TW201003317A - Negative photosensitive resin composition - Google Patents

Negative photosensitive resin composition Download PDF

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TW201003317A
TW201003317A TW098114165A TW98114165A TW201003317A TW 201003317 A TW201003317 A TW 201003317A TW 098114165 A TW098114165 A TW 098114165A TW 98114165 A TW98114165 A TW 98114165A TW 201003317 A TW201003317 A TW 201003317A
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Taiwan
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weight
resin composition
photosensitive resin
negative photosensitive
ethyl
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TW098114165A
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Chinese (zh)
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TWI471697B (en
Inventor
Byung-Uk Kim
Hyoc-Min Youn
Ki-Hyuk Koo
Tae-Hoon Yeo
Jin-Sun Kim
Joo-Pyo Yun
Dong-Myung Kim
Su-Youn Choi
Sang-Gak Choi
Hong-Dae Shin
Sang-Hoon Lee
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Dongjin Semichem Co Ltd
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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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/285—Polyhydroxy dicarboxylic acids having five or more carbon atoms, e.g. saccharic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention is to provide a negative photosensitivity resin composition, which has superior resolution, insulation, flatness, chemical resistance and adhesion. In particular, in forming the organic insulation film for LCD element with high high aperture ratio and for reflection type LCD element, it has noticeable superiority over the conventional photosensitivity resin in photosensitivity, residue ratio and UV transmittance o, therefore suitable for use as organic insulation film. The present invention relates to a negative photosensitivity resin, in particular a negative photosensitivity resin composition comprising (a) (i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or the mixing; (ii) unsaturated compound containing epoxy; and (iii) acrylic acid copolymer obtained from copolymerizing olefin series unsaturated compound; (b) photoinitiator containing 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl acetyloxime); (c) polyfunction monomer having ethylenically unsaturated bond; (d) silicon compound having epoxy base or amino; and (e) solution.

Description

201003317 六、發明說明： 【發明所屬之技術領域】 發明領域 本發明和-種負型感光性樹脂組成物相關，更詳細來 說，是關於-種因其解析度、絕緣性、平坦性、耐化學性 及黏著力俱優，特別是在形成高開口率液晶顯示元件與反 射型液晶顯示元件的有機絕緣膜時，感光度、殘膜率及μ ^ €射率與習知的感紐樹脂相比顯著較優，故適於作爲有 機絕緣膜使用的感光性樹脂組成物。201003317 VI. Description of the Invention: [Technical Field of the Invention] Field of the Invention The present invention relates to a negative photosensitive resin composition, and more specifically, to a resolution, insulation, flatness, and resistance Excellent chemical and adhesive properties, especially when forming an organic insulating film of a high aperture ratio liquid crystal display element and a reflective liquid crystal display element, sensitivity, residual film rate, and μ ^ % transmittance are similar to those of the conventional sensory resin phase. The ratio is remarkably excellent, and therefore it is suitable as a photosensitive resin composition used as an organic insulating film.

【前冬好J 發明背景 有機絕緣膜被使用來使配置在T F T型液晶顯示元件和 積體電路元件的層間之配線間形成絕緣。參照圖式來說明 使用有機絕緣膜之T F T型高開口率液晶顯示元件的構造。第 1圖為具有高開口率的TFT型液晶顯示元件單元的平面圖。 第1圖中閘線2a橫向配置，儲荷電極線3a在相隔預定間隔的 位置與其平行配置。數據線5配置為垂直通過閘線2a及儲荷 電極線3a。而，半導體層6依圖案形態形成在與資料線5相 鄰位置的閘線2a上，從資料線5引出的漏電極8和形成資料 線5時一同形成的源電極7，在半導體層6上被配置成彼此相 對且預定的部分重疊之狀態。 第2圖所示為沿著第1圖的h 一]2，切斷的斷面圖。如圖 所示，在下部基板1的上部全面形成有閘絕緣膜4。半導體 層6是通過共振識別依圖案形態形成在閘絕緣膜4上，在該 3 201003317 半導體層6上於形 電極7互相隔離地被::線5時-同被形成的漏電極8及源 機絕=9 Hi前述構造物的下部基板1上面塗布了有 接觸孔（未圖，的有機絕緣膜9上備有使源電極露出的 領域的部分通過接編料錢躲膜9上，在4目當於像素 電極7相接觸的同時，像素電極 >成為和間電極2及資料線5的—部分重#的狀態。在 、機、錄膜9發揮使像素電極1G與資料線5之間絕緣， 並且使下部平坦化的機能。 = 卩边者'夜日日顯示态（LCD )的顯示品質提升，tft 型回開口率液晶顯示元件的構造也發生變化，增厚有機絕 緣膜的膜厚並提高平坦性再做使關情況逐漸增加。不僅 如此，逛要求被應用在LCD製造工程的有機絕緣膜要具有 優異之透射率。 tft型反射型液晶顯示元件係如以下列專利文獻1、下 列專利文獻2、下列專利文獻3所載，被設計成包含附有反 射機能之像素電極的特定反射塑液晶顯示器。 前述之反射型液晶顯示元件中，有機絕緣膜是利用光 刻術設計成有凸部及凹部。因為表面粗糙度之故，凸部及 凹部的微細形態是以微米級來形成，而為了調節及形成接 觸孔’習知主要是使用正型有機絕緣膜。 過去以來’用以形成液晶顯示元件之有機絕緣膜的感 光性樹脂組成物，是由PAC、黏著劑、溶劑等成分組成， 而前述黏著劑，主要是使用丙烯酸樹脂。但是，過去以來， 4 201003317 感光性樹脂的情況’因為有硬化後發生有色化而難以達成 在層間絕緣膜所要求的高透射率，而且體積發生收縮的問 題，故而迫切需求對於此點的改善。 [先前技術文獻] [專利文獻] [專利文獻1]大韓民國特許公開第2006_0038788號說明書 [專利文獻2]大韓民國特許公開第2〇〇8_〇〇24643號說明書 ( [專利文獻3]大韓民國特許公開第2008-0018606號說明書 【發明内容】 發明概要 發明所欲解決的課題 本發明之目的係為解決如前所述之習知技術的問題， 而提供一種解析度、絕緣性、平坦性 '对化學性及黏著力 俱優，特別是在形成高開口率液晶顯示元件與反射型液晶 顯不凡件的有機絕緣膜時，感光度、殘膜率及UV透射率與 ί:丨 習知之感光性樹脂相比顯著較優，故而適合於作為有機絕 、’彖膜使用的負型感光性樹脂組成物，以及使用前述負型感 光性樹脂組成物之液晶顯示元件的有機絕緣膜形成方法。 用以解決課題的手段 為達成前述技術課題，本發明提供一種負型感光性樹 月:組成物，特徵在於其含有，a) i)不飽㈣酸、不飽和竣 义軒或其等之混合物；W含有環氧基的不飽和化合物； 及，111)使烯烴系不飽和化合物共聚而獲得之两烯酸 (Acrylle)系共聚物；b)含有[1- [9-乙基-6- (2—甲 5 201003317 基苯曱醯基）一9H—咔唑一3 —基]一1一（0—乙醯肟）的 光起始劑；c)含乙烯性不飽和鍵的多官能性單體；d)含 有環氧基或胺基的矽系化合物；以及，e)溶劑。 另外，本發明提供一種使用前述負型感光性樹脂組成 物之液晶顯示元件的有機絕緣膜形成方法。 另外，本發明提供一種液晶顯示元件，特徵在於其包 含利用前述液晶顯示元件之有機絕緣膜形成方法所形成的 有機絕緣膜。 發明效果 依據本發明之負型光阻劑組成物，因解析度、絕緣性、 平坦性、耐化學性及黏著力倶優，特別是在形成高開口率 液晶顯示元件與反射型液晶顯示元件的有機絕緣膜形成 時，感光度、殘膜率及UV透射率與習知之感光性樹脂相比 顯著較優，故適合於作爲有機絕緣膜使用。 圖式簡單說明 第1圖具有高開口率的TFT型液晶顯示元件單元之示意 平面度。 第2圖沿著第1圖之第1圖的Π — Π ’線切斷的斷面圖。 I；實施方式;3 較佳實施例之詳細說明 用以實施發明的態樣 以下將就本發明的實施態樣做詳細說明。 本發明之負型感光性樹脂組成物的特徵是，含有a) i) 不飽和羧酸、不飽和羧酸酐，或其等之混合物；ii)含有環 201003317 氧基之不飽和化合物；及iii )使稀烴系不飽和化合物共聚 而得到之丙稀糸共聚物；b)含有[1 — [9 —乙基一 6 — ( 2 一 曱基苯曱醯基）一9H—咔唑一3—基]一1一（Ο—乙醯肟） 的光起始劑；c)具有乙烯性不飽和鍵的多官能性單體；d) 含有環氧基或胺基的矽系化合物；及，e)溶劑。 本發明所使用之前述a)的丙烯酸系共聚物可以採用i) 不飽和羧酸、不飽和羧酸酐，或其等之混合物；ii)含有環 氧基的不飽和化合物；及iii)烯烴系不飽和化合物作爲單 體，在溶劑及聚合起始劑的存在下進行自由基反應加以製 造。 使用於本發明之前述a) i)的不飽和羧酸、不飽和羧酸 酐、或其等之混合物，可以單獨使用丙烯酸、甲基丙烯酸 等的不飽和單羧酸；馬來酸、富馬酸、曱基顺丁烯二酸、中 康酸、衣康酸等不飽和二羧酸；或這些不飽和二羧酸的酸 酐等，或混合2種以上供使用，特别是使用丙烯酸、甲基丙 烯酸，或馬來酸酐，對於共聚反應性和顯影液，即鹼性水 溶液的溶解性上較為合適。 前述不飽和羧酸、不飽和羧酸酐，或其等之混合物， 以在全體總單體中含有5到40重量％為佳，較佳的是含有10 到30重量％。其含量不滿5重量％時，會有難於在鹼性水溶 液中溶解的問題，超過40重量％時，會有對於鹼性水溶液 的溶解性變得太大的問題。 本發明所使用之前述a) ii)的含有環氧基之不飽和化 合物可以使用，丙稀酸縮水甘油醋、甲基丙烯酸縮水甘油 7 201003317 酯、α—乙基丙烯酸縮水甘油酯、α—n—丙基丙烯酸縮水甘 油酯、α—η—丁基丙烯酸縮水甘油酯、丙烯酸—β—曱基縮 水甘油酯、曱基丙烯酸一 (3_甲基縮水甘油酯、丙烯酸 —乙基縮水甘油酯、曱基丙烯酸_β—乙基縮水甘油酯、丙 烯酸一3, 4—環氧丁酯、甲基丙烯酸一 3, 4—環氧丁酯、丙 烯酸一 6, 7—環氧庚酯、甲基丙烯酸—6, 7 一環氧庚酯、α 一乙基丙烯酸一6, 7—環氧庚酯、〇—乙烯苯曱基縮水甘油 醚、m—乙烯苯甲基縮水甘油醚，或ρ_乙烯苯甲基縮水甘 油縫等’前述化合物可以單獨或混合2種以上供使用。 前述含有環氧基之不飽和化合物，尤以使用曱基丙稀 酸縮水甘油酯、甲基丙烯酸一 β一甲基縮水甘油酯、甲基丙 烯酸一6, 7—環氧庚酯、〇—乙烯苯甲基縮水甘油醚、爪― 乙烯笨甲基縮水甘油醚或p_乙烯苯甲基縮水甘油醚時，就 提高共聚反應性及所獲得之圖案的耐熱性而言，較為合適。 m述含有環氧基之不飽和化合物，以在全體總單體中 含有5到70重量％為佳，較佳的是含有2〇到6〇重量％。其含 量不滿5重量％時，會有所得到的圖案之耐熱性降低的問 題，超過70重量％時’有共聚物的保存安定性降低的問題。 另外，在製造本發明的丙烯酸系共聚物時所使用的前 述iii)之烯烴系不飽和化合物可以使用，甲基丙烯酸甲酯、 乙基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸仲丁酯、 甲基丙烯酸叔丁酯、丙烯酸甲酯、丙烯酸異丙酯、曱基丙 烯酸環己酯、2~甲基環己基甲基丙烯酸酯、二環戊烯基丙 烯酸酯、二環戊烷基丙烯酸酯、二環戊烯基甲基丙烯酸酯、 201003317 二環戊烷基甲基丙烯酸酯、i —金剛烷基丙烯酸酯、1 —金 剛烷基甲基丙烯酸酯、甲基丙烯酸雙環戊烷基氧化乙酯、 甲基丙烯酸異冰片酯、環己基丙烯酸酯、2—甲基環己基丙 烯酸酯、丙烯酸雙環戊烷基氧化曱酯、丙烯酸異冰片酯、 甲基丙烯酸苯酯、丙烯酸苯酯、丙烯酸苄酯、2—羥乙基曱 基丙烯酸酯、苯乙烯、σ—曱基苯乙烯、m—甲基苯乙烯、 P —曱基苯乙烯、乙烯基曱苯、P —曱氧基苯乙烯、1，3—丁 二烯、異戊二烯，或2, 3 —二曱基-1,3—丁二烯等，前述化 合物可以單獨或混合2種以上來使用。 前述烯烴系不飽和化合物，尤以使用苯乙烯、二環戊 烷基甲基丙烯酸酯，或者p—曱氧基苯乙烯時，在對於共聚 反應性以及作爲顯影液的鹼性水溶液的溶解性方面上較為 合適。 前述烯烴系不飽和化合物以相對於全體單體含有10到 70重量％為佳，較佳的是含有20到50重量％。其含量在前述 範圍内時，可以同時解決丙烯酸系共聚物的保存安全性降 低，丙烯系共聚物難以在顯影液的鹼性水溶液中溶解等的 問題。 將如前所述之單體聚合成丙烯酸系共聚物時所使用的 溶劑，可以使用甲醇、異丙醇、四氫呋喃、乙二醇單甲醚、 乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二 乙二醇單甲醚、二乙二醇單乙醚、乙二醇二曱醚、乙二醇 二乙醚、乙二醇曱乙醚、丙二醇單曱醚、丙二醇單乙醚、 丙二醇丙、丙二醇丁醚、丙二醇曱鍵醋酸g旨、丙二醇乙醚醋 9 201003317 酸酯、丙二醇丙醚醋酸酯、丙二醇丁醚醋酸酯、丙二醇甲基 乙基丙酸酯、丙二醇乙瞇丙酸酯、丙二醇丙醚丙酸酯、丙二 醇丁醚丙酸酯、甲苯、二曱苯、甲乙酮、環己酮、4_羥基 —4—曱基一2—戊酮、乙酸甲酯 '乙酸乙酯、乙酸丙酯、 乙酸丁酯、2—羥基丙酸乙酯、2_羥基_2一甲基丙酸曱 酯、2—羥基—2—甲基丙酸乙酯、羥基乙酸甲酯、羥基乙 酸乙酯、羥基乙酸丁酯、乳酸曱酯、乳酸乙酯、乳酸丙酯、 乳酸丁酯、3 —經基丙酸甲酯、3 _羥基丙酸乙酯、;3 一經基 丙酸丙酯、3 —羥基丙酸丁酯、2 —羥基一3 —甲基丁酸甲 酉旨、曱氧基乙酸甲酷、甲氧基乙酸乙醋、甲氧基乙酸丙自旨、 甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙 氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸曱酯、丙氧 基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基 乙酸曱酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙 酸丁酯、2—曱氧基丙酸曱酯、2 —甲氧基丙酸乙酯、2—甲 氧基丙酸丙酯、2 —曱氧基丙酸丁酯、2—乙氧基丙酸曱酯、 2—乙氧基丙酸乙酯、2—乙氧基丙酸丙酯、2—乙氧基丙酸 丁酯、2_ 丁氧基丙酸甲酯、2—丁氧基丙酸乙酯、2—丁氧 基丙酸丙酯、2—丁氧基丙酸丁酯、3 —曱氧基丙酸曱酯、3 —曱氧基丙酸乙酯、3—曱氧基丙酸丙酯、3 —曱氧基丙酸 丁酯、3—乙氧基丙酸甲酯、3 —乙氧基丙酸乙酯、3—乙氧 基丙酸丙酯、3—乙氧基丙酸丁酯、3 —丙氧基丙酸甲酯、3 —丙氧基丙酸乙醋、3—丙氧基丙酸丙S旨、3—丙氧基丙酸 丁酯、3—丁氧基丙酸曱酯、3—丁氧基丙酸乙酯、3—丁氧 10 201003317 基丙酸丙酯，或3—丁氧基丙酸丁酯等之類的醚類等，前述 化合物可以單獨或混合2種以上來使用。 為將如上所述之單體聚合成丙烯酸系共聚物而使用的 聚合起始劑，可以使用自由基聚合起始劑，具體而言，可 以使用2，2—偶氮二異丁腈、2，2—偶氮二（2，4—二曱基戍 腈）、2, 2—偶氮二（4—曱氧基一2, 4—二曱基戊腈）、1，1 —偶氮二（環己基一1 一曱猜）或2，2—偶氮二異丁酸二甲 醋等。 前述a )之丙稀酸系共聚物可以使如上所述之單體在溶 劑和聚合起始劑的存在下進行自由基反應而聚合，也可以 利用對於一般之已聚合的聚合物為不溶性之過量的溶劑予 以析出而製造，以包含1)在具備冷卻裝置的聚合反應器中 倒入單體、聚合溶劑及聚合起始劑使聚合物進行聚合的步 驟；2)使前述聚合中止的步驟；3)前述聚合中止後使反 應器冷卻以使聚合物析出的步驟；4 )分離前述已析出之聚 合物的步驟；及，5)將前述已分離的聚合物溶解於溶劑的 步驟進行製造者為佳。這種情況與習知所使用的懸浮聚合 或乳液聚合和總體聚合等製程相比，使用了相對單純且簡 單的製程，並且使用有單分散分子量的丙烯酸系共聚物， 藉而可以在與後述之含有[1—[9 一乙基一 6— (2 —曱基苯 曱醯）一9H—咔唑一3 —基]—1— (0—乙醯肟）的光起始 劑一起在形成液晶顯示元件之有機絕緣膜時，使感光度、 殘膜率及UV透射率進一步提高，特別是，即使省略習知之 負型感光性樹脂的後烘處理依然可顯示出非常優異的感光 11 201003317 度。 為了前述1)步驟的聚合而使用之單體、聚合起始劑、 聚合溶劑係如前所述，冷卻裝置當然可以使用公知的冷卻 裝置，具體的一個例可以使用冷卻套。 