylene triethoxy sulphur, ethylene tris(2-methoxyethoxy), and n_(2_amino B 3-aminopropylmercaptodimethoxydecane, N-(2-aminoethyl)_3_aminopropyltrimethoxy oxanthine, 3-aminopropyltriethoxylate , 3_glycidoxypropyltrimethoxy money, 3_glycidoxypropylmethyldimethoxycarbazide, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy基石夕烧, 3_Chloropropylmethyl-methoxy methoxy sulphate, 3-chloropropyltrimethoxy sulphate, 3-methylpropanoloxypropyltrimethoxy ketone, 3-hydrogenthio Propyltrimethoxy oxalate and the like. Specific examples of the antioxidant include 2,2,-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like. . Specific examples of the ultraviolet absorber include 2_(3_tris-butyl-2-hydroxy-5-methylphenyl)-5-vaporized benzotriazole, alkoxybenzophenone, and the like. . Specific examples of the anti-coagulant include sodium polyacrylate. The photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the colorant is first mixed with the solvent, and then dispersed by a ball mill to the extent that it is lowered. At this time, it may be further required; if it is used as a dispersant, the adhesive resin containing (meth)acrylic acid may be blended in whole or in part. Adding the remaining (meth)acrylic acid-containing adhesive resin, photopolymerizable compound, and photopolymerization 315272 23 1285298 starting agent to the obtained dispersion (hereinafter also referred to as a grinding main component), or An additive is added as necessary, and if necessary, an additional solvent is added to the desired concentration to obtain a photosensitive resin composition. The photosensitive resin composition thus prepared is applied onto a substrate to remove a volatile component such as a solvent to form a layer, and the layer is exposed and developed by a mask to form a pattern. The substrate may, for example, be a glass substrate, a tantalum substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyimide substrate, a polyimide substrate, an A1 substrate, a GaAs substrate, or the like. Substrate, etc. These substrates may also be subjected to a pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion coating treatment, a sputtering treatment, a gas phase reaction treatment, or a vacuum evaporation (deposition) treatment. Other colored images can be formed on these substrates. When the substrate is used in the case of a substrate, a charge coupled device (CCD), a thin film transistor (TFT) or the like may be further formed on the surface of the substrate. The photosensitive resin composition is applied onto the substrate (including a substrate on which another colored pattern is formed), and is preferably applied to the substrate or the like by a general spin coater, a liquid-saving plating machine or a shaftless plating machine, and then The volatile component such as a solvent is dried by heating (preheating). The heating operation is generally carried out at about 40 to 120 ° C for about 1 to 5 minutes. By doing so, the photosensitive resin composition solid can form a layer having good flatness on the substrate or the substrate on which the other colored pattern has been formed. The formed layer is exposed and developed by a mask. For the exposure, i-light (wavelength 365 nm), h-light, g-light, or the like can be used, and i-light (wavelength 3 65 nm) is preferably used. The light source used for i-ray (wavelength 365nm) is super 24 315272 1285298 T% pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.; ΗΒ_751〇5ΑΑ 0P1) The <soil' exposure I is generally in the range of 50 to 400 mJ/cm2. For the development, a developing solution containing a basic compound and a surfactant described later is generally used. After exposure and development, if necessary, heat hardening (post-heating) of about 1 Torr to 60 minutes may be carried out at 150 ° C to 230 ° C. Specifically, a photosensitive resin composition is applied onto a substrate as follows, and after exposure (photohardening) and development, a black matrix or a colored pixel can be formed. Once the photosensitive resin composition is spin-plated onto a substrate (generally glass), the solvent is removed by preheating to obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 3/zm. The coating film thus obtained is irradiated with ultraviolet rays for the purpose of the black matrix or the image of the mask. At this time, in order to uniformly expose the exposed portion to the parallel light and to position the mask and the substrate in the correct position, it is preferable to use a device such as a mask locator. Then, the hardened film is contacted with a dilute alkali solution to dissolve the unexposed portion, and then developed to obtain a black matrix or a pixel of interest. After development, it can be further used