TW200912544A - Photosensitive composition, cured film formed by it, and element having the cured film - Google Patents

Photosensitive composition, cured film formed by it, and element having the cured film Download PDF

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Publication number
TW200912544A
TW200912544A TW097131863A TW97131863A TW200912544A TW 200912544 A TW200912544 A TW 200912544A TW 097131863 A TW097131863 A TW 097131863A TW 97131863 A TW97131863 A TW 97131863A TW 200912544 A TW200912544 A TW 200912544A
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TW
Taiwan
Prior art keywords
group
acrylic resin
decane
carbon atoms
acid
Prior art date
Application number
TW097131863A
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Chinese (zh)
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TWI442185B (en
Inventor
Masahide Senoo
Toru Okazawa
Mitsuhito Suwa
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Toray Industries
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Publication of TW200912544A publication Critical patent/TW200912544A/en
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Publication of TWI442185B publication Critical patent/TWI442185B/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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive 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
    • G03F7/075—Silicon-containing compounds
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035—Materials
    • G02B2006/12069—Organic material
    • 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
    • G02F1/133357—Planarisation layers
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable

Abstract

This invention is to provide a photosensitive composition capable of resulting in cured films with characteristics of high heat resistance and high transparency, having excellent adhesion to substrates, and is useful for forming planarizing films for TFT substrates, interlayer insulation films or core and clad materials of optical waveguides. The said photosensitive composition comprises (a) polysiloxane, (b) acrylic resin, (c) quinonediazide compound, and (d) solvent, with the mixing ratio between (a) polysiloxane and (b) acrylic resin of polysiloxane/acrylic resin=80/20 to 20/80 by weight, while (a) polysiloxane is synthesized through reacting one or more organosilanes of general formula (1). (R1 represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or an aryl group of 6 to 15 carbon atoms, with each of the plural of R1 being the same or different. R2 represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an acyl group of 2 to 6 carbon atoms, or an aryl group of 6 to 15 carbon atoms, with each of the plural of R2 being the same or different. And n represents an integer of 0 to 3.)