前述聚合溶劑的使用量是以重量比計，以使用會使得 所使用之固形分總量成為5至50重量％的聚合溶劑為佳，若 使用10到45重量％則更佳。若聚合溶劑的量過多，反應轉 換率會下降，在後處理程序中收率的損失大，在成本方面 也不佳；若溶劑的量過少，則不僅不易調節分子量，之後 的聚合物析出也會變得困難。 另外，前述聚合起始劑的量以重量比計相對於單體總 量100重量份宜使用0.01到30重量份，較佳為使用1到20重 量份。 若前述聚合起始劑的量過少，聚合物的分子量就會過 度增加，若過多，則分子量會變得過低，有感光度降低， 同時圖案形狀變差的情形。 另外，在前述1)步驟中，聚合溫度宜在比聚合起始劑 的10小時半衰期溫度高的溫度下進行，以40到80°c為佳， 45到75°C較佳。這種情況，可以得到未反應單體的含量更 為減少的聚合物，可以得到較高的聚合收率。另外，聚合 反應時間以1到24小時為佳，較佳為2到20小時左右。另外， 若於聚合時攪拌反應器内部，可以使聚合轉換率更加提高。 此外，在2)使前述聚合中止的步驟，當然可以使用公 知的聚合中止方法，其一例可以採用將類似亞磷酸酯這樣 12 201003317 的阻聚劑倒入聚合反應物的做法。前述阻聚劑的使用量當 然可以由熟習該項技術者做適當的調節，合適的是在聚合 反應物中使用100到3,000ppm的量。 另外，在前述3)步驟，使前述聚合已被中止的聚合反 應器冷卻以析出聚合物，其中前述冷卻和析出溫度以-30到 40°C為佳，-20到30°C較佳。前述析出溫度如果過低，未反 應物會一起被析出而變得常產生殘留的揮發氣體；若析出 溫度過高，則不僅使得收率降低，也不易控制分子量，而 且有析出物與聚合溶劑不易分離的情形。另外，在前述析 出溫度範圍内，當需求高分子量的聚合物，同時聚合溶劑 的極性低時，宜儘量在高析出溫度下進行析出。 此外，前述析出時間以0.5到10小時為佳，較佳的是1 到7小時。若前述析出時間過短，因為不會產生充分的分 離，所以不僅不易除去未反應物和添加物等，而且會造成 收率的降低，若沉降時間過長，則因析出物的自反應而有 引發變質的情形。 另外，在前述4 )分離所析出之聚合物的步驟中，前述 分離當然可以應用公知的分離方法，可舉過濾為其具體的 一例。 另外，在前述5 )使已分離的聚合物溶解於溶劑的步驟 中，前述溶劑只要是可以溶解前述聚合物的溶劑即可使 用，具體例可以使用曱醇、乙醇、丙醇、異丙醇、丁醇、 己醇、醇類；四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、 曱基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單曱醚、 13 201003317 二乙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇 甲乙醚、丙二醇單乙醚、丙二醇單乙醚、丙二醇丙醚、丙 二醇丁醚、丙二醇甲乙醚醋酸酯、丙二醇乙醚醋酸酯、丙 一醇丙_醋酸醋、丙二醇丁醚醋酸醋、丙二醇甲乙醚丙酸 西旨、丙二醇單乙基丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙 醚丙酸酯、丙二醇丁醚丙酸酯、曱苯、二甲苯、甲乙酮等。 前述溶劑的使用量宜使聚合物固形分的含量達到10至50重 量％。這種情況，可以使所製造的丙烯酸系共聚物之保存 安定性更加提高。 本發明十，前述丙烯酸系聚合物，其聚苯乙烯換算重 量平均分子量（Mw )為1，〇〇〇-4〇,〇〇〇，以3 ,〇〇〇_2〇 〇〇〇較佳。 負型感光性樹脂組成物之前述聚苯乙烯換算重量平均分子 量不滿1，000時，有顯影性、殘膜率等降低，同時圖案形狀' 对熱性等變差的問題’超過4_叫，職接觸孔及圖案 顯影變差的問題。 X明所使用之則述b) &光起始齊|，特徵為含有D [9一乙基一 6— (2—曱基苯甲醯基）—9h—咔唑u - 1- (〇-乙酷月亏）。前述[卜[9—乙基一 6— (2一甲基 甲醯基）-9H-十坐-3 —基]—卜（〇—乙觀）可二 用市售產品，可以使用Ciba咖响❿心丨$公司〖[Previous Winter J Background] An organic insulating film is used to insulate between wirings disposed between layers of a T F T type liquid crystal display element and an integrated circuit element. The configuration of a T F T type high aperture ratio liquid crystal display element using an organic insulating film will be described with reference to the drawings. Fig. 1 is a plan view showing a TFT type liquid crystal display element unit having a high aperture ratio. In Fig. 1, the brake wire 2a is disposed laterally, and the storage electrode wire 3a is disposed in parallel with the predetermined interval. The data line 5 is configured to pass vertically through the gate line 2a and the storage electrode line 3a. Further, the semiconductor layer 6 is formed in a pattern form on the gate line 2a adjacent to the data line 5, and the drain electrode 8 drawn from the data line 5 and the source electrode 7 formed together when the data line 5 is formed are on the semiconductor layer 6. The state is configured to be opposed to each other and the predetermined portions are overlapped. Fig. 2 is a cross-sectional view taken along line h-2 of Fig. 1 and cut away. As shown in the figure, a gate insulating film 4 is entirely formed on the upper portion of the lower substrate 1. The semiconductor layer 6 is formed on the gate insulating film 4 by resonance recognition in a pattern form, and on the semiconductor layer 6 of the 3 201003317, the drain electrode 8 and the source electrode are formed when the shape electrodes 7 are isolated from each other: the line 5 The lower substrate 1 of the above-mentioned structure is coated with a contact hole (not shown, the organic insulating film 9 is provided with a portion of the field in which the source electrode is exposed, and the portion of the substrate is etched through the film, in the 4 mesh. While the pixel electrode 7 is in contact with each other, the pixel electrode > is in a state of being partially overlapped with the inter-electrode 2 and the data line 5. The motor and the recording film 9 are used to insulate between the pixel electrode 1G and the data line 5. And the function of flattening the lower part. = The display quality of the 'day-day display state (LCD) is increased, and the structure of the tft-type return aperture liquid crystal display element is also changed, and the film thickness of the organic insulating film is thickened. In addition, the organic insulating film that is required to be applied in the LCD manufacturing engineering should have excellent transmittance. The tft type reflective liquid crystal display element is as follows: Patent Document 1, the following patents Document 2 Patent Document 3 discloses a specific reflective plastic liquid crystal display which is designed to include a pixel electrode with a reflective function. In the above reflective liquid crystal display device, the organic insulating film is designed to have convex portions and concave portions by photolithography. The surface roughness is such that the fine shape of the convex portion and the concave portion is formed in a micron order, and in order to adjust and form the contact hole, it is conventionally to use a positive organic insulating film. In the past, the organic layer for forming a liquid crystal display element has been used. The photosensitive resin composition of the insulating film is composed of a component such as PAC, an adhesive, a solvent, and the like, and the above-mentioned adhesive is mainly an acrylic resin. However, in the past, 4 201003317 The case of a photosensitive resin was caused by hardening. In the case of coloring, it is difficult to achieve the high transmittance required for the interlayer insulating film, and the volume is contracted. Therefore, there is an urgent need for improvement in this point. [Prior Art Document] [Patent Document] [Patent Document 1] Republic of Korea Licensed Open 2006_0038788 Specification [Patent Document 2] Korean Republic of China Patent No. 2〇〇8_〇〇24643 [Patent Document 3] Korean Patent Application Publication No. 2008-0018606 SUMMARY OF INVENTION Technical Problem The object of the present invention is to solve the problems of the prior art as described above and to provide a resolution. Insulation, flatness' is excellent in chemical properties and adhesion, especially in the formation of organic insulating films with high aperture ratio liquid crystal display elements and reflective liquid crystal display elements, sensitivity, residual film rate and UV transmittance. ί: The photosensitive resin is significantly superior to the conventional photosensitive resin, and is therefore suitable for use as an organic photosensitive resin composition, a negative photosensitive resin composition, and a liquid crystal display element using the negative photosensitive resin composition. A method of forming an insulating film. Means for Solving the Problem In order to achieve the above-mentioned technical problems, the present invention provides a negative photosensitive tree: composition, characterized in that it contains, a) i) unsaturated (tetra) acid, unsaturated bismuth or a mixture thereof W an unsaturated compound containing an epoxy group; and, 111) an acrylic acid (Acrylle) copolymer obtained by copolymerizing an olefinic unsaturated compound; b) containing [1- [9-ethyl-6- ( 2—A 5 201003317 phenyl fluorenyl)- 9H-carbazole-3-yl] photoinitiator of 1-1-1(0-acetamidine); c) polyfunctional single containing ethylenically unsaturated bond a compound; d) an oxime compound containing an epoxy group or an amine group; and, e) a solvent. Further, the present invention provides a method of forming an organic insulating film using a liquid crystal display element of the above negative photosensitive resin composition. Further, the present invention provides a liquid crystal display element characterized by comprising an organic insulating film formed by the method of forming an organic insulating film of the liquid crystal display element. Advantageous Effects of Invention The negative photoresist composition according to the present invention is excellent in resolution, insulation, flatness, chemical resistance, and adhesion, particularly in forming a high aperture ratio liquid crystal display element and a reflective liquid crystal display element. When the organic insulating film is formed, the sensitivity, the residual film ratio, and the UV transmittance are remarkably superior to those of the conventional photosensitive resin, and therefore it is suitable for use as an organic insulating film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic plan view of a TFT type liquid crystal display element unit having a high aperture ratio. Fig. 2 is a cross-sectional view taken along line Π - ’ ' of Fig. 1 of Fig. 