according to its necessity, from 150 to 23 (rCT 1 〇 to 6 〇 minutes of heat hardening (post-heating). After exposure, the imaging solution used generally uses basic compounds and interface activity. An aqueous solution of the agent. The basic compound may be an inorganic or organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide 315272 25 1285298 potassium, disodium hydrogen phosphate, and phosphoric acid II*^, 虱Sodium, Shi Xiian 酉夂 dihydrogen ammonium dihydrogen, ammonium dihydrogen ammonium sulphate, dihydrogen sulphate, sodium sulphate, potassium sulphate, sodium sulphate, potassium carbonate, sodium bicarbonate, potassium bicarbonate , sodium borate, potassium borate, ammonia, etc. Specific examples of the organic test compound of lion's blood may be exemplified by tetramethylammonium hydroxide, hydrogendidecylamine, trimethylethylamine, monoisopropylamine. , diiso-oxidized 2-hydroxyethyltrimethylammonium, monomethylamine, monoethylamine, diethylamine, propylamine, ethanolamine, etc. These inorganic and organic properties must be double The compound can be used alone or in combination of two or more. The alkaline compound in the developing solution is good, 0.03 to 5 The concentration of the better % is 0.01 to 10 mass. The surfactant in the photographic imaging solution can be any nonionic surfactant, anionic surfactant or cationic surfactant. Nonionic surfactant Specific examples thereof include polyepoxybutyl ketone, polyethylene oxide aryl ether, polyethylene oxide alkyl aryl ether, other polyepoxy derivatives, and ethylene oxide/ Epoxy-acrylic poly-flocculating polymer, sorbitol sulphate, 1 g day, polyoxo-oxyethylene sorbitan fatty acid vinegar, polyethylene oxide sorbitol fatty acid ester, glycerol fatty acid ester, Polyethylene oxide fatty acid ester, polyepoxyethane alkylamine, etc. Specific examples of the anionic surfactant include higher alcohol sulfates of sodium lauryl sulfate or sodium oleyl sulfate, and lauryl sulfate. An alkylsulfate of sodium or ammonium lauryl sulfate, an alkyl aryl sulfonate of sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate, etc. Specific examples of the cationic surfactant can be mentioned Such as stearylamine hydrochloride or 315272 26 1285298 ammonium lauryl trimethylated ammonium salt Or a grade 4 ammonium salt, etc. These surfactants may be used singly or in combination of two or more kinds thereof. The concentration of the surfactant in the developing solution is generally 〇〇1 to ι〇 mass. / is appropriate, or 0. 05 It is more preferably 8% by mass, more preferably 5% by mass, and more preferably ❶. The photosensitive resin composition is coated and dried, and the obtained dried film (image formation) is exposed to light for each operation. , the black matrix can be formed, and the color number necessary for the color film is repeated (4) to operate as a color filter. ^ The color filter film is generally arranged on the substrate by a black matrix and three primary colors of red, green and blue. Thus, the coloring material corresponding to the photosensitive resin composition of the present invention containing the color is subjected to the above operation to form a black matrix of the color or a halogen-containing other color of the desired photosensitive resin. The black matrix or the three primary color elements can be disposed on the substrate in the same manner as the corresponding colored material. #然, The photosensitive resin composition of the present invention is also suitable for those containing only one of the black matrix or the three primary colors, two colors, or three colors. The black matrix of the light shielding layer may also be formed, for example, in a chrome layer or the like. The color filter made of the photosensitive resin composition of the present invention can reduce the difference in film thickness in the surface. For example, in a film of 1 to thick, the difference in in-plane film thickness is less than 1515 cm, and may even be Up to 5^m. Therefore, the obtained color filter film has excellent smoothness and transparency, and it can be made into a liquid crystal display panel of high quality at a high production rate because the device is obviously not used in the color liquid. The photosensitive resin composition of the present invention can be widely used as an ultraviolet curable ink or a photoresist, and is therefore suitable for use in a color liquid crystal display device or a 27 315272 1285298 image element to form a halogen (colored image). EMBODIMENT OF THE INVENTION The embodiments of the present invention have been described above, but the embodiments of the present invention disclosed above are merely illustrative, and the scope of the present invention is not limited to the embodiments. The scope of the present invention is to be construed as being limited by the scope of the appended claims. Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. The % and parts referred to in the following contents and amounts are based on quality unless otherwise specified. The components used in this embodiment are as follows, and the following are also briefly shown. (a_l) CI·Red Pigment-254 (a-2) CI Yellow Pigment-139 (a-3) CI·Green Pigment _36 (a_4) CI·Yellow Pigment-150 (b-Ι) Adhesive Resin: Methacrylic Acid Copolymer with benzyl methacrylate [proportion of methacrylic acid unit and benzyl methacrylate unit is mass to enthalpy ratio (Morby)] 30:70, acid value is 113, converted to polyphenylene The average molecular weight in the lean weight is 25,000' in the methyl acrylate contained in the adhesive resin, and the mass fraction of the adhesive resin is 〇· 〇 8 %. (b-2) Adhesive resin: copolymerization of mercaptoacrylic acid with benzoyl methacrylate: [ratio of methyl methic acid unit to benzyl methacrylic acid level = ratio (molby) 〕30:70, the acid value is 113, the average knife 换算 in the weight of polystyrene is 25'000 ' 315272 28 1285298 of the amount of methyl propyl acrylate contained in the adhesive resin. The mass fraction of the adhesive resin is 〇 28%. (b-3) point resin: methyl propyl [methyl propyl phthalic acid mono... A, bis = acrylic acid... poly ^ θ L 〃, the ratio of this methyl methacrylate unit, another i Moore Ratio)]3 (4), the acid value is (1), and the weight average molecular weight of the polystyrene is 25, and the mass fraction of the adhesive resin in the methacrylic acid contained in the adhesive resin is 〇45%. ) (::) = Resin: the ratio of methyl propyl phthalic acid to benzyl methacrylic acid copolymer (4) acid unit and benzyl methacrylate material: ri t (morbi) π The acid value is ιΐ3, and the weight average molecular weight of the polystyrene is 25'000', and the mass fraction of the adhesive resin is q.68%. (b_M with m-propyl propylene _ and benzyl methacrylate varnish copolymer j methacrylic acid unit and benzyl methacrylate vinegar unit ratio: Libi (Morbi) 30:70, The acid value is 113, the average knives in the weight of polystyrene is 25, and the 黏' adhesive resin does not contain methacrylic acid. (4) Adhesive resin: copolymerization of methyl acrylate and benzyl methacrylate ^The ratio of methacrylic acid unit to benzyl methacrylic acid® unit is =Riebi (Morbi) 30:70, acid value is 113, the average knife in the weight of polystyrene is 35 , 〇〇〇 'Adhesive resin does not contain methacrylic acid.) (b_7) Adhesive resin: copolymerization of methacrylic acid and benzyl methacrylate vinegar = ratio of methacrylic acid unit to benzyl methacrylic acid _ unit For: Ribbi (Malbi)] 30:70' acid value is 113, the weight of polystyrene is converted to 35 in the average knife, 〇〇〇, the amount of methacrylic acid contained in the adhesive resin, adhesion The mass fraction of the resin was 〇39%. ) 29 315272 1285298 (b_8) Adhesive resin · Copolymer of methacrylic acid and benzyl methacrylate [mass ratio of methacrylic acid unit to benzyl methacrylate unit is mass ratio (molby)] 27:73, the acid value is 83, the weight average molecular weight of the converted polystyrene is 25,000, and the adhesive resin does not contain methacrylic acid. (b_9) Adhesive resin: copolymer of methacrylic acid and benzyl methacrylate [mass ratio of methacrylic acid unit to stupid methyl methacrylate unit is mass ratio (molby)] 27:73, The acid value was 83, the weight average molecular weight of the converted polystyrene was 25,000, and the amount of methacrylic acid contained in the adhesive resin was 〇·4% by mass for the adhesive resin. (b-10) Adhesive polymer: copolymer of methacrylic acid and benzyl methacrylate [mass ratio of methacrylic acid unit to benzoyl methacrylate unit is mass ratio (molby)] 35 : 65, the acid value is 135, the weight average molecular weight of the converted polystyrene is 28,000, the amount of methylpropionic acid contained in the adhesive resin, and the mass fraction of the adhesive resin is 〇·1 〇%. (b-11) Adhesive resin: copolymer of methacrylic acid and benzyl methacrylate [mass ratio of mercaptoacrylic acid unit to benzyl methacrylate unit is mass ratio (molby)] 30:70, the acid value was 113, the weight average molecular weight of the converted polystyrene was 25,000, and the amount of methacrylic acid contained in the adhesive resin was 0.02% by mass of the adhesive resin. (e-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) (d-1) Photopolymerization initiator: 2-mercapto-2-morpholino 4 -(4-methylthiophenyl)propanone·1-ketone (4-2) photopolymerization initiator. 2,4-bis(dimethyl group)>><6-Pepperyl group_1, 3,5-three.