Description

200912544 九、發明說明： 【發明所屬之技術領域】 本發明ί系關於用以形成液晶顯示元件、有· EL顯示元 件等之薄膜電晶體（TFT)基板用平坦化膜，半導體元件之層 間絕緣膜，或光波導之芯、覆材的感光性組成_，由其形 成之硬化膜、及具有該硬化膜之元件。 【先前技術】 近年來，於液晶顯示器、有機EL顯示器等，爲實現更 高精細、高解析度’已知有提升顯示裝置之開口率的方法（ 參考專利文獻1 )。此係於TFT基板上部設置透明平坦化膜 作爲保護膜’以使資料線與像素電極能重疊，比習知技術 更提升開口率之方法。 作爲如此之TFT基板用平坦化膜的材料，必須具有高 耐熱性、高透明性等特性’且爲結合TFT基板電極與IT0 電極須形成50ym〜數Mm左右之孔圖案，一般係用正型感 光性材料。代表性材料已知有’組合丙烯酸樹脂與醌二疊 氮化合物（參考專利文獻2、3) ’這些材料耐熱性不足，基 板經高溫處理則硬化膜著色’有透明性變差之問題。 具有高耐熱性、高透明性等特性之其它材料已知有聚 矽氧烷，爲賦予正型感光性已知有於其組合醌二疊氮化合 物之材料（參考專利文獻4)。此材料透明性高，基板經高溫 處理透明性亦不下降，可得高度透明之硬化膜。然而，此 材料與基板之密著性低’前敘由丙烯酸樹脂構成之材料亦 有與基板的密著性不足之問題。 -6- 200912544 已知有，作爲聚矽氧烷與丙烯酸樹脂的倂用系，$ 田聚 矽氧烷、（甲基）丙烯酸系聚合物及潛在性酸觸媒構成$ _ 料（參考專利文獻5)，含具酸分解基之有機基的聚砂氧％ 得自含有含矽基之丙烯酸樹脂及酸產生劑的材料_ 1專 利文獻6)。然而，這些材料中以醌二疊氮化合物用作彳替# 性酸觸媒、酸產生劑，則因聚矽氧烷、丙烯酸樹脂與^ 疊氮化合物之相溶性差，塗膜起白化，不得高透明膜。M 已知有由拒水性矽氧烷樹脂、丙烯酸樹脂及醌二疊氮化ι合_ 物構成之材料（參考專利文獻7 )，因膜表面拒水性高，有與 密封劑的密著性差之問題。 專利文獻1 日本專利特開平9 - 1 5 2 6 2 5號公報（申請 專利範圍第1項） 專利文獻2 特開200 1 -28 1 8 5 3號公報（申請專利範圍 第1項） 專利文獻3 特開200 1 -28 1 86 1號公報（申請專利範圍 第1項） 專利文獻4 特開2006- 1 7 8436號公報（申請專利範圍 第1項） 專利文獻5 特開200 1 -5 55 54號公報（申請專利範圍 第6項） 專利文獻6 特開2005-22 1 7 1 4號公報（申請專利範圍 第7項） 專利文獻7 特開2004-473 3號公報（申請專利範圍第 1項） 200912544 【發明内容】 發明所欲解決之課題 本發明係基於如上實情而作，其目的在提供，可得具 有高耐熱性、高透明性等特性’且與基板之密著性良好的 硬化膜之感光性組成物。本發明之另…目的在提供，由該 感光性組成物形成之TFT基板用平坦化膜、層間絕緣膜、 芯或覆材等硬化膜，及具有該硬化膜之顯示元件、半導體 元件、光波導等元件。 用以解決課題之手段 本發明係含有（a)聚矽氧垸、（b)丙燦酸樹脂、（c)醌二疊 氮化合物、（d)溶劑之感光性組成物，其中（a)聚砍氧院/ (b) 丙燦酸樹脂之混合比率爲重量比20/80以上80/20以下，且 (a)聚矽氧烷係由使一般式（1)之有機矽烷的1種以上反應所 合成之聚矽氧烷。 («〇R2)‘n (1) (式中R1表氫、碳原子數1~1〇之烷基、碳原子數2~10之烯 基、碳原子數6~15之芳基中任一，複數之R1可各係相同 或不同；R2表氫、碳原子數1~6之院基、碳原子數2〜6之 醯基、碳原子數6~15之芳基中任一，複數之R2可各係相 同或不同；η表0至3之整數） 發明效果 由本發明之感光性組成物可得具有高耐熱性、高透明 性等特性，且與基板之密著性良好的硬化膜。得到之硬化 膜適用作TFT基板用平坦化膜、層間絕緣膜。 200912544 【實施方式】 本發明之感光性組成物係含有（a)聚矽 樹脂、（c)醌二疊氮化合物、（d)溶劑之感光 聚矽氧烷有與基板之密著性低的問； 下。亦即，聚矽氧烷中之矽烷醇基與基板 熱硬化時反應形成化學鍵。可是，因聚矽 施加外力則力集中於硬化膜與基板之界面 故。丙烯酸樹脂則因伸縮性高，施加外力 力減輕。因之，與基板的密著性較爲良好 與硬化膜之間不形成化學鍵，密著性不足 相對於此，倂用聚矽氧烷與丙烯酸樹 之間形成化學鍵，且因膜的伸縮性高，與 升。唯聚矽氧烷與丙烯酸樹脂相溶性差， 之，膜多白濁，不得高度透明的硬化膜。 聚矽氧烷與丙烯酸樹脂，以避免相分離。 本發明之感光性組成物中，（a)聚矽氧 脂的混合比率係重量比聚矽氧烷/丙烯酸 8 0/20以下，較佳者聚矽氧烷/丙烯酸樹脂: 烯酸樹脂少於20%則基板與硬化膜的密著 充分。另一方面，聚矽氧烷少於20%則基 著性提升效果不充分，且硬化膜之透過率 本發明之感光性組成物含有U)聚矽_ 之聚矽氧烷係由使一般式（1)之有機矽烷白< 合成之聚矽氧烷。 氧烷' (b)丙烯酸 :性組成物。 ® ’理由應係如 表面之氫氧基於 氧烷伸縮性低， ，而易起剝離之 時硬化膜延伸而 。然而，因基板 〇 脂以於基板與膜 基板之密著性提 易起相分離。因 故必須選擇最適 烷與（b)丙烯酸樹 樹脂 20/80以上 :7 5/25 ~30/70。丙 性之提升效果不 板與硬化膜的密 降低。 烷，用於本發明 1種以上反應所 200912544 (七丨如R2)4_n σ) (式中R1表氫、碳原子數1〜10之院基、碳原子數2〜10之燒 基、碳原子數6~15之芳基中任一，複數之Rl可各係相同 或不同；R2表氫、碳原子數1〜6之院基、碳原子數2~6之 醯基、碳原子數6~15之芳基中任一，複數之R2可各係相 同或不同；η表0至3之整數） 一般式（1)之有機矽烷中，R1表氫、碳原子數i〜10之 院基、碳原子數2~10之稀基、碳原子數6~15之方基中任 一’複數之R1可各係相同或不同。這些院基、烯基、芳基 皆可係無取代體或取代體，可依組成物特性作選擇。 烷基之具體例有，甲基、乙基、正丙基、異丙基、正 丁基、三級丁基、正己基' 正癸基、三氟甲基、3,3，3-三氟 丙基、3-環氧丙氧丙基、2-(3,4-環氧環己基）乙基、[(3-乙 基-3-環氧丙基）甲氧基]丙基、3_胺丙基、3_锍丙基、3異氰 酸酯丙基等。 嫌基之具體例有，乙烯基、3-丙烯醯氧丙基、3-甲基 丙嫌醯氧丙基。芳基之具體例有苯基、甲苯基、對羥苯基、 -10- 1 -封羥苯乙基、2 -對羥苯乙基、4 -羥-5 -對羥苯羰氧戊基、 萘基等。 —般式（1)之R2表氫、碳原子數1~6之烷基、碳原子數 2〜6之醯基、碳原子數6〜15之芳基中任―，複數之R2可各 係相同次不同。m些烷基、醯基、芳基皆可係無取代體或 取代體’可依組成物特性作選擇。烷基之具體例有甲基、 2基、正丙基、異丙基、正丁基。醯基之具體例有乙醯基 寺。芳基之具體例有苯基等。一般式（1)之11表〇至3之整 200912544 數。n = 0時係4官能性矽烷，n=l時係三官能性矽烷，n = 2 時係二官能性矽烷，n = 3時係一官能性矽烷。 一般式（1)之有機矽烷的具體例可列舉以下之有機矽 烷。即，四甲氧矽烷、四乙氧矽烷、四乙醯氧矽烷、四苯 氧矽烷等四官能性矽烷，甲基三甲氧矽烷、甲基三乙氧矽 烷、甲基三異丙氧矽烷、甲基三正丁氧矽烷、乙基三甲氧 矽烷、乙基三乙氧矽烷、乙基三異丙氧矽烷、乙基三正丁 氧矽烷、正丙基三甲氧矽烷、正丙基三乙氧矽烷、正丁基 ^ 三甲氧矽烷、正丁基三乙氧矽烷、正己基三甲氧矽烷、正 己基三乙氧矽烷、癸基三甲氧矽烷、乙烯基三甲氧矽烷、 乙烯基三乙氧矽烷、3 -甲基丙烯醯氧丙基三甲氧矽烷、3-甲基丙烯醯氧丙基三乙氧矽烷、3 -丙烯醯氧丙基三甲氧矽 烷、苯基三甲氧矽烷、苯基三乙氧矽烷、對羥苯基三甲氧 矽烷、1-(對羥苯基）乙基三甲氧矽烷、2-(對羥苯基）乙基三 甲氧矽烷、4-羥-5-(對羥苯羰氧基）戊基三甲氧矽烷、三氟 甲基三甲氧矽烷、三氟甲基三乙氧矽烷、3,3,3，-三氟丙基 三甲氧矽烷、3-胺丙基三甲氧矽烷、3-胺丙基三乙氧矽烷、 3 -環氧丙氧丙基三甲氧矽烷、3 -環氧丙氧丙基三乙氧矽 烷、2-(3,4-環氧環己基）乙基三甲氧矽烷、2-(3,4-環氧環己 基）乙基三乙氧矽烷、[(3-乙基-3-環氧丙基）甲氧基]丙基三 甲氧矽烷、[(3-乙基-3-環氧丙基）甲氧基]丙基三乙氧矽烷、 3 -锍丙基三甲氧矽烷、3 -三甲氧矽烷丙基琥珀酸等三官能 性矽烷，二甲基二甲氧矽烷、二甲基二乙氧矽烷、二甲基 二乙醯氧矽烷、二正丁基二甲氧矽烷、二苯基二甲氧矽烷、 (3-環氧丙氧丙基）甲基二甲氧基矽烷、（3-環氧丙氧丙基）甲 -11- 200912544 基二乙氧矽烷等二官能性矽烷，三甲基甲氧矽烷、三正丁 基乙氧矽烷、（3·環氧丙氧丙基）二甲基甲氧矽烷、（3-環氧 丙氧丙基）二甲基乙氧矽烷等一官能性矽烷等。這些有機矽 烷可單獨或組合2種以上使用。這些有機矽烷之中，基於 硬化膜的耐皸裂性與硬度，以使用三官能性矽烷爲較佳。 用於本發明之聚矽氧烷的樣態者，亦可係使前敘一般 式（1)之有機矽烷的1種以上，與矽石粒子反應所合成之聚 矽氧烷。以矽石粒子反應，即可提升圖案解析度。此應係 於聚矽氧烷中加入矽石粒子，則膜之玻璃轉移溫度提高， 熱硬化時圖案的崩壞受抑之故。 矽石粒子之數量平均粒徑係以2~ 200nm爲佳，5〜7〇nm 更佳。小於2nm則提升圖案解析度之效果不足，大於200nm 則硬化膜會使光散射，透明性差。於此，矽石粒子之數量 平均粒徑採用比表面積法換算値時，係將矽石粒子乾燥後 煅燒’測定得到之粒子的比表面積後，假定粒子係球，由 比表面積求出粒徑。所用之機器無特殊限制，可用 ASAP2020(商品名，Micromeritics 公司製）等。200912544 IX. EMBODIMENT OF THE INVENTION The present invention relates to a planarization film for a thin film transistor (TFT) substrate for forming a liquid crystal display element, an EL display element, or the like, and an interlayer insulating film for a semiconductor element. Or a photosensitive composition of the core of the optical waveguide, the coating material, a cured film formed therefrom, and an element having the cured film. [Prior Art] In recent years, in order to achieve higher definition and higher resolution, liquid crystal displays, organic EL displays, and the like have been known (see Patent Document 1). This is a method in which a transparent planarizing film is provided on the upper portion of the TFT substrate as a protective film ′ so that the data lines and the pixel electrodes can overlap each other, and the aperture ratio is higher than that of the prior art. As a material for the flattening film for a TFT substrate, it is necessary to have characteristics such as high heat resistance and high transparency, and a hole pattern of about 50 μm to several Mm must be formed in combination with the TFT substrate electrode and the IT0 electrode, and a positive photosensitive image is generally used. Sexual material. Representative materials are known as 'combined acrylic resin and quinonediazide compound (refer to Patent Documents 2 and 3). These materials have insufficient heat resistance, and when the substrate is subjected to high temperature treatment, the cured film is colored, and the transparency is deteriorated. A material having a property of high heat resistance and high transparency is known as a polysiloxane, and a material in which a quinonediazide compound is known to impart positive photosensitive properties is known (refer to Patent Document 4). The material has high transparency, and the substrate is not deteriorated by high-temperature treatment, and a highly transparent cured film can be obtained. However, this material has a low adhesion to the substrate. The material composed of an acrylic resin has a problem that the adhesion to the substrate is insufficient. -6- 200912544 It is known that, as a polysiloxane and an acrylic resin, a phthalocyanine, a (meth)acrylic polymer, and a latent acid catalyst constitute a material (refer to the patent literature). 