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the Invention The embodiments of the present invention will be described in detail below. The negative photosensitive resin composition of the present invention is characterized by comprising a) i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof; ii) an unsaturated compound containing a ring of 201003317 oxy; and iii) An acrylonitrile copolymer obtained by copolymerizing a dilute hydrocarbon unsaturated compound; b) containing [1 - [9-ethyl-6-(2-mercaptophenyl)- 9H-carbazole-3-yl group a photoinitiator of 1-1 (Ο-acetamidine); c) a polyfunctional monomer having an ethylenically unsaturated bond; d) an anthracene compound containing an epoxy group or an amine group; and, e) Solvent. The acrylic copolymer of the above a) used in the present invention may be i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof; ii) an epoxy group-containing unsaturated compound; and iii) an olefin system. The saturated compound is produced as a monomer by a radical reaction in the presence of a solvent and a polymerization initiator. As the unsaturated carboxylic acid, the unsaturated carboxylic anhydride, or a mixture thereof, of the above a) i) of the present invention, an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid may be used alone; maleic acid or fumaric acid; Or an unsaturated dicarboxylic acid such as mercapto maleic acid, mesaconic acid or itaconic acid; or an acid anhydride of these unsaturated dicarboxylic acids, or a mixture of two or more thereof, particularly using acrylic acid or methacrylic acid Or maleic anhydride, which is suitable for copolymerization reactivity and solubility of a developing solution, that is, an alkaline aqueous solution. The above unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof or the like is preferably contained in an amount of 5 to 40% by weight, preferably 10 to 30% by weight based on the total of the total monomers. When the content is less than 5% by weight, there is a problem that it is difficult to dissolve in an alkaline aqueous solution, and when it exceeds 40% by weight, the solubility in an alkaline aqueous solution may become too large. The epoxy group-containing unsaturated compound of the above a) ii) used in the present invention may be used, glycidyl acrylate vinegar, glycidyl methacrylate 7 201003317 ester, α-ethyl methacrylate glycidyl ester, α-n - glycidyl propyl acrylate, glycidyl α-η-butyl acrylate, β-mercapto glycidyl acrylate, methacrylic acid mono (3-methyl glycidyl ester, acrylic acid ethyl glycidyl ester,曱β-ethylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, methacrylic acid —6, 7-epoxyheptyl ester, α-ethyl acrylate-6, 7-epoxyheptyl ester, fluorene-vinyl phenyl fluorenyl ether, m-vinyl benzyl glycidyl ether, or ρ-vinyl benzene The above compound may be used singly or in combination of two or more kinds thereof. The above-mentioned epoxy group-containing unsaturated compound, in particular, glycidyl thioglycolate, methacrylic acid-β-methyl shrinkage Glyceride, methacrylic acid-6, 7- In the case of oxyheptyl ester, hydrazine-vinyl benzyl glycidyl ether, claw-ethylene methyl glycidyl ether or p_vinyl benzyl glycidyl ether, in terms of improving copolymerization reactivity and heat resistance of the obtained pattern More preferably, the epoxy group-containing unsaturated compound is preferably contained in an amount of 5 to 70% by weight, preferably 2 to 6 % by weight, based on the total monomer. The content is less than 5% by weight. In the case of the problem, the heat resistance of the obtained pattern is lowered, and when it exceeds 70% by weight, the problem of the storage stability of the copolymer is lowered. Further, the above iii used in the production of the acrylic copolymer of the present invention. The olefin-based unsaturated compound can be used, methyl methacrylate, methyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, isopropyl acrylate , cyclohexyl methacrylate, 2~methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, 201003317 dicyclopentane Methyl Oleate, i-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methyl ring Hexyl acrylate, dicyclopentanyl decyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-mercaptobenzene Ethylene, m-methylstyrene, P-nonylstyrene, vinyl anthracene, P-nonyloxystyrene, 1,3-butadiene, isoprene, or 2,3-didecyl -1,3-butadiene or the like, the above compounds may be used singly or in combination of two or more. The olefin-based unsaturated compound, in particular, when styrene, dicyclopentyl methacrylate or p-nonyloxy styrene is used, in terms of copolymerization reactivity and solubility in an aqueous alkaline solution as a developing solution More suitable. The above olefin-based unsaturated compound is preferably contained in an amount of 10 to 70% by weight, preferably 20 to 50% by weight based on the total of the monomers. When the content is within the above range, the problem that the storage safety of the acrylic copolymer is lowered and the propylene-based copolymer is difficult to dissolve in the alkaline aqueous solution of the developer can be solved at the same time. The solvent used in the polymerization of the monomer as described above into an acrylic copolymer may be methanol, isopropanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or methyl cellosolve acetic acid. Ester, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol diterpene ether, ethylene glycol diethyl ether, ethylene glycol oxime ether, propylene glycol monoterpene ether, Propylene glycol monoethyl ether, propylene glycol c, propylene glycol butyl ether, propylene glycol hydrazine linkage acetic acid g, propylene glycol ether vinegar 9 201003317 acid ester, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol acetam Propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, diphenylbenzene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-indenyl-2-pentanone, methyl acetate 'acetic acid B Ester, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, decyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyl Ethyl acetate, butyl glycolate, decyl lactate, ethyl lactate, propyl lactate Butyl lactate, 3-propyl methyl propionate, ethyl 3-hydroxypropionate, 3-propyl propyl propionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutyric acid formazan , methoxyacetic acid methyl ketone, methoxyacetic acid ethyl vinegar, methoxyacetic acid propylene, methoxy butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, ethoxy acetate Ester, butyl ethoxyacetate, decyl propyl acetate, ethyl propoxy acetate, propyl propoxy propyl acetate, butyl propoxy acetate, decyl acetoacetate, ethyl butoxide , butyl butoxyacetate, butyl butoxyacetate, decyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxyl Butyl propionate, decyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxypropane Methyl ester, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, decyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, 3-methoxypropionic propionate, 3-methoxyl Butyl acrylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropane Methyl ester, 3-propoxypropionic acid ethyl acetate, 3-propoxypropionic acid propane S, 3-propoxy propionic acid butyl ester, 3-butoxy propionate decyl ester, 3-butoxy group Ethyl propionate, 3-butoxy 10 201003317 propyl propyl propionate, or an ether such as butyl 3-butoxypropionate, and the like may be used alone or in combination of two or more. A radical polymerization initiator can be used for the polymerization initiator used for polymerizing the monomer as described above to form an acrylic copolymer. Specifically, 2,2-azobisisobutyronitrile can be used. 2-azobis(2,4-dimercaptophthalonitrile), 2,2-azobis(4-hydrazino-2,4-dimercaptophthalonitrile), 1,1-azobis ( Cyclohexyl-1 曱 )) or 2,2-azobisisobutyric acid dimethyl vinegar and the like. The acrylic acid copolymer of the above a) may be polymerized by subjecting a monomer as described above to a radical reaction in the presence of a solvent and a polymerization initiator, or may be in an excess of insolubleness to a generally polymerized polymer. The solvent is produced by precipitation to include 1) a step of pouring a monomer, a polymerization solvent, and a polymerization initiator in a polymerization reactor equipped with a cooling device to polymerize the polymer; 2) a step of stopping the polymerization; 3 a step of cooling the reactor after the suspension of the polymerization to precipitate the polymer; 4) a step of separating the precipitated polymer; and 5) a step of dissolving the separated polymer in a solvent. . This case uses a relatively simple and simple process compared to conventional processes such as suspension polymerization or emulsion polymerization and bulk polymerization, and uses an acrylic copolymer having a monodisperse molecular weight, which can be described later. A photoinitiator containing [1-[9-ethylhexyl-6-(2-mercaptophenylhydrazine)-9H-carbazole-3-yl]-1-(0-acetamidine) together