丫30 315272 1285298 azine (d-3) photopolymerization initiator: 2-benzyl-2-didecylamino-; ι_(4_morphine-phenyl)butan-1-one (e- Ι) Photopolymerization starting adjuvant: 2,4-diethyl thioxanthone (e-2) photopolymerization starting adjuvant bis(diethylamino)benzophenone with (f) solvent: propylene glycol single Methyl ether acetate (g) epoxy compound [o-cresol novolac type epoxy resin, "81;]^1-EPOXY ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.) Example 1 Preparation of photosensitive resin composition 1 and resin solution 1 (a_l) (a-2) Polyacetic pigment dispersant (b-1) (c-1) (d_l) (d-2) (e-1) (f) (g) Photosensitive resin composition after mixing 1 5 · 36 parts by mass L 34 parts by mass 2.54 parts by mass 5 · 〇 4 parts by mass 3 · 3 6 parts by mass 5 · 5 0 parts by mass 0 · 5 0 quality Parts 0 · 50 parts by mass 79.91 parts by mass 0. 84 parts by mass. The mass ratio of the content of methacrylic acid in the photosensitive resin composition 1 to the solid content of the photosensitive resin composition is 0.02% 〇 and 315272 31 1285298 (bl) 5.00 parts by mass (f) 45.00 parts by mass, and the resin solution 1 is obtained. . Take the 5 inch square #173 7 glass substrate manufactured by Corning Company, and wash it with neutral detergent, water and alcohol in order. Further, the above photosensitive resin composition 1 was spun on the glass substrate, and then preheated in a heating box at 1 Torr for 3 minutes to remove volatile components. After cooling, the ultrahigh pressure mercury lamp manufactured by Ushio Electric Co., Ltd. under an atmospheric condition was irradiated with an exposure amount of 15 〇mJ/cm 2 to obtain a coating film A. Further, the photosensitive resin composition 1 is replaced with the resin solution 1, and as in the above operation, the film B is obtained. Further, the substrate of the coating film A obtained by preheating in the middle stage is immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 4% of potassium hydroxide without exposure. The image was imaged at 23 I for 8 sec seconds, washed with water and dried to obtain substrate C. (Assess) The above coating film A was heated under atmospheric conditions for 22 minutes (rc heating for 6 minutes, coating film A: weight loss ratio was 8.5%. The reduced portion was not completely removed and contaminated the heating box, but the contamination inside the heating box The material is deposited from the inner wall and adhered to the coating film, thereby improving the production rate. The coating film B has a weight loss ratio of 15% by the same treatment as described above. The transmittance of the substrate C is 100%' Light _ lipid composition. In terms of film thickness (DEKTAK 3 (the difference between the inner thickness of the muscle core is 18A. 315272 32 1285298 Example 2 [modulation of photosensitive resin composition G] 4.574 parts by mass 1 · 9 60 parts by mass 1 · 502 parts by mass 4 · 7 2 2 parts by mass 3 · 8 6 3 parts by mass 1 · 0 3 0 parts by mass 〇 · 343 parts by mass 81 · 960 parts by mass (a-3) (a-4 ) Polyester-based pigment dispersant (b_l〇) (c_l) (d-3) (e-2) (Ο The photosensitive resin composition G is obtained after mixing. Take a glass substrate [manufactured by Corning Incorporated, #1737] to The photosensitive resin composition G is applied by a spin-on method, and then pre-heated at 1 ° C for 3 minutes to remove volatile components, thereby obtaining a photosensitive resin composition layer. After the layer is cooled, it is irradiated with light (wavelength 365 nm) without a mask. The light source of i-light is an ultra-high pressure mercury lamp with an exposure of 150 mJ/cm2. Secondly, the exposed glass substrate The resin composition layer is immersed in a developing solution (that is, an aqueous solution containing 0.05% of potassium hydroxide and 2% of sodium butylnaphthalene sulfonate), and is washed with pure water. Under the condition of heating at 22 〇t for 2 ,, a transparent image is formed. There is no residue on the image. On the substrate on which chlorophyll has been formed, the photosensitive resin is coated by spin coating. The substance is further removed at a distance of 1. (: drying for 3 minutes to remove volatile components, that is, forming a photosensitive resin composition layer. Secondly, the glass substrate is immersed in the development of 315272 33 1285298 liquid (that is, the mass fraction is each hydrogen) The image was developed in potassium oxide (05%, sodium butyl naphthalene sulfonate, 2% aqueous solution), washed with pure water, and then heated under atmospheric conditions for 22 minutes (rc) to form a transparent image. Coating the photosensitive resin composition 1 to form a chlorophyll partial brightness value before and after