5) The polyaluminum having an organic group having an acid-decomposing group is obtained from a material containing a mercapto group-containing acrylic resin and an acid generator (Patent Document 6). However, in these materials, the bismuth azide compound is used as the acid catalyst and the acid generator, and the compatibility of the polyoxyalkylene, the acrylic resin and the azide compound is poor, and the coating film is whitened. Highly transparent film. M is known as a material composed of a water-repellent siloxane resin, an acrylic resin, and a quinone dimide (refer to Patent Document 7), because the surface water repellency is high, and the adhesion to the sealant is poor. problem. Patent Document 1 Japanese Patent Laid-Open No. Hei 9 - 1 5 2 6 2 5 (Application No. 1) Patent Document 2 Patent Publication No. 200 1 -28 1 8 5 No. 3 (Application No. 1) Patent Literature 3 JP-A-200 1-28 1 86 1 (Patent No. 1 of the Patent Application) Patent Document 4 JP-A-2006- 1 7 8436 (Application No. 1) Patent Document 5 Special Opening 200 1 - 5 55 Publication No. 54 (Application No. 6) Patent Document 6 JP-A-2005-22 1 7 1 4 (Application No. 7) Patent Document 7 JP-A-2004-473 No. 3 (Application No. 1) OBJECTS OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a hardening property having high heat resistance and high transparency, and having good adhesion to a substrate. A photosensitive composition of the film. Another object of the present invention is to provide a flattening film for a TFT substrate, an interlayer insulating film, a cured film such as a core or a clad material, and a display element, a semiconductor element, and an optical waveguide having the cured film. And other components. Means for Solving the Problems The present invention relates to a photosensitive composition comprising (a) a polyfluorene oxide, (b) a propionic acid resin, (c) a quinonediazide compound, and (d) a solvent, wherein (a) a polymer (b) The mixing ratio of the acrylic acid resin is 20/80 or more and 80/20 or less by weight, and (a) the polyoxyalkylene is one or more kinds of the organic decane of the general formula (1). The polyoxyalkylene synthesized. («〇R2)'n (1) (wherein R1 represents hydrogen, an alkyl group having 1 to 1 ring of carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R1 of the plural number may be the same or different; R2 represents hydrogen, a group of 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, plural In the photosensitive composition of the present invention, a cured film having high heat resistance, high transparency, and the like, and having good adhesion to a substrate can be obtained. The obtained cured film is suitably used as a planarizing film for a TFT substrate or an interlayer insulating film. 200912544 [Embodiment] The photosensitive composition of the present invention contains (a) a polyfluorene resin, (c) a quinonediazide compound, and (d) a solvent, and the photosensitive polyoxyalkylene has a low adhesion to a substrate. ; Next. That is, the stanol group in the polyoxyalkylene reacts with the substrate to form a chemical bond upon thermal hardening. However, due to the application of an external force by the polyfluorene, the force is concentrated on the interface between the cured film and the substrate. The acrylic resin is high in stretchability and the external force is applied. Therefore, the adhesion to the substrate is good and no chemical bond is formed between the cured film, and the adhesion is insufficient. In contrast, the chemical bond is formed between the polysiloxane and the acrylic tree, and the film has high flexibility. , and rise. Only the polyoxyalkylene has poor compatibility with the acrylic resin, and the film is white and turbid, and the cured film is not highly transparent. Polyoxyalkylene and acrylic resin to avoid phase separation. In the photosensitive composition of the present invention, the mixing ratio of (a) polyxanthene is less than or less than 80/20 of polyoxyalkylene/acrylic acid, preferably polyoxyalkylene/acrylic resin: less than olefinic resin At 20%, the adhesion between the substrate and the cured film is sufficient. On the other hand, if the polysiloxane is less than 20%, the effect of improving the adhesion is insufficient, and the transmittance of the cured film contains the U) polyfluorene-based polysiloxane. (1) Organic decane white < Synthetic polyoxyalkylene. Oxytomane' (b) Acrylic: a sexual composition. The reason for ® ' should be such that the surface of the hydroxyl group is low in oxygen olefin, and the hardened film extends when it is easy to peel off. However, the substrate grease is easily separated by the adhesion between the substrate and the film substrate. Therefore, it is necessary to select the optimum alkane and (b) acrylic