forms a liquid crystal When the organic insulating film of the element is displayed, the sensitivity, the residual film ratio, and the UV transmittance are further improved. In particular, even after the post-baking treatment of the conventional negative photosensitive resin is omitted, the excellent photosensitive film 11 201003317 degree can be exhibited. The monomer, the polymerization initiator, and the polymerization solvent used for the polymerization in the above step 1) are as described above, and a known cooling device can be used as the cooling device. A specific example can be a cooling jacket. The above-mentioned polymerization solvent is preferably used in a weight ratio, preferably a polymerization solvent which makes the total amount of the solid component used 5 to 50% by weight, more preferably 10 to 45% by weight. If the amount of the polymerization solvent is too large, the reaction conversion rate is lowered, the loss of the yield in the post-treatment procedure is large, and the cost is not good; if the amount of the solvent is too small, the molecular weight is not easily adjusted, and the subsequent polymer precipitation is also caused. It has become difficult. Further, the amount of the polymerization initiator is preferably 0.01 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight based on the total amount of the monomers. When the amount of the polymerization initiator is too small, the molecular weight of the polymer is excessively increased. If the amount is too large, the molecular weight is too low, and the sensitivity is lowered, and the pattern shape is deteriorated. Further, in the above step 1), the polymerization temperature is preferably carried out at a temperature higher than the 10-hour half-life temperature of the polymerization initiator, preferably 40 to 80 ° C, preferably 45 to 75 ° C. In this case, a polymer having a reduced content of unreacted monomers can be obtained, and a higher polymerization yield can be obtained. Further, the polymerization reaction time is preferably from 1 to 24 hours, preferably from about 2 to 20 hours. Further, if the inside of the reactor is stirred during the polymerization, the polymerization conversion ratio can be further improved. Further, in the step of 2) stopping the polymerization, it is of course possible to use a known polymerization suspension method, and an example thereof may be a method of pouring a polymerization inhibitor similar to phosphite such as 12 201003317 into a polymerization reaction product. The amount of the above-mentioned polymerization inhibitor to be used can be appropriately adjusted by those skilled in the art, and it is suitable to use an amount of from 100 to 3,000 ppm in the polymerization reaction. Further, in the above step 3), the polymerization reactor in which the polymerization has been suspended is cooled to precipitate a polymer, wherein the aforementioned cooling and precipitation temperatures are preferably from -30 to 40 ° C, more preferably from -20 to 30 ° C. When the precipitation temperature is too low, unreacted materials are precipitated together to cause residual volatile gas; if the precipitation temperature is too high, not only the yield is lowered, but also the molecular weight is difficult to control, and precipitates and polymerization solvents are difficult to be obtained. Separation situation. Further, in the above precipitation temperature range, when a polymer having a high molecular weight is required and the polarity of the polymerization solvent is low, it is preferred to carry out precipitation at a high precipitation temperature as much as possible. Further, the aforementioned precipitation time is preferably from 0.5 to 10 hours, preferably from 1 to 7 hours. When the precipitation time is too short, since sufficient separation does not occur, not only the unreacted materials and the additives are easily removed, but also the yield is lowered. If the sedimentation time is too long, the precipitates are self-reactive. A situation that causes deterioration. Further, in the step of separating the precipitated polymer in the above 4), it is of course possible to apply a known separation method to the above separation, and it is specifically exemplified by filtration. Further, in the step of dissolving the separated polymer in a solvent in the above 5), the solvent may be used as long as it can dissolve the polymer, and specific examples thereof may be decyl alcohol, ethanol, propanol or isopropanol. Butanol, hexanol, alcohols; tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, thiol cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monoterpene ether, 13 201003317 Diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, Propylene glycol ethyl ether acetate, propylene glycol propyl acetate vinegar, propylene glycol butyl ether acetate vinegar, propylene glycol methyl ether propionate, propylene glycol monoethyl propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl Ether propionate, toluene, xylene, methyl ethyl ketone, and the like. The solvent is preferably used in an amount such that the solid content of the polymer reaches 10 to 50% by weight. In this case, the storage stability of the produced acrylic copolymer can be further improved. According to a tenth aspect of the invention, the acrylic polymer has a polystyrene-equivalent weight average molecular weight (Mw) of 1, 〇〇〇-4〇, 〇〇〇, and 3, 〇〇〇_2〇 〇〇〇. When the polystyrene-equivalent weight average molecular weight of the negative-type photosensitive resin composition is less than 1,000, the developability, the residual film ratio, and the like are lowered, and the pattern shape 'the problem of deterioration of heat and the like' exceeds 4%. Contact hole and pattern development problems. X Ming used to describe b) & light start Qi |, characterized by containing D [9-ethyl-6-(2-mercaptobenzylidene)-9h-carbazole u - 1- (〇 - B cool month loss). The above [Bu [9-ethyl-6-(2-methylmethyl decyl)-9H-Ten-3-yl]-Bu (〇-Buan) can be used in two commercial products, you can use Ciba coffee ❿心丨$Company〗

Irgacure OXE 02為其一你f。么、+.，丄 1則述光起始劑，可以單獨使〗 前述[1-[9 一乙基一 6— (2—甲基笨甲醯基）—9h—十 -3-基卜卜⑺—乙_)’或將—般的枝始劑盘[ - [9一乙基一 6 —(2一甲基笨甲醯基)—9h—咔唑一 2—基 14 201003317 —1 — (〇—乙醯肟）混合使用。 可與前述[1 一 [9 一乙基一 6 —（2 —曱基苯曱醯基）一 9H—咔唑一3 —基]—1— (Ο—乙醯肟）混合使用的光起始 劑之例，可以使用三嗪系、二苯乙醇酮、苯乙酮系、咪唑 系或咕噸酮系等的化合物，具體例可以單獨使用2, 4—雙 (三氯曱基）一6 — p—曱氧基苯乙烯一s —三嗪、2 —p—曱 氧基苯乙稀一 4,6 —雙（三氯曱基）一 s—三°秦、2，4一三氣 甲基一 6—三嗪、2,4一三氯甲基一4—甲基萘基一6—三嗪、 二苯甲酉同、p—(二乙氨基）二笨曱酮、2,2 —二氯一4 —苯 氧基苯乙酮、2,2—二乙氧基苯乙酮、2—十二烷基噻噸酮、 2,4一二曱基噻噸酮、2,4—二乙基噻噸酮、2,2—雙一 2—氯 笨基—4,5,4,5-四苯基一2—1,2—二咪唑，Ciba Specialty Chemicals公司的 Irgacure 369、Irgacure 651、Irgacure 907、 Darocur TPO、Irgacure 819等化合物，或可進一步混合2種 以上來使用。 前述光起始劑，以相對於丙烯酸系共聚物100重量份含 有0.001到30重量份為佳，較佳的是含有0.01到20重量份。 當其含量不滿0.001重量份時，會有因低感光度造成殘膜率 惡化的問題，超過30重量份時，在保存安定性上會產生問 題，有因高硬化度而導致顯影時圖案的黏著力降低的問題。 另外，本發明所使用之前述c)的具有乙烯性不飽和鍵 的多官能性單體，通常是至少具有2個以上的乙烯系雙鍵之 交聯性單體，可以使用1, 4一丁二醇二丙烯酸酯、二丙烯酸 -1,3-丁二醇酯、乙二醇二丙烯酸酯、三羥曱基丙烷二丙烯 15 201003317 酸酯、三羥曱基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、 季戊四醇四丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二 丙烯酸酯、二季戊四醇六二丙烯酸酯、二季戊四醇三二丙 烯酸酯、二季戊四醇二丙烯酸酯、山梨糖醇三丙烯酸酯、 雙酚A二丙烯酸酯衍生物、二季戊四醇聚丙烯酸酯，或其等 之曱基丙烯酸酯類等。 前述具有乙烯性不飽和鍵的多官能性單體，以相對於 丙烯酸系共聚物100重量份含有10至100重量份為佳，較佳 為含有10到60重量份。其含量不滿10重量份時，有因感光 性樹脂的低硬化度而導致難以使接觸孔及圖案具體化的問 題，超過100重量份時，有因高硬化度而造成顯影時接觸孔 及圖案的解析度降低的問題。 另外，本發明中所使用之前述d)的含有環氧基或胺基 之矽系化合物，可以單獨使用（3—縮水甘油氧基丙基）三 曱氧基碎烧、（3 —縮水甘油氧基丙基）二乙氧基石夕烧、（3 一縮水甘油氧基丙基）甲基二甲氧基矽烷、（3—縮水甘油 氧基丙基）三甲氧基矽烷、（3—縮水甘油氧基丙基）二曱 基乙氧基石夕烧、（3 —縮水甘油氧基丙基）二甲基乙氧基石夕 烷、3,4—環氧丁基三甲氧基矽烷、3,4一環氧丁基三乙氧基 矽烷、2— (3,4一環氧環已基）乙基三甲氧基矽烷、2— (3,4 一環氧環已基）乙基三乙氧基石夕烧或氨丙基三甲氧基石夕烧 等，或混合2種以上來使用。 前述含有環氧基或胺基的矽系化合物，以相對於丙烯 酸系共聚物1⑻重量份含有0.0001到5重量份為佳，較佳的 16 201003317 是含有0.005到2重量份。其含量不滿〇 〇〇〇1重量份時，會有 I TO電極和感光性樹脂的粘著力下降，硬化後的耐熱特性下 降的問題，超過5重量份時，在顯影液内會有非曝光部分的 白化現象，以及顯影後產生接觸孔和圖案的膜渣“⑶爪） 的問題。 另外，本發明中所使用之前述e)的溶劑要讓層間絕緣 膜具有平坦性並且不產生樹脂塗層斑地形成均勻的圖案輪 廓。 前述溶劑可以使用甲醇、乙醇等的醇類；四氫呋喃的 醚類；乙二醇單甲醚、乙二醇單乙醚等之乙二醇醚類；甲 基溶纖劑乙酸酯、乙基溶纖劑乙酸酯等之乙二醇烷醚乙酸 酯類；二乙二醇單曱醚、二乙二醇單乙基醚、二乙二醇二 甲基醚等之二乙二醇類；丙二醇甲醚、丙二醇乙醚、丙二 醇丙醚、丙二醇丁醚等的丙二醇單烷醚類；丙二醇曱醚醋 fecSs、丙一醇乙鱗醋酸醋、丙二醇丙喊醋酸酿、丙二醇丁 醚醋酸酯等的丙二醇烧醚醋酸酯類；丙二醇甲醚丙酸酯、 丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸 酯等的丙二醇烷醚醋酸酯類；甲苯、二甲苯等的芳香族烴 類；甲乙酮、環己酮' 4一羥基一4—甲基一2—戊酮等的酮 類，或乙酸甲醋、乙酸乙g旨、乙酸丙g旨、乙酸丁醋、2 —經 基丙酸乙酯、2—羥基一2—甲基丙酸甲酯、2一羥基一 2 — 甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸 丁 S曰乳酸甲醋、乳酸乙g旨、乳酸丙醋、乳酸丁醋、3 一經 基丙酸曱酯、3—羥基丙酸乙酯、3 —羥基丙酸丙酯、3一羥 17 201003317 基丙酸丁酯、2—羥基一3 —甲基丁酸甲酯、甲氧基乙酸甲 酯、曱氧基乙酸乙酯、曱氧基乙酸丙酯、甲氧基乙酸丁酯、 乙氧基乙酸曱酯、乙氧基乙酸乙酯 '乙氧基乙酸丙酯、乙 氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧 基乙酸丙酯、丙氧基乙酸丁酯'丁氧基乙酸甲酯、丁氧基 乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2 —甲氧基 丙酸甲酯、2—甲氧基丙酸乙酯、2—甲氧基丙酸丙酯、2 — 曱氧基丙酸丁酯、2—乙氧基丙酸甲酯、2—乙氧基丙酸乙 西旨、2—乙氧基丙酸丙醋、2—乙氧基丙酸丁自旨、2 — 丁氧基 丙酸曱S旨、2 — 丁氧基丙酸乙S旨、2 — 丁氧基丙酸丙S旨、2 — 丁氧基丙酸丁酯、3—曱氧基丙酸曱酯、3 —曱氧基丙酸乙 西旨、3 —甲氧基丙酸丙醋、3—乙氧基丙酸甲醋、3 —乙氧基 丙酸乙酯、3 —乙氧基丙酸丙酯、3—乙氧基丙酸丁酯、3 — 丙氧基丙酸曱酯、3—丙氧基丙酸乙酯、3 —丙氧基丙酸丙 酯、3 —丙氧基丙酸丁酯、3—丁氧基丙酸甲酯、3 — 丁氧基 丙酸乙酯、3 — 丁氧基丙酸丙酯、3 — 丁氧基丙酸丁酯等的 酯類等。 