the coating film is formed The change (measured by 〇SP-SP2〇0 (manufactured by 〇lymPus Optics Co., Ltd.)) is 〇99. Example 3 [Preparation of photosensitive resin composition 2 and resin solution 2] except that (bi) is (b) In the same manner as in Example 2, the photosensitive resin composition 2 and the resin solution 2 were obtained. The mass ratio of the content of methacrylic acid to the photosensitive resin composition solid content in the photosensitive resin composition 2 was 0.07. (Evaluation) The photosensitive resin composition 2 was 9 in the same manner as in Example 1 except that the photosensitive resin composition 2 and the resin solution 2 were used, and under the atmospheric conditions, 22 (TC was heated for 6 minutes, the weight loss ratio was measured, and the photosensitive resin composition 2 was 9 · 1%, resin solution 2 is 2丨·4%. The reduced damage is not completely removed and the heating box is contaminated, but the contaminants in the heating box are again dropped from the inner wall and adhered to the coating film, thereby improving the production rate. The light transmittance of the substrate was 100%, and the photosensitive resin composition was not contained in the residue. The difference in in-plane film thickness was 22 Α. In the same manner as in Example 1, except that the photosensitive resin composition was changed to the photosensitive resin composition 2, the change in the luminance value of the green pixel portion was determined to be 1.22. [Example 4] [Preparation of photosensitive resin composition] 315272 34 1285298 The photosensitive resin composition 3 and the resin solution 3 were obtained in the same manner as in Example 1 except that the change (b-1) was (b_3). The mass ratio of the content of methacrylic acid in the photosensitive resin composition 3 to the solid content of the photosensitive resin composition was 0.11%. (Evaluation) The weight loss ratio was measured in the same manner as in Example 1 except that the photosensitive resin composition 3 and the resin solution 3 were used, and the weight loss ratio was measured by heating at 220 ° C for 60 minutes under atmospheric conditions, and the photosensitive resin composition 3 was 9· 6%, the resin solution 3 is 2 6 · 4 . The reduced portion is not completely removed and contaminates the heating chamber, but the contaminants in the heating chamber are dropped from the inner wall and adhered to the coating film, thereby improving the production rate. The light transmittance of the substrate was 100%, and the photosensitive resin composition was not contained in the residue. The difference in intima thickness was 24 Α. In the second embodiment, except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 3, the change in the luminance value of the green pixel was 0.87 as in the operation of Example 2. [Example 5] [Preparation of photosensitive resin composition] The photosensitive resin composition 4 and the resin solution 4 were obtained in the same manner as in Example 除 except that the change (b-Ι) was (b-7). The mass ratio of the content of methacrylic acid in the photosensitive resin composition 4 to the solid content of the photosensitive resin composition was 0.10 〇 / 〇〇 (assessment) except that the photosensitive resin composition 4 and the resin solution 4 were used, the same as the examples. The operation of 1 is carried out under atmospheric conditions by 22 (rc heating for 6 minutes, 315272 35 1285298, the weight loss ratio is 8.6% of the photosensitive resin composition 4, and the resin solution 4 is 24.2 °/. The reduction portion is not completely The heating box is contaminated, but the contaminants in the heating box are dropped from the inner wall and adhered to the coating film, thereby improving the production rate. The transmittance of the substrate is 100%, and the photosensitive resin composition is not contained in the residue. The difference in film thickness was 23 A. In the second embodiment, except that the photosensitive resin composition was changed to the photosensitive tree composition, the change in the brightness value of the green pixel was determined in the same manner as in Example 2. 1.1 9. Example 6 [Preparation of photosensitive resin composition 5 and resin solution 5] The photosensitive resin composition was obtained in the same manner as in Example 除 except that (b-Ι) was changed to (b-9). 