resin 20/80 or more: 7 5/25 ~ 30/70. The effect of the improvement of the C is not the same as that of the cured film. Alkane, used in one or more kinds of reaction schemes of the present invention 200912544 (seven as R2) 4_n σ) (wherein R1 represents hydrogen, a carbon atom number of 1 to 10, a carbon atom of 2 to 10, a carbon atom; Any of the 6 to 15 aryl groups, the plural Rl may be the same or different; R2 represents hydrogen, a carbon atom number of 1 to 6, a carbon number of 2 to 6 thiol, a carbon number of 6~ Any one of 15 aryl groups, the plural R2 may be the same or different; n is an integer of 0 to 3). In the organic decane of the general formula (1), R1 represents hydrogen, and the number of carbon atoms is i10. Any of the plural R1 groups having a carbon number of 2 to 10 and a carbon number of 6 to 15 may be the same or different. These bases, alkenyl groups, and aryl groups may be unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl 'n-decyl, trifluoromethyl, 3,3,3-trifluoro. Propyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, [(3-ethyl-3-epoxypropyl)methoxy]propyl, 3_ Amine propyl, 3 锍 propyl, 3 isocyanate propyl, and the like. Specific examples of the base are vinyl, 3-propenyloxypropyl, and 3-methylpropane. Specific examples of the aryl group are a phenyl group, a tolyl group, a p-hydroxyphenyl group, a -10- 1 -hydroxyphenylethyl group, a 2-p-hydroxyphenethyl group, a 4-hydroxy-5-p-hydroxyphenylcarbonyloxypentyl group, Naphthyl and the like. - R2 in the general formula (1), hydrogen in the range of 1 to 6 carbon atoms, fluorenyl group having 2 to 6 carbon atoms, or aryl group having 6 to 15 carbon atoms, and the plural R2 may be various The same is different. The alkyl group, the fluorenyl group, and the aryl group may be unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group are a methyl group, a 2 group, a n-propyl group, an isopropyl group, and an n-butyl group. The specific example of the base is the Yijiji Temple. Specific examples of the aryl group include a phenyl group and the like. The general formula (1) is 11 to 3, and the total number is 200912544. When n = 0, it is a tetrafunctional decane, n = 1 is a trifunctional decane, n = 2 is a difunctional decane, and n = 3 is a monofunctional decane. Specific examples of the organic decane of the general formula (1) include the following organic decanes. That is, tetrafunctional decane such as tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, tetraphenoxy decane, methyltrimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, Tri-n-butoxy oxane, ethyl methoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy oxane, n-propyl trimethoxy decane, n-propyl triethoxy decane , n-butyl ^ trimethoxy decane, n-butyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3 - methacrylic acid methoxypropyl trimethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, 3- propylene oxypropyl trimethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, p-Hydroxyphenyltrimethoxy decane, 1-(p-hydroxyphenyl)ethyltrimethoxy decane, 2-(p-hydroxyphenyl)ethyltrimethoxy decane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy) Amyl trimethoxy decane, trifluoromethyltrimethoxy decane, trifluoromethyl triethoxy decane, 3,3,3,-trifluoropropyltrimethoxy decane , 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy decane, 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropyltriethoxy decane, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, [(3-ethyl-3-epoxypropyl)methoxy] Propyltrimethoxydecane, [(3-ethyl-3-epoxypropyl)methoxy]propyltriethoxyoxane, 3-mercaptopropyltrimethoxydecane, 3-trimethoxydecanepropylsuccinic acid, etc. Trifunctional decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl diethoxy decane, di-n-butyl dimethoxy decane, diphenyl dimethoxy decane, (3- Difunctional decane such as glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyl-11- 200912544 bis ethoxy decane, trimethylmethoxy decane, three positive A monofunctional decane such as butyl ethoxy hydride, (3) glycidoxypropyl) dimethyl methoxy decane or (3-glycidoxypropyl) dimethyl ethoxy decane. These organic decane may be used alone or in combination of two or more. Among these organic decanes, trifunctional decane is preferably used based on the cleavage resistance and hardness of the cured film. The polyoxane of the present invention may be one obtained by reacting one or more kinds of organic decanes of the above general formula (1) with a vermiculite particle. By reacting with vermiculite particles, the resolution of the pattern can be improved. This should be based on the addition of vermiculite particles to the polyoxane, and the glass transition temperature of the film is increased, and the collapse of the pattern during heat hardening is suppressed. The number average particle diameter of the vermiculite particles is preferably 2 to 200 nm, more preferably 5 to 7 nm. When the thickness is less than 2 nm, the effect of improving the resolution of the pattern is insufficient. When the thickness is more than 200 nm, the cured film scatters light and has poor transparency. Here, when the number average particle diameter of the vermiculite particles is converted by the specific surface area method, the vermiculite particles are dried and then calcined to measure the specific surface area of the particles, and then the particle spheres are assumed, and the particle diameter is determined from the specific surface area. The machine to be used is not particularly limited, and ASAP2020 (trade name, manufactured by Micromeritics Co., Ltd.) or the like can be used.