前述溶劑尤以從溶解性、與各成分的反應性，以及容 易形成塗膜的乙二醇醚類、乙烯烷醚醋酸酯類及二乙二醇 類所組成的族群中選擇1種以上來使用為佳。 前述溶劑以含有使全體感光性樹脂組成物的固形分含 量變成10到5 0重量％為佳，含有前述範圍的固形分之組成 物宜用0.1〜0·2μιη的微孔濾膜（milliporefilter)等過濾之 後再使用。較佳的是，含有15到40重量％。前述全體組成 18 201003317 物的固形分含量不滿10重量％時，有塗布厚度變薄’塗布 平板性降低的問題’超過50重量％時，有塗布厚度變厚， 塗布時造成塗布詨備難以操作的問題。 由如前所述的成分組成之本發明的負型感光性樹脂組 成物根據需要玎以另外含有，f)光敏劑，以及g)界面活 性劑。 前述〇光敏劑’對於所使用的紫外線波長有適當的感 光度，藉由比光起始劑還快的光起始反應使能量移轉到光 起始劑，有助於光起始劑的光起始反應速度。 前述光敏劑玎以單獨使用DETX、ΙΤΧ、N—丁基吖啶 酮、或2—乙基己基一二甲基氨基苯甲酸酯等，或混合2種 以上來使用。 前述光敏劑，以相對於前述b)的光起始劑100重量份 含有0.001到100重量份為佳，其含量在前述範圍内時，在 提高負型感光性樹脂組成物的光硬化速度上較佳。Irgacure OXE 02 is one for you. 、,+.,丄1, the photoinitiator, can be used alone to make the above [1-[9-ethyl-1-6-(2-methylacylmethyl)- 9h-ten-3-ylbub (7)-B_)' or the general branching agent tray [- [9-ethyl-6-(2-methyl-methyl)- 9-carbazole-2-yl 14 201003317 —1 — ( 〇- 醯肟 醯肟) mixed use. Light start-up which can be used in combination with the above [1 -[9-ethylhexyl-6-(2-nonylphenylhydrazino)-9H-carbazole-3-yl]-1-(indole-ethene) As an example of the agent, a compound such as a triazine, a benzophenone, an acetophenone, an imidazole or a xanthone may be used, and in particular, 2,4-bis(trichloroindenyl)-6 may be used alone. P-nonyloxystyrene-s-triazine, 2-p-decyloxyphenethyl-4,6-bis(trichloroindenyl)-s-trisyl, 2,4-trimethylmethyl a 6-triazine, 2,4-trichloromethyl-4-methylnaphthyl- 6-triazine, benzophenone, p-(diethylamino) dioxin, 2,2 - 2 Chloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-diylthioxanthone, 2,4-diethyl Thiophenone, 2,2-di- 2,4-chlorophenyl-4,5,4,5-tetraphenyl-2,2-diimidazole, Irgacure 369, Irgacure 651, Irgacure by Ciba Specialty Chemicals Compounds such as 907, Darocur TPO, and Irgacure 819 may be used in combination of two or more. The photoinitiator is preferably contained in an amount of 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, per 100 parts by weight of the acrylic copolymer. When the content is less than 0.001 part by weight, there is a problem that the residual film ratio is deteriorated due to low sensitivity. When the amount exceeds 30 parts by weight, there is a problem in preservation stability, and the pattern is adhered due to high curing degree. The problem of reduced force. Further, the polyfunctional monomer having an ethylenically unsaturated bond of the above c) used in the present invention is usually a crosslinkable monomer having at least two ethylene double bonds, and can be used as a 1,4 Diol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trishydroxypropyl propane dipropylene 15 201003317 acid ester, trishydroxypropyl propane triacrylate, pentaerythritol triacrylate , pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, double A phenol A diacrylate derivative, a dipentaerythritol polyacrylate, or a mercapto acrylate thereof or the like. The above polyfunctional monomer having an ethylenically unsaturated bond is preferably 10 to 100 parts by weight, preferably 10 to 60 parts by weight, per 100 parts by weight of the acrylic copolymer. When the content is less than 10 parts by weight, the contact hole and the pattern are difficult to be specified due to the low degree of hardening of the photosensitive resin. When the content exceeds 100 parts by weight, the contact hole and the pattern are developed due to high curing degree. The problem of reduced resolution. Further, in the above-mentioned d), the epoxy group- or amine group-containing oxime compound used in the present invention may be used alone (3-glycidoxypropyl) tridecyloxy calcination, (3-glycidyloxygen) Propyl)diethoxy sulphur, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)trimethoxynonane, (3-glycidyloxy) Propyl propyl) dimethyl ethoxylate, (3 - glycidoxypropyl) dimethyl ethoxy oxane, 3, 4-epoxybutyl trimethoxy decane, 3, 4 ring Oxybutyl butyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxylate Or aminopropyltrimethoxy zebra or the like, or a mixture of two or more types. The above-mentioned epoxy group- or amine group-containing oxime compound is preferably contained in an amount of 0.0001 to 5 parts by weight based on 1 part by weight of the acryl-based copolymer, and preferably 16 201003317 is contained in an amount of 0.005 to 2 parts by weight. When the content is less than 1 part by weight, the adhesion between the I TO electrode and the photosensitive resin is lowered, and the heat resistance after curing is lowered. When the content exceeds 5 parts by weight, there is a non-exposed portion in the developer. The whitening phenomenon, and the problem of the film slag "(3) claws which generate contact holes and patterns after development. In addition, the solvent of the above e) used in the present invention is such that the interlayer insulating film is flat and does not cause resin coating spots. A uniform pattern profile is formed in the ground. The solvent may be an alcohol such as methanol or ethanol; an ether of tetrahydrofuran; a glycol ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; and methyl cellosolve B. Ethylene glycol alkyl ether acetates such as acid esters, ethyl cellosolve acetates, etc.; diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, etc. Glycols; propylene glycol monoether ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol oxime ether fecSs, propylene glycol acetate, propylene glycol, acetic acid, propylene glycol butyl ether Propylene glycol such as acetate Ethyl acetates; propylene glycol alkyl ethers such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; a ketone such as methyl ethyl ketone or cyclohexanone ' 4-hydroxy-4-methyl-2-pentanone, or methyl acetate, acetic acid, acetic acid, butyl acetate, 2-propionic acid Ethyl ester, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid butyl S-lactic acid methyl vinegar, lactate B g, lactic acid propyl vinegar, lactic acid butyl vinegar, 3- propyl propyl propionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxyl 17 201003317 butyl propionate, 2-hydroxy one 3-methyl methyl butyrate, methyl methoxyacetate, ethyl decyloxyacetate, propyl methoxyacetate, butyl methoxyacetate, decyl ethoxyacetate, ethyl ethoxyacetate 'Ethyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, Butyl oxyacetate, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methoxypropane Ethyl acetate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid, 2-ethoxyl Propionate propionate, 2-ethoxypropionic acid butyl, 2 -butoxypropionate 曱S, 2 -butoxypropionic acid B, 2 -butoxypropionic acid C, 2 - butyl butoxypropionate, decyl 3-methoxypropionate, 3-oxetoxypropionic acid, 3-methoxypropionic acid propyl vinegar, 3-ethoxypropionic acid methyl vinegar, 3—Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, decyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, 3 — Esters such as butyl butoxypropionate. In particular, one or more selected from the group consisting of a solvent, a reactivity of each component, and a glycol ether, a vinyl ether ether acetate, and a diethylene glycol which are easy to form a coating film are used. It is better. The solvent is preferably contained in an amount of 10 to 50% by weight based on the total photosensitive resin composition, and a composition containing a solid content in the above range is preferably a microporous filter of 0.1 to 0.2 μm. Filter and use. Preferably, it contains 15 to 40% by weight. When the solid content of the whole composition 18 201003317 is less than 10% by weight, the coating thickness is reduced, and the problem of the coating flatness is lowered. When the content exceeds 50% by weight, the coating thickness is increased, and the coating preparation is difficult to handle during coating. problem. The negative photosensitive resin composition of the present invention consisting of the above-mentioned components contains, as needed, f) a photosensitizer, and g) an interfacial activator. The aforementioned bismuth photosensitizer has an appropriate sensitivity to the wavelength of ultraviolet light used, and the light is initiated by the light-initiating reaction faster than the photoinitiator to transfer the energy to the photoinitiator, which contributes to the light-initiating agent. The initial reaction rate. The photosensitizer 使用 is used alone or in combination of two or more kinds of DETX, hydrazine, N-butyl acridone, or 2-ethylhexyl-dimethylaminobenzoate. The photosensitizer is preferably contained in an amount of 0.001 to 100 parts by weight based on 100 parts by weight of the photoinitiator of the above b), and when the content is within the above range, the photocuring speed of the negative photosensitive resin composition is improved. good.