5 and resin solution 5. Photosensitive resin composition 5 The mass ratio of the content of the medium methacrylic acid to the solid content of the photosensitive resin composition was 0.10%. (Evaluation) Except that the photosensitive resin composition 5 and the resin solution 5 were used, the same as in Example 1 under atmospheric conditions of 22 ( The rc was heated for 6 minutes, and the weight loss ratio was determined. The photosensitive resin composition 5 was 9_5%, and the resin solution 5 was 279%. The reduced portion was not completely removed and the heating box was contaminated, but the contaminants in the heating box were again Since the inner wall is dropped and adhered to the coating film, the production rate thereof is improved. The light transmittance of the substrate is 100%, and there is no photosensitive resin composition in the residue. The difference in in-plane film thickness is 19 A. The photosensitive resin composition was changed to the photosensitive resin composition 5, and the change in the brightness value of the green pixel fraction 315272 36 1285298 was determined to be 1.42 in the same manner as in Example 2. Comparative Example 1 [Photosensitive resin composition 6 And the preparation of the resin solution 6] The photosensitive resin composition 6 and the resin solution 6 are obtained in the same manner as in the example 除 except that the change (b-Ι) is (b-4). The photosensitive resin composition 6 is obtained. Methacrylic acid content to photosensitive resin group The mass ratio of the solid matter was 0.17%. (Evaluation) Except that the photosensitive resin composition 6 and the resin solution 6 were used, the weight loss ratio was measured in the same manner as in Example 1 under the conditions of 22 (rc heating for 6 minutes under atmospheric conditions, The photosensitive resin composition 6 is 1 〇·6%, and the resin solution 6 is 371%. The reduced portion is not completely removed and the heating box is contaminated, and the contaminants in the heating box are dropped from the inner wall and attached to the coating film to reduce it. The light transmittance of the substrate was 100%, and there was no photosensitive resin composition in the residue. The difference in in-plane film thickness was 28 Å. In Example 2, the photosensitive resin composition was changed to be photosensitive. In the same manner as in Example 2 except for the composition of the ruthenium 6, the change in the partial brightness value of the green pixel was measured to be 1.72. Comparative Example 2 [Preparation of photosensitive resin composition 7 and resin solution 7] ^ In the same manner as in Example 1, except that the change (b-Ι) was (b-5), the photosensitive resin composition 7 and Resin solution 7. The mass ratio of the content of methacrylic acid in the photosensitive resin composition 7 to the solid content of the photosensitive resin composition was 0% 〇 315272 37 1285298 (Assessed) Except that the photosensitive resin composition 7 and the resin solution 7 were used, the same was carried out. In the operation of Example 1, the light transmittance of the substrate was 97%, and the residue of the photosensitive resin composition remained on the substrate. The difference in in-plane thickness was 32A. In the second embodiment, except that the photosensitive resin composition 变更 was changed to the photosensitive sirolimus composition 7, the change in the green chlorophyll partial brightness value was determined to be 3.02 in the same manner as in the operation of Example 2. Comparative Example 3 [Preparation of Photosensitive Resin Composition 8 and Resin Solution 8] The photosensitive resin composition 8 and the resin were obtained in the same manner as in Example 1 except that (b-Ι) was changed to (b-6). Solution 8. The mass ratio of the content of methacrylic acid in the photosensitive resin composition 8 to the solid content of the photosensitive resin composition was 0%. (Evaluation) Except that the photosensitive resin composition 8 and the resin solution 8 were used, the light transmittance of the substrate was 96% as in the operation of Example 1, and the residue of the photosensitive resin composition remained on the substrate. The difference in in-plane thickness was 22A. In the second embodiment, except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 8, the change in the chlorophyll partial brightness value was determined to be 2.89 as in the operation of Example 2. Comparative Example 4 [Preparation of Photosensitive Resin Composition 9 and Resin Solution 9] The photosensitive resin composition 9 and the resin were obtained in the same manner as in Example 1 except that (b-Ι) was changed to (b-8). Solution 9. Photosensitive resin composition 9 315272 38 1285298 The mass ratio of the content of methacrylic acid to the solid content of the photosensitive resin composition is 0% 评定 (Assessed) Except that the photosensitive resin composition 9 and the resin solution 9 are used, the same applies. In the operation of Example 1, the light transmittance of the substrate was 95%, and the