砂石粒:子之具體例有以下粒子。亦即，以異丙醇爲分 散媒之粒徑12nm的IPA-ST、以甲基異丁基酮爲分散媒之 粒徑12nm的MIBK-ST、以異丙醇爲分散媒之粒徑45ηιη的 IPA-ST-L、以異丙醇爲分散媒之粒徑1〇〇11111的ipA_st_zl、 以丙二醇一甲醚爲分散媒之粒徑15nm的PGM-ST(以上商品 名’日產化學工業（股）製）’以r-丁內酯爲分散媒之粒徑 12nm的OSCAR 101、以r -丁內酯爲分散媒之粒徑60nm的 OSCAR 105、以—丙酮醇爲分散媒之粒徑ΐ2〇ηηι的OSCAR -12- 200912544 106、分散溶液係水之粒徑5~80nm的CATALOID-S(以上商 品名，觸媒化成工業（股）製），以丙二醇一甲醚爲分散媒之 粒徑16nm的Quartron PL-2L-PGME、以7" -丁內酯爲分散媒 之粒徑17nm的Quartron PL-2L-BL、以二丙酮醇爲分散媒 之粒徑17nm的QuartronPL-2L-DAA、分散溶液係水之粒徑 18〜20nm的Quartron PL-2L、GP-2L(以上商品名，扶桑化學 工業（股）製），粒徑100nm之矽石（Si〇2)SG-S0100(商品名， 共立材料（股）製），粒徑 5~50nm之 REOLOSIL(商品名， : Tokuyama(股）製）等。這些矽石粒子可單獨或組合2種以上 使用。 使用矽石粒子時混合比率無特殊限制，但以S i原子莫 耳數相對於聚合物全體之Si原子莫耳數在5 0 %以下爲佳。 矽石粒子多於50%則聚矽氧烷與醌二疊氮化合物之相溶性 惡化，硬化膜之透明性差。矽石粒子的S 1原子莫耳數相對 於聚合物全體之Si原子莫耳數比，可由IR的來自Si-C鍵 之尖峰與來自Si-◦鍵之尖峰的積分比求出。尖峰多有重疊 I 而無法求出時，可藉1H-NMR、1 3C-NMR、IR、TOF-MS等 決定粒子以外之單體的構造，再由元素分析法中產生之氣 體與殘留灰渣（假定全係SiO 2)之比率求出。 用於本發明之聚矽氧烷，對於提升與丙烯酸樹脂的相 溶性，形成無相分離之均勻硬化膜極其重要。因之，聚矽 氧烷中苯基含有率係以相對於Si原子30莫耳％以上爲佳， 40莫耳％以上更佳。苯基含有率低於30莫耳％則聚矽氧烷 與丙烯酸樹脂在塗布、乾燥、熱硬化等當中起相分離，膜 白濁，硬化膜之透過率低。苯基含有率之較佳上限値係7 〇 -13- 200912544 莫耳％。苯基含有率高於70莫耳％則熱硬化時交聯不足， 硬化膜之耐藥物性差。苯基含有率可例如作聚矽氧烷之 29Si-NMR測定，由鍵結於其苯基之S:的尖峰面積與不鍵 結於苯基之S i的尖峰面積之比求出。 用於本發明之聚矽氧烷，其與丙烯酸樹脂的相溶性之 提升更重要。因而，較佳者係採用以含環氧基之有機矽烷 共聚的聚矽氧烷。以含環氧基之有機矽烷共聚合，聚合得 之聚矽氧烷即含環氧基，或環氧基經水解得之醇式羥基。 這些基與丙烯酸樹脂中之羰基部位起相互作用，提升聚矽 氧烷與丙烯酸樹脂的相溶性。含環氧基之有機矽烷的共聚 比率係以1 ~ 2 0莫耳％爲佳，3 ~ 1 5莫耳％更佳。環氧基之共 聚比率低於1莫耳％則相溶性提升效果不足，高於20莫耳 %則聚矽氧烷之親水性高，顯像時未曝光部之膜減量大，硬 化膜之膜均勻性變差。 含環氧基之有機矽烷的較佳具體例有3-環氧丙氧丙基 三甲氧矽烷、3-環氧丙氧丙基三乙氧矽烷、2-(3,4-環氧環 己基）乙基三甲氧矽烷、2-(3,4-環氧環己基）乙基三乙氧矽 烷、3-環氧丙氧丙基甲基二甲氧矽烷' 3-環氧丙氧丙基甲 基二乙氧矽烷、3 -環氧丙氧丙基二甲基甲氧矽烷、3 -環氧 丙氧丙基二甲基乙氧矽烷等。這些有機矽烷可單獨或組合 2種以上使用。這些有機矽烷之中，基於硬化膜的耐皸裂 性與硬度，係以三官能性矽烷爲較佳。 用於本發明之聚矽氧烷的重量平均分子量（Mw)無特殊 限制，較佳者爲以GPC (凝膠滲透層析）測定經聚苯乙烯換 算達 1000~100000，更佳者 2000~5000(^Mw 小於 1000 則塗 -14- 200912544 膜性差，大於1 00000則形成圖案時於顯像液之溶解度低。 本發明中’聚矽氧烷係由一般式（1)之有機矽烷等單體 經水解及部分縮合所合成。水解及部分縮合可採用一般方 法。例如，於混合物添加溶劑、水、必要時之觸媒，以5 0〜1 5 0 °C加熱攪拌〇 . 5〜1 00小時左右。攪拌中，必要時可藉蒸餾 去除水解副產物（甲醇等醇類）、縮合副產物（水）。 該反應溶劑無特殊限制，通常係用如同後敘（d)溶劑 者。溶劑之添加量係相對於有機矽烷等單體1 〇 〇重量份以 1 0~ 1 000重量份爲佳。用於水解反應之水的添加量係相對於 水解性基1莫耳以0.5〜2莫耳爲佳。 必要時添加之觸媒無特殊限制，但以用酸觸媒、鹼觸 媒爲佳。酸觸媒之具體例有鹽酸、硝酸、硫酸、氟酸、磷 酸、乙酸、三氟乙酸、甲酸、多元羧酸或其酐、離子交換 樹脂。鹼觸媒之具體例可列舉以下化合物。即，三乙胺、 三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、二 乙胺、三乙醇胺 '二乙醇胺、氫氧化鈉、氫氧化鉀、具有 胺基之烷氧矽烷 '離子交換樹脂等。觸媒之添加量係以相 對於有機矽烷等單體100重量份0.01 ~1〇重量份爲佳。 從組成物之儲存安定性的觀點，水解、部分縮合後之 聚矽氧烷溶液係以不含觸媒爲佳。因而，必要時可將觸媒 去除。去除方法無特殊限制，較佳者爲水洗，及/或離子交 換樹脂處理。水洗係以適當之疏水性溶劑稀釋聚矽氧烷溶 液後，以水洗淨數次得有機層，以蒸發器濃縮之方法。離 子交換樹脂處理係使適當之離子交換樹脂接觸聚矽氧烷溶 液之方法。 -15- 200912544 本發明之感光性組成物含有（b)丙烯酸樹脂。丙烯酸樹 脂無特殊限制，較佳者有不飽和羧酸之聚合物。不飽和羧 酸有例如丙烯酸 '甲基丙烯酸、伊康酸、巴豆酸、順丁烯 二酸、延胡索酸等。這些可單獨或與其它可共聚之乙烯式 不飽和化合物組合使用。可共聚之乙烯式不飽和化合物有 例如丙烯酸甲酯、甲基丙烯酸甲酯、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、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正 丁酯、丙烯酸二級丁酯、甲基丙烯酸二級丁酯、丙烯酸異 丁酯、甲基丙烯酸異丁酯、丙烯酸三級丁酯、甲基丙烯酸 三級丁酯、丙烯酸正戊酯、甲基丙烯酸正戊酯、丙烯酸2-羥乙酯、甲基丙烯酸2 -羥乙酯、丙烯酸環氧丙酯、甲基丙 烯酸環氧丙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、苯乙 烯、對甲苯乙烯、鄰甲苯乙烯、間甲苯乙烯、α -甲苯乙烯、 丙烯酸三環[5.2.1.02’6]癸-8-酯、甲基丙烯酸三環[5.2.1.0〃] 癸-8 -酯等。 用於本發明之丙烯酸樹脂的重量平均分子量（Mw)無特 殊限制，較佳者爲以 GPC測定經聚苯乙烯換算達 5000~50000，更佳者 8000~35000。Mw 小於 5000 則熱硬化 時圖案崩壞而解析度差，大於5 0000則聚矽氧烷與丙烯酸 樹脂起相分離，膜白濁，硬化膜之透過率低。 用於本發明之丙烯酸樹脂係以具鹼可溶性爲佳，。丙烯 酸樹脂的酸値係以50~150mgK〇H/g爲佳，70~130mgKOH/g 更佳。樹脂酸値小於50mgK〇H/g則顯像時易有不溶殘渣， 而酸値大於150mgK〇H/g則顯像時未曝光部之膜減量大。 -16- 200912544 用於本發明之丙烯酸樹脂係以於側鏈附加有乙烯式不 飽和基的丙烯酸樹脂爲佳。於側鏈附加乙烯式不飽和基’ 熱硬化時丙烯酸樹脂起交聯，硬化膜之耐藥物性提升。較 佳不飽和當量之範圍係5 00〜1 5 00。不飽和當量小於500則 熱硬化時丙烯酸樹脂交聯密度過高，硬化膜易起皸裂。不 飽和當量大於1 5 00則熱硬化時丙烯酸樹脂交聯不足。因 而，硬化膜之耐藥物性提升效果不足。乙烯式不飽和基有 乙烯基、烯丙基’、甲基丙烯醯基等。於丙烯酸樹脂附加乙 烯式不飽和基之方法有，使用含羥基、胺基、環氧丙基等 官能基與乙烯式不飽和基之化合物，使此官能基與丙烯酸 樹脂中的羰基反應之方法。於此所謂含羥基、胺基、環氧 丙基等官能基與乙烯式不飽和基之化合物有，丙烯酸2羥 乙酯、甲基丙烯酸2-羥乙酯、丙烯酸2_胺乙酯、甲基丙稀 酸2-胺乙酯 '丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯等。 本發明之感光性組成物含有（c)醌二疊氮化合物。含有 醒二疊氮化合物之感光性組成物，可成爲曝光部能以顯像 V 液去除之正型。所用之醌二疊氮化合物無特殊限制，較佳 化合物係’以萘醌二疊氮磺酸酯結合於具有酚式經基之化 合物者。以該化合物之酚式羥基的鄰位及對位各自獨立係 氮或一般式（2)的取代基中任一之化合物爲佳。Sand particles: The specific examples of the sub particles include the following particles. That is, IPA-ST having a particle diameter of 12 nm using isopropyl alcohol as a dispersing medium, MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersing medium, and a particle diameter of 45 ηηη using isopropyl alcohol as a dispersing medium IPA-ST-L, ipA_st_zl with a particle size of 1〇〇11111 using isopropanol as a dispersing medium, PGM-ST with a particle size of 15 nm using propylene glycol monomethyl ether as a dispersing medium (above trade name 'Nissan Chemical Industry Co., Ltd.') OSCAR 101 having a particle size of 12 nm using r-butyrolactone as a dispersing medium, OSCAR 105 having a particle diameter of 60 nm using r-butyrolactone as a dispersing medium, and a particle size of 分散2〇ηηι using acetol as a dispersing medium OSCAR -12- 200912544 106, CATALOID-S (the above trade name, Catalyst Chemical Industry Co., Ltd.) with a particle size of 5 to 80 nm in a dispersion solution, and a particle size of 16 nm with propylene glycol monomethyl ether as a dispersion medium. Quartron PL-2L-PGME, Quartron PL-2L-BL with a particle size of 17 nm with 7"-butyrolactone as a dispersing medium, Quartron PL-2L-DAA with a particle size of 17 nm with diacetone alcohol as a dispersing medium, dispersion system Quartron PL-2L, GP-2L (product name, manufactured by Fuso Chemical Industry Co., Ltd.) with water particle size of 18 to 20 nm, vermiculite (Si〇2) SG-S0100 with a particle size of 100 nm (trade name, commensal material (stock) system), REOLOSIL (product name, : Tokuyama Co., Ltd.) with a particle size of 5 to 50 nm. These vermiculite particles may be used alone or in combination of two or more. The mixing ratio is not particularly limited when the vermiculite particles are used, but the Mo number of the Si atoms is preferably 50% or less with respect to the total number of Si atoms of the polymer. When the vermiculite particles are more than 50%, the compatibility of the polyoxyalkylene with the quinonediazide compound is deteriorated, and the transparency of the cured film is poor. The molar ratio of the S 1 atomic mole of the vermiculite particles to the Si atom of the entire polymer can be determined from the integral ratio of the peak of the Si-C bond from the IR to the peak derived from the Si-◦ bond. When there are many overlaps in the peak and it is impossible to determine, the structure of the monomer other than the particles can be determined by 1H-NMR, 13 C-NMR, IR, TOF-MS, etc., and the gas and residual ash generated by the elemental analysis method can be used. The ratio of (assuming all SiO 2 is assumed) is obtained. The polyoxyalkylene used in the present invention is extremely important for forming a uniform cured film having no phase separation for improving the compatibility with the acrylic resin. Therefore, the phenyl group content in the polysiloxane is preferably 30 mol% or more with respect to Si atoms, more preferably 40 mol% or more. When the phenyl group content is less than 30 mol%, the polysiloxane is phase-separated from the acrylic resin in coating, drying, thermal curing, etc., the film is cloudy, and the transmittance of the cured film is low. The preferred upper limit of the phenyl content is 7 〇 -13- 200912544 mole %. When the phenyl group content is higher than 70 mol%, crosslinking is insufficient at the time of thermosetting, and the cured film is inferior in drug resistance. The phenyl group content can be determined, for example, by 29Si-NMR measurement of polyoxyalkylene, and the ratio of the peak area of S: bonded to the phenyl group to the peak area of S i not bonded to the phenyl group is determined. The polyoxyalkylene used in the present invention is more important in its compatibility with an acrylic resin. Therefore, it is preferred to use a polyoxyalkylene copolymer copolymerized with an epoxy group-containing organic decane. The polyoxyalkylene oxide obtained by copolymerization of an epoxy group-containing organodecane contains an epoxy group or an alcoholic