前述g)的界面活性劑發揮使感光性組成物的塗布性和 顯影性提高的作用。 可以使用聚氧乙烯辛基苯基醚、聚 l7l、F172、F173 (商品名：大日本The surfactant of the above g) functions to improve the coatability and developability of the photosensitive composition. Polyoxyethylene octylphenyl ether, poly l7l, F172, F173 (trade name: Dainippon)

前述界面活性劑， 氧乙烯壬基苯基醚、F 油墨公司）、FC 430、FC心,/士 Λ (商品名：住友3μ公司）或ΚΡ 341 (商品名：信越化學工業社）等。 Θ 目對於前述〇的丙稀酸系共聚物励 重量份含有0·__重量份為佳，其含量在前述範圍内 夺在提问負里感光性組成物的塗布性和顯影性上較佳。 19 201003317 另外，本發明的負型感光性樹脂組成物可依需要在前 述組成物中添加熱聚合抑制劑、消泡劑等有相溶性的添加 劑，根據用途可以添加顏料。 另外，本發明提供使用如前所述之負型感光性樹脂的 液晶顯示元件之有機絕緣膜形成方法及包含前述有機絕緣 膜的液晶顯不元件。 本發明的液晶顯示元件之有機絕緣膜形成方法可以完 全應用到如第1圖及大韓民國特許公開第2006-0038788 號、第2008-002464號、第2008-0018606號所記載之TFT型 液晶顯示元件及TFT型反射型液晶顯示元件的有機絕緣膜 之形成。 前述液晶顯示元件的有機絕緣膜形成方法，對應於使 用公知的感光性樹脂組成物來形成有機絕緣膜，特徵在於 使用前述負型感光性樹脂組成物，而除了前述負型感光性 樹脂組成物以外的其餘事項，當然可以採用由熟習該項技 術者適當選擇出的公知方法。更具體的形成液晶顯示元件 之有機絕緣膜的方法之一例係如下所載。 首先，將本發明的負型感光性樹脂組成物用喷塗法、 輥塗法、旋轉塗布法等塗布於基板表面，利用預烘除去溶 劑以形成塗膜。此時，前述預烘宜在70〜110°c的溫度實施 1〜15分鐘。 之後，根據預先準備的圖案，將可見光、紫外線、遠 紫外線、電子束、X射線等照射於前述已形成之塗膜，用顯 影液顯影除去不需要的部分，藉而形成預定的圖案。 20 201003317 別述顯影液以使用鹼性水溶液爲佳，具體的可以使用 氣氧化鈉、氫氧化鉀、；E炭酸鈉等的無機鹼類；η一丙胺等的 1級胺類；二乙胺、η一丙胺等的2級胺類；三曱胺、曱基二 乙胺、二曱基乙胺 '三乙胺等的3級胺類；二曱基乙醇胺、 甲基二乙醇胺、三乙醇胺等的醇胺類；或四甲基氫氧化銨、 四己基氫氧化銨等的4級銨鹽的水溶液等。此時，前述顯影 液係將驗性化合物溶解成0.1〜10重量％的濃度來使用，也 可以適量添加如甲醇、乙醇等之類的水溶性有機溶劑及界 面活性劑。 另外，用如前所述之顯影液顯影後，以超純水洗淨30 9〇秒除去不要的部分並加以乾燥形成圖像，對前述已形 成之圖案照射紫外線等的光之後，將圖案以烤箱等的加熱 裝置在150〜250。(：的溫度施行加熱處理3〇〜9〇分鐘可以得 到最終圖案。 如釗所述之依據本發明的負型感光性樹脂組成物，因 姑著力、解析度、絕緣性、平坦性、耐化學性及等的性能 俱優’特別是在形成高開口率液晶顯示元件與反射型液晶 顯不凡件的有機絕緣膜時，感光度、殘膜率及UV透射率與 優良，故而適於作爲有機絕緣膜使用。 以下，雖提示合適的實施例以供理解本發明，惟下述 ' %例僅為本發明之例示，本發明的範圍並不限於下述實 施例。 實施例 實施例1 (丙烯醆系共聚物的製造） 21 201003317 將異丙醇400重量份、甲基丙烯酸30重量份和苯乙烯30 重量份、曱基丙稀酸縮水甘油@旨25重量份、丙稀酸2 —經基乙 酯15重量份的混合溶液倒入具備冷卻器和攪拌器的2L長頸 燒瓶（Flask)。將前述液狀組成物在混合容器中以600rpm 充分混合後，添加2, 2’ 一偶氮二（2, 4一二曱基戊腈）15 重量份。使前述聚合混合溶液緩緩昇溫至50°C，維持此溫 度6小時得到共聚物溶液。將亞填酸酯5OOppm當作阻聚劑添 加到所獲得之聚合物中。使前述聚合已經被中止的長頸燒 瓶溫度下降至18°C，使之停滯1小時後得到生成的析出物並 加以過濾。加入作為溶劑之丙二醇單乙醚丙酸酯，使前述 過濾所得的析出物85重量份變成析出物含量為45重量％， 得到丙烯酸系共聚物。所得的聚合物溶液之丙烯酸系聚合 物的重量平均分子量是11,000。此時，重量平均分子量是使 用GPC測定的聚苯乙烯換算平均分子量。 (負型感光性樹脂組成物的製造） 將含有前述已製成的丙烯酸系共聚物的聚合物溶液 100重量份，作為光起始劑的[1 —[9 —乙基一6 —（2—甲基 苯曱醯基）一9H—咔唑一3 —基]—1— (0—乙醯肟）20重 量份，作為多官能性單體的二季戊四醇六丙烯酸酯40重量份 及三羥曱基丙烷三丙烯酸酯10重量份、作爲矽系化合物的2 —(3, 4—環氧環己基）乙基三曱氧基矽烷1重量份，以及2 重量份之石夕系界面活性劑F 171加以混合。在前述混合物中 加入二乙二醇二曱醚使固形分濃度變成35重量％而溶解之 後，用0.2μιη的微孔濾膜過濾以製造負型感光性樹脂組成物 22 201003317 塗布溶液。 實施例2 除了使用10重量份的[1—w L 乙基一 6— (2—曱基苯 曱酸基）一9H—n卡唾一 3—基]1 (〇—乙酿肪）作為光 方法實施，製造負型感 起始劑外，以和前述實施例1相同的 光性樹脂組成物塗布溶液。 實施例3 除了使用5重量份之[1 一 r^ L 乙基〜ό—(2—曱基苯曱 酿基）一阳一11卡嗤—3 —基]—r 乙醯肟）作為光起 始劑外，以和前述實施例1相同的太 J的方法實施，製造負型感光 性樹脂組成物塗布溶液。 實施例4 乙基一6— (2—曱基苯甲 〇~~乙醢將），10重量 除了使用 醯基）一 9H — η卡。坐一 成物塗布溶液 實施例5 份的Irg_ 819作為光起始劑’ 5重量份的對二甲氨基苯 甲酸異转及5重量份的N—丁基。丫_作為光增減劑外 以和前述實施州相同的方法實施，製造負型感光性樹脂： 除使用5重量份的[卜[9—乙基—6—(2—甲基苯㈣ 基）-9H-十坐-3 —基(〇—乙_)，1〇重量份 的toe TPO作為光起始劑，並追加使用5重量份 ^氨基苯曱酸異辛醋及5重量份_—丁基。丫相作為切 減劑外’以和前述實施例i相同的方法實施，製造負型感^ 23 201003317 性樹脂組成物塗布溶液。 實施例6 除使用5重量份的[：[一 [9—乙I — 丞0 甲基苯甲醯 基）一9H —咔唑一3— 基]—1— 7 . 乙fe肟），1〇重量份 的IrgaCUre 369作為光起始劑，作為光增減劑5重量份的對二 甲氨基苯甲酸異辛S旨及5重量份丁基十定綱外，以和 前述實施例1相_方法實施，製造負型感光賴脂組成物 塗布溶液。 實施例7 除使用5重量份的[卜[9—乙基—6一（2 一甲基苯甲酿 基）—州―°卡哇—3 —基]—卜（〇一乙醯肪），5重量份的 IrgaCUre 369作為光起始劑，5重量份的2—乙基己基—4一二 曱基氨f醋及5重量份的N-丁基十定綱作為光增減劑外， 以和前述實施韻目同的方法實施，製造貞型感光性樹脂組 成物塗布溶液。 比較例1 在前述實施例4,除了不使用[i — [9 一乙基—6— (2一 曱基苯曱醯基）一 9H—咔唑一 3一基]一；! —（〇_乙醯肟）， 而使用20重量份819作為光起始劑外，以和前述 實施例4相同的方法實施，製造負型感光性樹脂組成物塗布 溶液。 比較例2 在前述實施例5，除了不使用[1 —[9一乙基—6— ( 2一 曱基苯曱醯基）—9H —咔唑一3 —基]一 1一（〇 一乙醯肟）， 24 201003317 而使用20重量份的Irgacure TPO作為光起始劑外，以和前述 實施例5相同的方法實施，製造負型感光性樹脂組成物塗布 溶液。 比較例3 在前述實施例6，除了不使用[1一 [9 —乙基一 6—（2 — 曱基苯曱醯基）一9Η—咔唑一3 —基]—1— (Ο—乙醯肟）， 而使用20重量份的Irgacure 369作為光起始劑外，以和前述 實施例6相同的方法實施，製造負型感光性樹脂組成物塗布 溶液。 比較例4 (正感光性樹脂組成物） (丙烯酸系共聚物的製造） 以和前述實施例1相同的方法製造丙烯酸系共聚物。 (1，2—醌二疊氮化合物的製造） 使1莫耳的4, 4’ 一[1—[4 一 [1 一 [4 一羥苯基]—1 一甲 基乙基]苯基]亞乙基]雙（苯）酚和2莫耳的1，2—二疊氮基 萘醌一 5—磺酸[氯化物]進行縮合反應，製造4, 4’ 一 [1 一 [4 一 [1一 [4 一經基苯基]一 1一曱基乙基]苯基]亞乙基]雙 酚1，2—二叠氮基萘醌一5 —磺酸酯。 (感光性樹脂組成物的製造） 將含有以前述實施例1所製造之丙烯酸系共聚物的聚 合物溶液100重量份及，前述所製造之4, 4’ 一[1—[4—[1 —[4一經基苯基]一 1一曱基乙基]苯基]亞乙基]雙盼1，2 — 二疊氮基萘醌一 5 —磺酸酯25重量份加以混合後，加入二乙 二醇二曱醚使該混合物之固形分濃度變成35重量％，使之 25 201003317 溶解’用0 · 2 μ m的微孔渡膜過渡以製造感光性樹脂组成物塗 布溶液。 用前述實施例1至7及比較例1至3所製造的負型感光性 樹脂組成物與比較例4所製造的正感光性樹腊組成物塗布 溶液，以如下所述之方法評估物性後，將其結果示於下表i。 1) 感光度一在玻璃（glass)基板上使用旋轉塗布法塗 布以前述實施例1至7及比較例1至3所製造的負型感光性樹 脂組成物與比較例4所製造的正感光性樹脂組成物溶液 後，在熱板上以90°C預烘2分鐘形成膜。 對前面所獲得之膜使用預定的圖案光罩（paUernmask) 照射在365mn的強度為15mW/cm2的紫外線6秒鐘。之後， 以四甲基氫氧化銨0.38重量份的水溶液在2yc顯影2分鐘 後，以超淨水洗淨1分鐘。 之後，對於在前面已經顯影的圖案照射在365 nm的強 度為15mW/cm2的紫外線34秒，在120。(：中烘3分鐘後，在 烤箱中以220°C加熱60分鐘使其硬化，得到圖案膜。 2) 殘膜率一測定於前述1)之感光度測定時所形成的 圖案膜的最低和圖案膜的最高高度。此時，厚度變化率是 以預烘所得到之膜厚爲基準，〇〜10%的情形表示為優秀， 10〜40%的情形表示為良好，超過40%的情形表示為差。 3) 透射率一測定於前述1)之感光度測試時，預烘後 的膜尽為3微米的塗膜之可見光的光吸收光譜（Spectrem)， 在40〇nm下’光線透射率在98%以上時表示為非常優秀， 92〜94%時表示為普通，92%以下時表示為差。 26 201003317 [表1] 分類 -- -ί ^施例 厂 '-^—— 比較你丨 1 2 3 4 ΓΓ 6 7 1 2 3 4 140 感光度 (mJ/cm2) 7 11 ---— 9 10 7 9 60 75 45 殘膜率 優秀 優秀 良好 良好 良好 優秀 良好 差 差 華 優秀 透射率 差 優秀 非常 非常 非常 優秀 優秀 優秀 差 普通 優秀 優秀 差 差 料表1可以確認’依據本發明，含有光起始劑卜 [9 一乙基—6 一（2〜甲基笨甲醯基）一 9H—咔唑一3一基] 一卜（〇—乙_)所製造的實施例1到7,感光度為5—u mJ/cm2 ’與比較例⑷相比非常優秀，在透射率方面愈 現有的正型絕緣膜相比顯示出相當優異的透射率’另一^ ^與不含光起始劑[H9—乙基—6— (2—甲基苯甲醯 -¾ ) 9 Η — σ卡 σ坐—α —发 1 -t / 土 j — 1— (〇—乙醯肟）的負型光阻 Γ目類似’顯示出優異的透射率。特別是，可以確認與比 較例1及3相比在殘膜率方面是相當優異的。 圖傻i使用依據本發明之㈣感光性樹脂組成物作為 料的高開口―元件和半透型液晶顯 光度、殘膜率及透射率。確^夠传到非常優異的感 習就本發明所記載之具體例進行了說明，惟熟 應該明白在本發明的技術思想範圍内可以進 夕7的變形及修正’而這樣的變形及修正當然屬於 27 201003317 本發明之申請專利範圍。 【圖式簡單說明】 第1圖具有高開口率的TFT型液晶顯示元件單元之示 意平面圖。 第2圖沿著第1圖的Π — Π ’線切斷的斷面圖。 【主要元件符號說明】 1…下基板 6…半導體層 2…閘門電極 7…電源電極 2a…閘線 8…漏極電極 3a…存儲電極線 9…有機絕緣膜 4···閘極絕緣膜 5…數據線 10…圖元電極 28The above surfactants, oxyethylene decyl phenyl ether, F ink company, FC 430, FC heart, / Λ Λ (trade name: Sumitomo 3μ company) or 341 341 (trade name: Shin-Etsu Chemical Industry Co., Ltd.). The content of the acrylonitrile-based copolymer in an amount of 0 _ _ by weight is preferably in the range of the above-mentioned range, and the coating property and developability of the photosensitive composition are preferably within the above range. Further, in the negative photosensitive resin composition of the present invention, a compatible additive such as a thermal polymerization inhibitor or an antifoaming agent may be added to the above-mentioned composition as needed, and a pigment may be added depending on the use. Further, the present invention provides an organic insulating film forming method using a liquid crystal display element of a negative photosensitive resin as described above and a liquid crystal display element comprising the above organic insulating film. The method for forming an organic insulating film of a liquid crystal display device of the present invention can be fully applied to a TFT-type liquid crystal display device as described in FIG. 1 and the Korean Patent Publication No. 2006-0038788, No. 2008-002464, and No. 2008-0018606. Formation of an organic insulating film of a TFT type reflective liquid crystal display element. In the method of forming an organic insulating film of the liquid crystal display device, an organic insulating film is formed by using a known photosensitive resin composition, and the negative photosensitive resin composition is used, and the negative photosensitive resin composition is used. The rest of the matter can of course be carried out using well-known methods appropriately selected by those skilled in the art. A more specific example of a method of forming an organic insulating film of a liquid crystal display element is as follows. First, the negative photosensitive resin composition of the present invention is applied onto the surface of the substrate by a spray coating method, a roll coating method, a spin coating method, or the like, and the solvent is removed by prebaking to form a coating film. At this time, the pre-baking is preferably carried out at a temperature of 70 to 110 ° C for 1 to 15 minutes. Thereafter, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or the like are applied to the formed coating film according to a pattern prepared in advance, and the unnecessary portion is removed by development with a developing solution to form a predetermined pattern. 