residue of the photosensitive resin composition remained on the substrate. The difference in in-plane thickness was 3 2 A. In the second embodiment, except that the photosensitive resin composition 变更 was changed to a photosensitive resin composition, the change in the greenness partial brightness value was 5.89, which was not the same as in the operation of Example 2. [Preparation of photosensitive resin composition 1 〇] Change (bl) to (b_5) and add 0.2 μ parts of malonic acid, and otherwise the same operation as in Example 1, that is, a photosensitive resin composition ι〇 The photosensitive resin composition has a mass ratio of methacrylic acid to the photosensitive resin composition solid content of 0%, and the mass ratio of the malonic acid to the photosensitive resin composition solid content is 1 〇0/〇. (Evaluation) Except that the photosensitive resin composition was used, the light transmittance of the substrate was the same as that of the operation of Example 100, and the residue of the photosensitive resin composition remained on the substrate. In the second embodiment, the photosensitive resin composition i is a photosensitive resin composition i" The change in brightness value is 6.42, so it is not good. Example 6 315272 39 1285298 [Preparation of photosensitive resin composition 1 1] Change (bl) to (b-5) and add 0.2 parts by mass of malonic acid, and otherwise the same as in the operation of Example 1, that is, photosensitivity Resin composition u. The mass ratio of the content of methacrylic acid in the photosensitive resin composition 11 to the solid content of the photosensitive resin composition is 0%, wherein the mass ratio of the content of malonic acid to the solid content of the photosensitive resin composition is (Evaluation) Except that the photosensitive resin composition was used, the light transmittance of the substrate was 100% in the same manner as in Example ,, and the residue of the photosensitive resin composition remained on the substrate. The difference in the thickness of the inner film was 82 A, which was not preferable. In the second embodiment, except that the photosensitive resin composition 变更 was changed to the photosensitive resin composition 10, the greenness partial brightness was measured in the same manner as in Example 2. The change of the value was 6.44, which was not preferable. Comparative Example 7 [Preparation of Photosensitive Resin Composition 12] The change of (b-Ι) was (b-11) except that the operation was the same as in Example ,, that is, the photosensitive resin was known. Composition 12. Photosensitive resin composition 丨2 in methyl propyl The mass ratio of the acid content to the solid content of the photosensitive resin composition was 0.005%. (Evaluation) The light transmittance of the substrate was the same as that of Example 1, except that the photosensitive resin composition 丨2 and the resin solution 12 were used. 98%, the residue of the photosensitive resin composition remained on the substrate. The difference in in-plane film thickness was 3 〇 A. In Example 2, except that the photosensitive resin composition was changed, the photosensitive resin was used as a photosensitive tree 40 315272 1285298. In the same manner as in Example 2, the change in the partial brightness value of the green pixel was measured to be 3.00. Comparative Example 8 [Modulation of photosensitive resin composition 13] Change (b-Ι) to (b-5) Further, 2 parts by mass of malonic acid of ruthenium and osmium was added, and the same operation as in Example 1 was carried out to obtain a photosensitive resin composition 13. The mass ratio of the content of methacrylic acid in the photosensitive resin composition to the solid content of the photosensitive resin composition was 0%, and the mass ratio of the content of malonic acid to the solid content of the photosensitive resin composition was 〇·1%. (Evaluation) Except that the photosensitive resin composition 13 was used, the light transmittance of the substrate was 98% in the same manner as in Example 1, and the residue of the photosensitive resin composition remained on the substrate. The difference in endometrial thickness is 52, which is not good. In the second embodiment, except that the photosensitive resin composition 变更 was changed to the photosensitive resin composition 13, the change in the greenness partial brightness value was determined to be 4.62, which was not preferable, as in the operation of Example 2. Comparative Example 9 [Preparation of photosensitive resin composition 14] Change (b-Ι) to (b-5) and add 0.02 part by mass of malonic acid, and other operations similar to those in Example 1 gave photosensitivity Resin composition 14. The mass ratio of the content of methacrylic