hydroxyl group obtained by hydrolysis of an epoxy group. These groups interact with the carbonyl moiety in the acrylic resin to enhance the compatibility of the polyoxyalkylene with the acrylic resin. The copolymerization ratio of the epoxy group-containing organic decane is preferably from 1 to 20 mol%, more preferably from 3 to 15 mol%. When the copolymerization ratio of the epoxy group is less than 1 mol%, the compatibility improvement effect is insufficient, and when it is more than 20 mol%, the hydrophilicity of the polyoxane is high, and the film of the unexposed portion is reduced at the time of development, and the film of the cured film is large. Uniformity deteriorates. Preferred specific examples of the epoxy group-containing organic decane are 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropyltriethoxy decane, and 2-(3,4-epoxycyclohexyl). Ethyltrimethoxyoxane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane' 3-glycidoxypropylmethyl Diethoxy decane, 3-glycidoxypropyl dimethyl methoxy decane, 3-glycidoxypropyl dimethyl ethoxy decane, and the like. These organic decane may be used alone or in combination of two or more. Among these organic decanes, trifunctional decane is preferred because of the cleavage resistance and hardness of the cured film. The weight average molecular weight (Mw) of the polyoxyalkylene used in the present invention is not particularly limited, and is preferably 1000 to 100,000 in terms of polystyrene by GPC (gel permeation chromatography), and more preferably 2000 to 5000. (^Mw is less than 1000, then coating-14-200912544 is poor in filminess, and when it is more than 100,000, the solubility in the developing solution is low when forming a pattern. In the present invention, 'polyoxyalkylene is a monomer such as an organic decane of the general formula (1). Hydrolyzed and partially condensed. Hydrolysis and partial condensation can be carried out by a general method. For example, adding a solvent, water and, if necessary, a catalyst to the mixture, heating and stirring at 50 to 150 ° C. 5~1 00 hours In the stirring, if necessary, the hydrolysis by-product (alcohol such as methanol) and the condensation by-product (water) may be removed by distillation. The reaction solvent is not particularly limited, and is usually used as a solvent (d). The amount is preferably from 10 to 1 000 parts by weight relative to 1 part by weight of the monomer such as organic decane. The amount of water used for the hydrolysis reaction is 0.5 to 2 moles relative to the hydrolyzable group 1 molar. Good. There is no special restriction on the catalyst added when necessary, but The acid catalyst and the alkali catalyst are preferred. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, and ion exchange resin. Specific examples thereof include the following compounds: namely, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine 'diethanolamine, sodium hydroxide And potassium hydroxide, an alkoxy oxane-ion exchange resin having an amine group, etc. The amount of the catalyst added is preferably 0.01 to 1 part by weight based on 100 parts by weight of the monomer such as organodecane. From a sexual point of view, the polyoxane solution after hydrolysis and partial condensation is preferably free of catalyst. Therefore, the catalyst can be removed if necessary. The removal method is not particularly limited, preferably water washing, and/or ion. The resin is treated by exchange resin. The water is washed with a suitable hydrophobic solvent to dilute the polyoxyalkylene solution, and then washed with water several times to obtain an organic layer, which is concentrated by an evaporator. The ion exchange resin treatment system contacts the appropriate ion exchange resin. Alkane solution -15- 200912544 The photosensitive composition of the present invention contains (b) an acrylic resin. The acrylic resin is not particularly limited, and a polymer of an unsaturated carboxylic acid is preferred. The unsaturated carboxylic acid is, for example, acrylic acid methacrylic acid. Itaconic acid, crotonic acid, maleic acid, fumaric acid, etc. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. The copolymerizable ethylenically unsaturated compounds are, for example, methyl acrylate, methacrylic acid. Methyl ester, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid Secondary butyl ester, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, butyl acrylate, butyl methacrylate, n-amyl acrylate, n-amyl methacrylate , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, Ethylene, p-styrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, tricyclo[5.2.1.0''6]癸-8-ester, methacrylic acid tricyclo [5.2.1.0〃] 癸-8 - Ester and the like. The weight average molecular weight (Mw) of the acrylic resin used in the present invention is not particularly limited, and is preferably 5,000 to 50,000 in terms of polystyrene by GPC, and more preferably 8,000 to 35,000. When the Mw is less than 5,000, the pattern collapses during thermal hardening and the resolution is poor. When the Mw is more than 50,000, the polyoxane is separated from the acrylic resin, the film is cloudy, and the transmittance of the cured film is low. The acrylic resin used in the present invention is preferably alkali-soluble. The acid oxime of the acrylic resin is preferably 50 to 150 mg K 〇 H / g, more preferably 70 to 130 mg KOH / g. When the resin strontium sulphate is less than 50 mg K 〇 H / g, the insoluble residue is likely to be formed when the image is formed, and when the acid strontium is larger than 150 mg K 〇 H / g, the film loss of the unexposed portion is large when the image is developed. -16- 200912544 The acrylic resin to be used in the present invention is preferably an acrylic resin having a vinyl group-unsaturated group added to its side chain. When the ethylenically unsaturated group is added to the side chain, the acrylic resin is crosslinked, and the cured film is improved in chemical resistance. The preferred range of unsaturated equivalents is from 5 00 to 1 5 00. When the unsaturated equivalent is less than 500, the crosslinking density of the acrylic resin is too high when the heat is hardened, and the cured film is liable to be cleaved. When the unsaturated equivalent is more than 1 500, the cross-linking of the acrylic resin is insufficient at the time of thermosetting. Therefore, the effect of improving the drug resistance of the cured film is insufficient. The ethylenically unsaturated group is a vinyl group, an allyl' group, a methacryloyl group or the like. The method of adding an ethylenically unsaturated group to an acrylic resin is a method of reacting the functional group with a carbonyl group in an acrylic resin using a compound having a functional group such as a hydroxyl group, an amine group or a glycidyl group and an ethylenically unsaturated group. Here, the compound having a functional group such as a hydroxyl group, an amine group or a glycidyl group and an ethylenically unsaturated group is a mixture of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl acrylate, and methyl group. 2-aminoethyl acrylate 'glycidyl acrylate, glycidyl methacrylate, and the like. The photosensitive composition of the present invention contains (c) a quinonediazide compound. The photosensitive composition containing the awake azide compound can be a positive type in which the exposed portion can be removed by the development V liquid. The quinonediazide compound to be used is not particularly limited, and a preferred compound is a compound in which a naphthoquinonediazide sulfonate is bonded to a compound having a phenolic thiol group. It is preferred that the ortho and para positions of the phenolic hydroxyl group of the compound are each independently a nitrogen or a compound of the general formula (2).