20 201003317 The developing solution is preferably an alkaline aqueous solution, and specific examples thereof include inorganic bases such as sodium oxysulfide, potassium hydroxide, and sodium carbonate; and amines such as η-propylamine; diethylamine; a secondary amine such as η-propylamine; a tertiary amine such as tridecylamine, decyldiethylamine or dimercaptoethylamine triethylamine; dimercaptoethanolamine, methyldiethanolamine, triethanolamine, etc. An alcohol amine; or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetrahexylammonium hydroxide. In this case, the developer may be used by dissolving the test compound in a concentration of 0.1 to 10% by weight, or a water-soluble organic solvent such as methanol or ethanol or the like may be added in an appropriate amount. Further, after developing with the developing solution as described above, it is washed with ultrapure water for 30 9 seconds to remove unnecessary portions and dried to form an image. After the formed pattern is irradiated with light such as ultraviolet rays, the pattern is Heating devices such as ovens are in the range of 150 to 250. The temperature of (: the temperature is subjected to heat treatment for 3 〇 to 9 〇 minutes to obtain a final pattern. The negative photosensitive resin composition according to the present invention as described in the above, due to the acuity, resolution, insulation, flatness, chemical resistance Excellent performance in terms of properties and the like, especially when forming an organic insulating film having a high aperture ratio liquid crystal display element and a reflective liquid crystal display element, the sensitivity, the residual film ratio, and the UV transmittance are excellent, and thus it is suitable as an organic insulation. The following examples are given to illustrate the invention, but the following '% are merely illustrative of the invention, and the scope of the invention is not limited to the following examples. Example 1 Manufacture of copolymers) 21 201003317 400 parts by weight of isopropyl alcohol, 30 parts by weight of methacrylic acid and 30 parts by weight of styrene, glycidyl methacrylate = 25 parts by weight, and acrylic acid 2 - by base 15 parts by weight of the mixed solution of the ester was poured into a 2 L long-necked flask (Flask) equipped with a cooler and a stirrer. After the liquid composition was thoroughly mixed in a mixing vessel at 600 rpm, 2, 2'-azobis was added ( 2, 4 one two 15 parts by weight of the valeronitrile. The polymerization mixture solution was gradually heated to 50 ° C, and the temperature was maintained for 6 hours to obtain a copolymer solution. 5OOppm of the sub-filler was added as a polymerization inhibitor to the obtained polymer. The temperature of the long-necked flask in which the above polymerization had been stopped was lowered to 18 ° C, and the resulting precipitate was obtained by allowing to stand for 1 hour and filtered. The propylene glycol monoethyl ether propionate as a solvent was added to precipitate the above-mentioned filtration. 85 parts by weight of the product became a precipitate content of 45% by weight to obtain an acrylic copolymer. The weight average molecular weight of the obtained acrylic polymer of the polymer solution was 11,000. At this time, the weight average molecular weight was polystyrene measured by GPC. Conversion average molecular weight (manufacture of negative photosensitive resin composition) 100 parts by weight of a polymer solution containing the above-mentioned prepared acrylic copolymer as a photoinitiator [1 - [9 - ethyl - 6 -(2-methylphenylhydrazino)- 9H-carbazole-3-yl]-1-(0-acetamidine) 20 parts by weight of dipentaerythritol hexaacrylate 40 as a polyfunctional monomer 10 parts by weight of trihydromethane propane triacrylate, 1 part by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane as a quinone compound, and 2 parts by weight of Shi Xi The surfactant F 171 is mixed, and diethylene glycol diterpene ether is added to the above mixture to make the solid content concentration 35% by weight and dissolved, and then filtered with a 0.2 μm microporous membrane to prepare a negative photosensitive resin. Matter 22 201003317 Coating solution. Example 2 In addition to using 10 parts by weight of [1-w L ethyl-6-(2-mercaptobenzoic acid)- 9H-n-Carpin-3-yl]1 (〇- In the same manner as in the above Example 1, the coating solution was applied as a photo-method, except that a negative-type sensitizer was produced. Example 3 In addition to using 5 parts by weight of [1 - r ^ L ethyl ~ fluorene - (2- mercapto phenyl hydrazone) - cation - 11 嗤 - 3 - yl] - r acetyl) as light The negative photosensitive resin composition coating solution was produced by the same method as that of the above-mentioned Example 1, except that the starting agent was used. Example 4 Ethyl-6-(2- mercaptobenzoquinone~~acetamidine), 10 weights except for the use of fluorenyl)-9H-n card. The solution coating solution of Example 5 was used as the photoinitiator '5 parts by weight of p-dimethylaminobenzoic acid and 5 parts by weight of N-butyl.丫_ is carried out as a light-reducing agent in the same manner as in the above-mentioned implementation state to produce a negative-type photosensitive resin: except 5 parts by weight of [Bu [9-ethyl-6-(2-methylphenyl(tetra)))) -9H-Ten-3 -based (〇-B_), 1 part by weight of toe TPO as a photoinitiator, and additionally used 5 parts by weight of aminobenzoic acid isooctyl vinegar and 5 parts by weight of _- base. The ruthenium phase was carried out as a reducing agent in the same manner as in the above Example i to produce a negative-type sensible coating composition solution. Example 6 Except 5 parts by weight of [:[1[9-ethylidene]methylbenzylidene)- 9H-carbazole-3-yl]-1-7. And parts by weight of IrgaCUre 369 as a photoinitiator, as a light-reducing agent, 5 parts by weight of p-dimethylaminobenzoic acid isooctane S and 5 parts by weight of butyl decyl, in combination with the above-mentioned Example 1 A negative photosensitive lysate composition coating solution was produced. Example 7 Except 5 parts by weight of [Bu [9-ethyl-6-(2-methylphenyl)-state-°Kawa-3-based]--(〇一乙醯肥), 5 parts by weight of IrgaCUre 369 as a photoinitiator, 5 parts by weight of 2-ethylhexyl-4-didecylamino vinegar, and 5 parts by weight of N-butyl decyl as a light-reducing agent, and The above-described method was carried out in the same manner as in the production of a ruthenium-type photosensitive resin composition coating solution. Comparative Example 1 In the foregoing Example 4, except that [i - [9-ethyl-6-(2-indolylbenzoyl)- 9H-carbazole-3-yl]]; In the same manner as in the above Example 4, a negative photosensitive resin composition coating solution was produced, except that 20 parts by weight of 819 was used as a photoinitiator. Comparative Example 2 In the foregoing Example 5, except that [1 -[9-ethyl-6-(2-indolylbenzoyl)-9H-carbazole-3-yl]-one-one (〇一乙) was not used.醯肟), 24 201003317 A negative photosensitive resin composition coating solution was produced in the same manner as in the above Example 5 except that 20 parts by weight of Irgacure TPO was used as a photoinitiator. Comparative Example 3 In the foregoing Example 6, except that [1 -[9-ethyl-6-(2-nonylphenylphenyl)- 9-oxindole- 3]-]-(Ο-B) was not used. In the same manner as in the above Example 6, 20 parts by weight of Irgacure 369 was used as a photoinitiator, and a negative photosensitive resin composition coating solution was produced. Comparative Example 4 (Positive photosensitive resin composition) (Production of acrylic copolymer) An acrylic copolymer was produced in the same manner as in the above Example 1. (Manufacture of 1,2-quinonediazide compound) 1 mol of 4, 4'-[1—[4-[1][4-hydroxyphenyl]-1 methylethyl]phenyl] Ethylene]bis(phenyl)phenol and 2 mol of 1,2-diazidonaphthoquinone-5-sulfonic acid [chloride] are subjected to a condensation reaction to produce 4, 4'-[1[[4][ 1-[4-monophenylene]-indenylethyl]phenyl]ethylidene]bisphenol 1,2-diazonaphthoquinone-5-sulfonate. (Production of Photosensitive Resin Composition) 100 parts by weight of the polymer solution containing the acrylic copolymer produced in the above Example 1 and the above-mentioned 4, 4'-[1 - [4 - [1 - [4-Phenyl-phenyl]-l-decylethyl]phenyl]ethylidene]bis 2,2 -diazonaphthoquinone-5-sulfonate 25 parts by weight, mixed, added to diethyl The diol dioxime ether made the solid content concentration of the mixture 35% by weight, so that 25 201003317 was dissolved, and the microporous membrane transition was carried out with 0. 2 μm to prepare a photosensitive resin composition coating solution. The negative photosensitive resin composition produced in the above Examples 1 to 7 and Comparative Examples 1 to 3 and the positive photosensitive wax composition coating solution produced in Comparative Example 4 were evaluated for physical properties by the method described below. The results are shown in the following table i. 1) Sensitivity - The positive photosensitive property produced by the negative photosensitive resin compositions manufactured by the above Examples 1 to 7 and Comparative Examples 1 to 3 and Comparative Example 4 were applied by spin coating on a glass substrate. After the resin composition solution, the film was prebaked on a hot plate at 90 ° C for 2 minutes to form a film. The film obtained in the foregoing was irradiated with ultraviolet rays having an intensity of 15 mW/cm 2 at 365 nm for 6 seconds using a predetermined pattern mask (paUernmask). Thereafter, it was developed with an aqueous solution of 0.38 parts by weight of tetramethylammonium hydroxide at 2 μc for 2 minutes, and then washed with ultraclean water for 1 minute. Thereafter, the pattern which had been developed in the front was irradiated with ultraviolet rays having a intensity of 15 mW/cm 2 at 365 nm for 34 seconds at 120. (: After baking for 3 minutes, it was cured by heating in an oven at 220 ° C for 60 minutes to obtain a patterned film. 2) Residual film rate was measured as the lowest sum of the pattern film formed when the sensitivity of the above 1) was measured. The highest height of the pattern film. At this time, the thickness change rate is based on the film thickness obtained by prebaking, and the case of 〇~10% is excellent, the case of 10 to 40% is good, and the case of more than 