acid in the photosensitive resin composition 14 to the solid content of the photosensitive resin composition is 0%. The mass ratio of the content of malonic acid to the solid content of the photosensitive resin composition is 〇·丨〇 /〇. (Evaluation) 315272 41 1285298 The light transmittance of the substrate was the same as that of Example 1, except that the photosensitive resin composition 14 was used. /. The residue of the photosensitive resin composition remains on the substrate. The difference in in-plane thickness is 54 A, which is not good. In the second embodiment, except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 14, the change in the chlorophyll partial brightness value was 4.74, which was not preferable, as in the operation of Example 2. Industrial Applicability According to the present invention, it is possible to provide a photosensitive resin composition which can be made into a picture having excellent flatness, such as a residue remaining in a part. Treatment of two additions: use / inventive photosensitive resin composition 'the next step of the hot material of the film two: the cause of the dyeing caused by the reduction of the production rate and the reduction of the image retention rate can be (four) balance to solve the M Bureau Produced into a high quality color filter film. 315272 42

Claims (1)

12852981285298 修（敗)正本 第92133008號專利申請案 申請專利範圍修正本 (96年2月14日） 1. 一種光敏性樹脂組成物，其特徵為光敏性樹脂組成物中 含構成單位為製自（甲基）丙烯酸之黏著樹脂及（甲基）丙 烯酸’該光敏性樹脂組成物之固形物中（甲基）丙烯酸之 含量為0.010至0.16質量％者。 2. 如申請專利範圍帛！項之光敏性樹脂組成物，其中，光 敏性樹脂組成物之固形物中黏著樹脂之含量為5至9〇 質量％者。 3. 如申請專利範圍第i或第2項之光敏性樹脂組成物，其 中更3光聚合性化合物、光聚合起始劑、及溶劑者。 4·如申請專利範圍帛i或第2項之光敏性樹脂組成物，其 中，更含著色劑者。 5·如申叫專利範圍第3項之光敏性樹脂組成物，其中，更 含著色劑者。 6·種圖案（pattern)，為使用如申請專利範圍第工至第$ 項之任一項中之光敏性樹脂組成物形成者。 7· -種濾色片，為含如申請專利範圍第6項之圖案者。 8·種液曰曰㈣不裝置，為具有如申請專利範圍帛7項之遽 色片所成者。 315272(修正版) 1Amendment (Paper No. 92133008) Patent Application Amendment (February 14, 1996) 1. A photosensitive resin composition characterized in that the photosensitive resin composition contains a constituent unit. The adhesive resin of (meth)acrylic acid and (meth)acrylic acid The content of (meth)acrylic acid in the solid content of the photosensitive resin composition is 0.010 to 0.16 mass%. 2. If you apply for a patent range! The photosensitive resin composition of the invention, wherein the content of the adhesive resin in the solid content of the photosensitive resin composition is from 5 to 9 % by mass. 3. The photosensitive resin composition of claim i or 2, wherein the photopolymerizable compound, the photopolymerization initiator, and the solvent are more preferred. 4. A photosensitive resin composition as claimed in claim 帛i or 2, wherein the coloring agent is further included. 5. The photosensitive resin composition of claim 3, wherein the coloring agent is further included. 6. A pattern which is formed by using a photosensitive resin composition as in any one of the claims of the present invention. 7· - A color filter, which is a pattern containing the sixth item of the patent application scope. 8. Seed liquid 曰曰 (4) It is not installed, and it is made up of 遽 color film with 7 items as the patent application scope. 315272 (revision) 1
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TWI396042B (en) * 2004-09-29 2013-05-11 Sumitomo Chemical Co Colored photosensitive resin composition
KR101221468B1 (en) * 2005-01-27 2013-01-11 주식회사 동진쎄미켐 Photosensitive resin composition
KR100655045B1 (en) * 2005-12-30 2006-12-06 제일모직주식회사 Photosensitive resin composition and black matrix thereof
KR101313538B1 (en) * 2006-04-06 2013-10-01 주식회사 동진쎄미켐 Negative photosensitive resin composition
KR101727101B1 (en) * 2008-08-26 2017-04-14 타무라 카켄 코포레이션 Photopolymer composition, solder resist composition for print circuit boards and print circuit boards
CN102686622B (en) * 2009-10-14 2015-06-17 电气化学工业株式会社 Resin composition and adhesive agent

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JP2554760B2 (en) * 1990-01-11 1996-11-13 東京応化工業株式会社 Positive photoresist composition
CN1205454A (en) * 1997-06-20 1999-01-20 智索股份有限公司 Photosensitive resin compsns. and display components using same
EP1012671B1 (en) * 1998-07-14 2003-09-24 Brewer Science, Inc. Photosensitive black matrix composition and process of making it
JP3940243B2 (en) * 1998-10-15 2007-07-04 三井化学株式会社 Copolymer, method for producing the same, and solution containing the same
JP2002022925A (en) * 2000-07-11 2002-01-23 Nippon Steel Chem Co Ltd Method for producing color filter and colored photosensitive resin composition
JP3938896B2 (en) 2001-09-25 2007-06-27 大日本印刷株式会社 Maleimide-based alkali-soluble copolymer, ionizing radiation curing resin composition, color filter, and liquid crystal display device
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