(式中R3、R4、R5各自獨立表碳原子數w〇之烷基、殘基 本基、取代苯基中任一；亦可由R3、R4、R5形成環） -17- 200912544 —般式（2)之取代基中，R3、R4、R5各自獨立表碳原子 數1〜10之烷基、羧基、苯基、取代苯基中任—。院基可係 無取代體或取代體，可依組成物特性作選擇。院基之具體 例有甲基、乙基 '正丙基、異丙基、正丁基、異丁基、三 級丁基、正己基、環己基、正庚基、正辛基、三氟甲基、 2-羧乙基等。取代於苯基之取代基可係羥基。亦可由R3、 R4、R5形成環，具體例有環戊環、環己環、金剛環、莽環。 酚式羥基之鄰位及對位若係上述以外，例如甲基時， 會隨熱硬化起氧化分解’硬化膜著色，無色透明性差。這 些醒二疊氮化合物可由，具酚式羥基之化合物與萘醌二疊 氮磺酸氯經習知酯化反應合成。 具酣式經基之化合物的具體例有以下（皆係本州化學 工業（股）製）。 -18- 200912544(wherein R3, R4 and R5 each independently represent an alkyl group having a number of carbon atoms, a residual basic group or a substituted phenyl group; or a ring may be formed by R3, R4 and R5) -17- 200912544 - (2) In the substituent, R3, R4 and R5 each independently represent an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. The base can be an unsubstituted or substituted body, and can be selected according to the characteristics of the composition. Specific examples of the base are methyl, ethyl 'n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, trifluoromethyl Base, 2-carboxyethyl, and the like. The substituent substituted with a phenyl group may be a hydroxyl group. Rings may also be formed by R3, R4, and R5, and specific examples thereof include a cyclopentane ring, a cyclohexane ring, a diamond ring, and an anthracene ring. When the ortho and the para position of the phenolic hydroxyl group are other than the above, for example, a methyl group is oxidatively decomposed by thermal curing, and the cured film is colored, resulting in poor colorless transparency. These azide diazide compounds can be synthesized by a conventional esterification reaction of a compound having a phenolic hydroxyl group with naphthoquinonediazidesulfonate. Specific examples of the compound having a thiol group are as follows (all are manufactured by Honshu Chemical Industry Co., Ltd.). -18- 200912544