40% is shown to be bad. 3) Transmittance As measured in the sensitivity test of the above 1), the pre-baked film has a light absorption spectrum (Spectrem) of visible light of a coating film of 3 μm, and the light transmittance is 98% at 40 〇 nm. The above is expressed as excellent, 92 to 94% is expressed as normal, and 92% or less is expressed as poor. 26 201003317 [Table 1] Classification --- - ^ ^例厂'-^—— Compare you丨1 2 3 4 ΓΓ 6 7 1 2 3 4 140 Sensitivity (mJ/cm2) 7 11 ---— 9 10 7 9 60 75 45 Excellent residual film rate Excellent good Good good Excellent good bad difference Excellent transmission difference Excellent Very very very Excellent Excellent Excellent poor Excellent excellent Excellent difference Table 1 Can confirm 'According to the invention, containing photoinitiator Examples 1 to 7 produced by using [9-ethyl-6-(1-methylphenylmethyl)- 9-carbazole- 3-yl]-b (b-b), sensitivity 5 -u mJ/cm2 ' is very excellent compared with the comparative example (4), and the more positive transmittance of the positive insulating film in terms of transmittance shows a superior transmittance 'another ^ ^ and a photoinitiator-free [H9- Ethyl-6-(2-methylbenzhydrazide-3⁄4) 9 Η — σ卡σ坐—α — hair 1 —t / soil j — 1—(〇—乙醯肟) negative resist Similar to 'showing excellent transmittance. In particular, it was confirmed that the residual film ratio was considerably superior to Comparative Examples 1 and 3. Fig. 1 shows the high opening-element and semi-transmissive liquid crystal sensitivities, residual film ratios, and transmittances of the (4) photosensitive resin composition according to the present invention. It is to be understood that the specific examples described in the present invention have been described in the present invention. However, it should be understood that the modifications and corrections of the present invention can be made within the scope of the technical idea of the present invention. The patent application scope of the present invention belongs to 27 201003317. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a TFT type liquid crystal display element unit having a high aperture ratio. Fig. 2 is a cross-sectional view taken along line Π - ’ ' of Fig. 1. [Main component symbol description] 1...lower substrate 6...semiconductor layer 2...gate electrode 7...power supply electrode 2a...gate line 8...drain electrode 3a...storage electrode line 9...organic insulating film 4···gate insulating film 5 ...data line 10...picture element electrode 28

Claims (1)

201003317 七、申請專利範圍： L種負型感光性樹脂組成物，特徵在於其含有冱）i)不 飽和叛酸、不飽和竣酸酐，或其等之混合物；ii)含有 環氧基之不飽和化合物；以及，出）使烯烴系不飽和化 合物共聚而得到的丙烯酸系共聚物；b)含有[i-[9 — 乙基一 6—（2 —曱基苯曱醯基）_9H 一咔唑—3 —基] 1一（〇—乙醯肟）的光起始劑；具有乙烯性不飽 和鍵的多B施性單體；d )含有環氧基或胺基的石夕系化 合物；及，e)溶劑。 2. 如申請專利第1項記載之負型感光性樹脂組成物，特徵 在於其係使用於液晶顯示元件的有機絕緣膜形成用。 3. 如申請專利範圍第丨項記載之負型感光性樹脂組成物， 特徵在於其含有a)丙烯酸系共聚物1〇〇重量份；b)含 有[1 —[9 一乙基一6一（2 一甲基苯曱醯基）—9H—咔唑 ―3—基]一1一（〇—乙醯肟）的光起始劑0.001到30重 量份；c)具有乙烯性不飽和鍵的多官能性單體1〇到1〇〇 重量份；d )含有環氧基或胺基的矽系化合物〇 〇〇1到5 重量份’以及’ e)使前述a) +b) +c) +d)成分的固 形分含量合計變成10到50重量％的溶劑。 4，如申請專利範圍第1項記載之負型感光性樹脂組成物， 特徵在於前述丙烯酸系共聚物是使〇不飽和羧酸、不飽 和羧酸酐’或其等之混合物5到40重量％ ; ϋ)含有環氧 基的不飽和化合物5到70重量％ ;以及及，出）烯烴系不 飽和化合物10到70重量％共聚而獲得者。 29 201003317 5. 如申請專利範圍第1項記載之負型感光性樹脂組成物， 特徵在於前述丙烯酸共聚物是以包含1 )將單體、聚合 溶劑及聚合起始劑倒入具備冷卻裝置的聚合反應器使 聚合物進行聚合的步驟；2)使前述聚合中止的步驟；3) 於前述聚合中止後使聚合反應器冷卻以析出聚合物的 步驟；4)分離前述已析出之聚合物的步驟；及，5)使 前述已分離之聚合物溶解於溶劑的步驟。 6. 如申請專利範圍第1項記載之用以形成液晶顯示元件之 有機絕緣膜之負型感光性樹脂組成物，特徵在於前述丙 烯酸共聚物以聚苯乙烯換算的重量平均分子量為1,000 到 40,000。 7. —種負型感光性樹脂組成物，特徵在於前述（b)的光 起始劑進一步含有從2,4—雙三氣甲基一6 — p—甲氧基 苯乙烯一 s—三嗪、2 — p—曱氧基苯乙烯一 4,6—雙（三 氯曱基）一s—三嘻、2,4 —三氣曱基一6 —三σ秦、2,4 —三 氣曱基一 4 一甲基萘基一 6—三嗪、二苯甲酮、ρ—(二乙 氣基）二苯曱酮、2,2 —二氣一4一苯氧基苯乙酉同、2,2 — 二乙氧基苯乙酮、2—十二烷基噻噸酮、2,4—二甲基噻 噸酮、2,4—二乙基噻噸酮、2,2—雙一 2 —氯苯基一4,5,4,5 —四苯基一2—1, 2 —二 σ米嗤，Irgacure 369、Irgacure 651、1巧8(：1^ 907、0&1'〇(：111'丁？0，以及11名&(：1^819所組 成的族群中選出之1種以上的光起始劑。 8 ·如申請專利範圍第1項記載之負型感光性樹脂組成物， 特徵在於前述（d)含有環氧基或胺基的矽系化合物是 30 201003317 從（3 —縮水甘油氧基丙基）三甲氧基矽烷、（3—縮水 甘油氧基丙基）三乙氧基矽烷、（3 —縮水甘油氧基丙基） 甲基二甲氧基矽烷、（3 —縮水甘油氧基丙基）三甲氧基 石夕院、（3—縮水甘油氧基丙基）二甲基乙氧基矽烷、（3 一縮水甘油氧基丙基）二甲基乙氧基矽烷、3，4一環氧 丁基二甲氧基矽烷、3, 4一環氧丁基三乙氧基矽烷、2_ (3, 4一環氧環己基）乙基三甲氧基矽烷、2一（ 3, 4—環 乳環己基）乙基三乙氧基矽烷，以及氨丙基三甲氧基矽 烷所組成的族群中選擇出之丨種以上。 9.如申請專利範圍第1項記載之負型感光性樹脂組成物， 特徵在於其進—步含有光敏劑、界面活性劑、黏著增進 劑、熱聚合抑制劑或消泡劑。 10:=顯示元件之有機絕緣膜形成方法，係使用申請 專利乾圍第1項至黛Q馆ώ 樹脂組成物。、項中之任—項記載的負型感光性 Τ至/代曰曰结貝 小兀仵 第10項节* ”又⑽具包含利用申請專利範圍 弟項δ己栽之液晶顯示元件的右 形成之有機絕緣膜。 、緣_成方法所 31201003317 VII. Patent application scope: L kinds of negative photosensitive resin composition, characterized in that it contains 冱) i) unsaturated tauric acid, unsaturated phthalic anhydride, or a mixture thereof; ii) epoxy group-containing unsaturated a compound; and, an acrylic copolymer obtained by copolymerizing an olefin-based unsaturated compound; b) containing [i-[9-ethyl-6-(2-mercaptophenyl)- 9H-carbazole- a photoinitiator of 1 -(〇-acetamidine); a poly-B-functional monomer having an ethylenically unsaturated bond; d) an anthracene compound containing an epoxy group or an amine group; e) Solvent. 2. The negative photosensitive resin composition according to the first aspect of the invention, which is characterized in that it is used for forming an organic insulating film of a liquid crystal display device. 3. The negative photosensitive resin composition as described in the scope of the patent application, characterized in that it contains a) an acrylic copolymer in an amount of 1 part by weight; b) contains [1 - [9-ethyl-ethyl- 6-( 2-Methylphenylhydrazinyl)-9H-carbazole-3-yl]- 1-1 (〇-acetamidine) photoinitiator 0.001 to 30 parts by weight; c) having ethylenically unsaturated bonds 1 to 1 part by weight of the functional monomer; d) an oxime compound containing an epoxy group or an amine group 1 to 5 parts by weight 'and 'e) such that the aforementioned a) + b) + c) + d) The solid content of the component is a total of 10 to 50% by weight of the solvent. 4. The negative photosensitive resin composition according to claim 1, wherein the acrylic copolymer is 5 to 40% by weight of a mixture of a hydrazine-unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or the like; ϋ) 5 to 70% by weight of an epoxy group-containing unsaturated compound; and olefinic unsaturated compound obtained by copolymerization of 10 to 70% by weight. In the negative photosensitive resin composition of the first aspect of the invention, the acrylic copolymer is characterized in that the acrylic copolymer is contained in a polymerization medium comprising a monomer, a polymerization solvent and a polymerization initiator. a step of polymerizing the polymer in the reactor; 2) a step of stopping the polymerization; 3) a step of cooling the polymerization reactor to precipitate a polymer after the polymerization is terminated; 4) a step of separating the polymer which has been precipitated; And, 5) a step of dissolving the separated polymer in a solvent. 6. The negative photosensitive resin composition for forming an organic insulating film of a liquid crystal display device according to claim 1, wherein the acrylic copolymer has a weight average molecular weight of from 1,000 to 40,000 in terms of polystyrene. 7. A negative photosensitive resin composition characterized in that the photoinitiator of the above (b) further contains from 2,4-bistrimethylmethyl-6-p-methoxystyrene-s-triazine , 2 — p—nonyloxystyrene—4,6-bis(trichloroindenyl)-s-three-indolent, 2,4-trisyl-fluorenyl- 6-tris-ziridine, 2,4-three-gas Base one 4-methylnaphthyl-6-triazine, benzophenone, ρ-(diethoxy)diphenyl fluorenone, 2,2-dione-tetraphenyloxyphenyridinium, 2, 2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,2-di- 2 Chlorophenyl-4,5,4,5-tetraphenyl-2-phenanthrene, Irgacure 369, Irgacure 651, 1-8 (:1^907,0&0&1;〇(:111 And a negative photosensitive resin composition as described in claim 1 of the patent application, It is characterized in that (d) the oxime compound containing an epoxy group or an amine group is 30 201003317 from (3 - glycidoxypropyl) trimethyl Base decane, (3-glycidoxypropyl) triethoxy decane, (3 - glycidoxypropyl) methyl dimethoxy decane, (3 - glycidoxypropyl) trimethoxy stone Xiyuan, (3-glycidoxypropyl) dimethyl ethoxy decane, (3-glycidoxypropyl) dimethyl ethoxy decane, 3, 4-epoxybutyl dimethoxy Basear, 3,4-epoxybutyltriethoxydecane, 2_(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2(3,4-cyclopentadienyl)ethyltri A negative photosensitive resin composition according to the first aspect of the invention, characterized in that it is further selected from the group consisting of ethoxy decane and aminopropyltrimethoxy decane. Contains a photosensitizer, a surfactant, an adhesion promoter, a thermal polymerization inhibitor or an antifoaming agent. 10:= Method for forming an organic insulating film of a display element, using the patent pending dry circumference item 1 to 黛Q museum 树脂 Resin composition , the item in the item - the negative type photosensitive Τ to / / 曰曰 曰曰 曰曰 兀仵 兀仵 兀仵 兀仵 10th section * ” Further, (10) includes an organic insulating film formed by the right side of the liquid crystal display element which has been used for the application of the patent range δ.
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TWI471697B (en) 2015-02-01

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