CH3 Bisphenol ACH3 Bisphenol A

BisOTBP-ABisOTBP-A

t-But-Bu

Bis26B-ABis26B-A

OH HO-OH HO-

H3C 'CHS BisP—MI 巳 KH3C 'CHS BisP-MI 巳 K

BisP—BBisP-B

BisP-DEKBisP-DEK

BisP-PRBisP-PR

-OH-OH

CIC—CIC TH3 OH HO-CIC—CIC TH3 OH HO-

BisP-OT CH3 όBisP-OT CH3 ό

BisP-APBisP-AP

BisP-NO BisP-ΌΕBisP-NO BisP-ΌΕ

-OH-OH

\\

£ 6 BisP-DP£ 6 BisP-DP

OH TrisP-PA -19- 200912544OH TrisP-PA -19- 200912544

萘醌二疊氮磺酸可使用4 -萘醌二疊氮磺酸或5 -萘醌二 疊氮磺酸。4-萘醌二疊氮磺酸酯化合物因於1線（波長3 6 5 nm) 範圍有吸收，適用於1線曝光。5-萘醌二疊氮磺酸酯化合物 因於諸多波長領域有吸收，適於以寬廣範圍波長曝光。以 依曝光波長選擇4 -萘醌二疊氮磺酸酯化合物、5 -萘醌二疊 氮磺酸酯化合物爲佳。亦可混合4-萘醌二疊氮磺酸酯化合 物與5 -萘醌二疊氮磺酸酯化合物使用。 醌二疊氮化合物之添加量無特殊限制，較佳者爲相對 於樹脂（聚矽氧烷+丙烯酸樹脂）100重量份爲1~20重,量份， 更佳者爲2〜1 5重量份。醌二疊氮化合物之添加量少於1重 量份則曝光部與未曝光部之溶解對比過低，不具實用之感 -20- 200912544 光性。爲得更良好之溶解對比，以2重量份以上爲佳。而 醌二疊氮化合物之添加量大於20重量份則硬化膜之無色 透明性差。此係由於，聚矽氧烷與醌二疊氮化合物之相溶 性變差而塗膜白化，或熱硬化時醌二疊氮化合物起分解而 著色。爲得更高透明性之膜，以1 5重量份以下爲佳。 本發明之感光性組成物含有（d)溶劑。所用之溶劑無特 殊限制，較佳者爲具有醇式羥基之化合物，及/或具有羰基 之環狀化合物。使用這些溶劑則聚矽氧烷、丙烯酸樹脂、 * 及醌二疊氮化合物均勻溶解，組成物經塗布成膜亦不白 化，可達高透明性。 該具有醇式羥基之化合物無特殊限制，較佳者爲大氣 壓力下沸點1 10~25 0°C之化合物。沸點高於25(TC則膜中溶 劑殘留量大，熟化時膜收縮大，不得良好之平坦性。而沸 點低於1 1 o°c則塗膜時乾燥過快而表面粗糙等，塗膜性惡 化。 具有醇式羥基之化合物的具體例有乙醯甲醇、3 -羥- 3-i : 甲基-2-丁酮、4-羥-3·甲基-2-丁酮、5-羥-2-戊酮、4-羥-4- 甲基-2-戊酮（二丙酮醇）、乳酸乙酯、乳酸丁酯、丙二醇一 甲酸、丙二醇一乙醚、丙二醇一正丙醚、丙二醇一正丁醚、 丙二醇一（三級丁基）醚、二丙二醇一甲醚、3 -甲氧-1-丁醇、 3 —甲基-3-甲氧-卜丁醇、苯甲醇等。這些之中以更具有羰基 之化合物爲佳，二丙酮醇尤佳。這些具有醇式羥基之化合 物可單獨或組合2種以上使用。 具有羰基之環狀化合物無特殊限制，較佳者爲大氣壓 力下沸點1 5 0〜2 5 0 °C之化合物。沸點高於2 5 01則膜中溶劑 -21- 200912544 殘留量大’熟化時膜收縮大，不得良好之平坦性。而沸點 低於1 50°C則塗膜時乾燥過快而表面粗糙等，塗膜性惡化。 具有羰基之環狀化合物的具體例可列舉以下化合物。 即’ r-丁內酯、r-戊內酯、<5-戊內酯、碳酸丙二酯、N-甲基吡咯烷酮、環戊酮、環己酮、環庚酮等。這些之中以 r -丁內酯爲尤佳。這些具有羰基之環狀化合物可單獨或組 合2種以上使用。 該具有醇式羥基之化合物與具有羰基之環狀化合物可 單獨或各予混合使用。混合使用時，其重量比率無特殊限 制’較佳者爲具有醇式羥基之化合物/具有羰基之環狀化合 物=99〜50/1〜50，更佳者97〜60/3〜40。具有醇式羥基之化合 物多於99重量％(具有羰基之環狀化合物少於i重量％)則聚 矽氧烷與醌二疊氮化合物之相溶性差，硬化膜白化，透明 性差。具有醇式羥基之化合物少於5 0重量％ (具有羰基之環 狀化合物多於50重量％)則聚矽氧烷中之未反應矽烷醇基 易起縮合反應，儲存安定性差。 本發明之感光性組成物只要無損於本發明之效果，亦 可含其它溶劑。其它溶劑有乙酸乙酯、乙酸正丙酯、乙酸 異丙酯、乙酸正丁酯 '乙酸異丁酯、丙二醇一甲醚乙酸酯、 乙酸3 -甲氧-1-丁酯、乙酸3 -甲-3-甲氧-1-丁酯、乙醯乙酸 乙酯等酯類，甲基異丁基酮、二異丙基酮、乙醯丙酮等酮 類，二乙醚、二異丙醚、二正丁醚、二苯醚、二甘醇乙基 甲醚等醚類等。 溶劑之添加量無特殊限制，較佳者爲相對於樹脂（聚矽 氧烷+丙烯酸樹脂）100重量份爲100〜1000重量份。 -22- 200912544 本發明之感光性組成物必要時可含有矽烷耦合劑、交 聯劑、交聯促進劑、增感劑、熱自由基產生劑、溶解促進 劑、溶解抑制劑、界面活性劑、安定劑、消泡劑等添加劑。 本發明之感光性組成物可含有矽烷耦合劑。含有矽烷 親合劑即可提升與基板之密著性。 矽烷耦合劑之具體例可列舉以下化合物。即，甲基三 甲氧矽烷、甲基三乙氧矽烷、二甲基二甲氧矽烷、二甲基 二乙氧矽烷、乙基三甲氧矽烷、乙基三乙氧矽烷、正丙基 三甲氧矽烷、正丙基三乙氧矽烷、正丁基三甲氧矽院、正 丁基三乙氧矽烷、苯基三甲氧矽烷、苯基三乙氧矽院、二 苯基二甲氧矽烷、二苯基二乙氧矽烷、乙烯基三甲氧矽烷、 乙烯基三乙氧矽烷、3 -甲基丙烯醯氧丙基三甲氧砂院、3-甲基丙烯醯氧丙基三乙氧矽烷、3-甲基丙烯醯氧丙基甲基 二甲氧矽烷、3 -甲基丙烯醯氧丙基甲基二乙氧矽院、3 -丙 烯醯氧丙基三甲氧矽烷、3 -胺丙基三甲氧矽烷、3 -胺丙基 三乙氧矽烷、3-三乙氧矽烷基- N-(l，3-二甲亞丁基）丙胺、 N -苯-3 -胺丙基三甲氧矽烷、3 -環氧丙氧丙基三甲氧砂烷、 3-環氧丙氧丙基三乙氧矽烷' 3-環氧丙氧丙基甲基二乙氧 矽烷、2-(3,4-環氧環己基）乙基三甲氧矽烷、2-(3,4-環氧環 己基）乙基三乙氧矽烷、[(3 -乙基-3-環氧丙基）甲氧基]丙基 三甲氧矽烷、[(3-乙基-3-環氧丙基）甲氧基]丙基三乙氧矽 烷、3 -锍丙基三甲氧矽烷、3 -锍丙基甲基二甲氧砂院、3-脲丙基三乙氧矽烷、3 -異氰酸酯丙基三乙氧矽烷、3 -三甲 氧矽烷丙基琥珀酸、N -三級丁基-3 - (3 -三甲氧矽烷丙基）琥 珀醯亞胺等。 -23- 200912544 砂丨/c親合劑之添加重無特殊限制’較佳者相對於樹脂 (聚矽氧烷+丙烯酸樹脂）1〇〇重量份爲0.1〜10重量份。添加 量小於0.1重量份則密著性提升效果不足，大於1 〇重量份 則保存中矽烷耦合劑互起縮合反應，造成顯像時有不溶殘 渣。 本發明之感光性組成物亦可含交聯劑。交聯劑係熱硬 化時將聚矽氧烷、丙烯酸樹脂交聯，組入樹脂中之化合物， 含有則硬化膜之交聯度提高。藉此，硬化膜之耐藥物性提 升’且熱硬化時圖案崩壞所致之圖案解析度下降受抑制。 交聯劑無特殊限制，較佳者有具選自一般式（3)之基、 環氧構造、環氧丙構造2個以上之化合物。該構造之組合 無特殊限制，所選之構造相同者爲較佳。 —(cH2〜〇_r6) ⑶ (R6表氫、碳原子數1~丨〇之烷基中任一；化合物中複數之 R6可各係相同或不同） 具有一般式（3)之基2個以上的化合物中，R6表氫 '碳 原子數1〜1〇之烷基中任一。化合物中複數之R6可各係相 同或不同。烷基之具體例有甲基、乙基、正丙基、異丙基' 正丁基、三級丁基、正己基、正癸基。 具有一般式（3)之基2個以上的化合物之具體例有如下 的三聚氰胺衍生物、尿素衍生物（商品名，三和化學（股）製）。 -24- 200912544As the naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid can be used. The 4-naphthoquinonediazide sulfonate compound is absorbed in the 1-line (wavelength 3 6 5 nm) range and is suitable for 1-line exposure. The 5-naphthoquinonediazide sulfonate compound is suitable for exposure over a wide range of wavelengths due to absorption in many wavelength domains. It is preferred to select a 4-naphthoquinonediazide sulfonate compound or a 5-naphthoquinonediazide sulfonate compound depending on the exposure wavelength. A 4-naphthoquinonediazide sulfonate compound may also be used in combination with a 5-naphthoquinonediazide sulfonate compound. The amount of the quinonediazide compound to be added is not particularly limited, and is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, per 100 parts by weight of the resin (polyoxyalkylene + acrylic resin). . When the amount of the quinonediazide compound added is less than 1 part by weight, the dissolution of the exposed portion and the unexposed portion is too low, and the practical feeling is not -20-200912544. In order to obtain a better dissolution contrast, it is preferably 2 parts by weight or more. When the amount of the quinonediazide compound added is more than 20 parts by weight, the colorless transparency of the cured film is poor. This is because the compatibility of the polyoxyalkylene with the quinonediazide compound is deteriorated and the coating film is whitened, or the quinodidiazide compound is decomposed and colored during thermal curing. In order to obtain a film having higher transparency, it is preferably 15 parts by weight or less. The photosensitive composition of the present invention contains (d) a solvent. The solvent to be used is not particularly limited, and is preferably a compound having an alcoholic hydroxyl group and/or a cyclic compound having a carbonyl group. By using these solvents, the polyoxyalkylene, the acrylic resin, the * and the quinonediazide compound are uniformly dissolved, and the composition is not whitened by coating, and the transparency is high. The compound having an alcoholic hydroxyl group is not particularly limited, and is preferably a compound having a boiling point of from 10 to 25 ° C at atmospheric pressure. The boiling point is higher than 25 (TC is the solvent residual amount in the film, the film shrinkage is large when aging, and the flatness is not good. When the boiling point is lower than 1 1 o °c, the film is dried too fast and the surface is rough, etc., film coating property Deterioration. Specific examples of the compound having an alcoholic hydroxyl group are acetonitrile methanol, 3-hydroxy-3-i: methyl-2-butanone, 4-hydroxy-3.methyl-2-butanone, 5-hydroxy- 2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monocarboxylic acid, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol-n-butyl Ether, propylene glycol mono(tributyl)ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-butanol, benzyl alcohol, etc. Further, a compound having a carbonyl group is preferred, and a diacetone alcohol is preferred. These compounds having an alcoholic hydroxyl group may be used singly or in combination of two or more. The cyclic compound having a carbonyl group is not particularly limited, and preferably has a boiling point of 15 at atmospheric pressure. 0~2 5 0 °C compound. Boiling point higher than 2 5 01 solvent in the film-21-200912544 Large residual amount 'The film shrinks when matured, and good flatness is not allowed. When the boiling point is lower than 150 ° C, the coating film is dried too fast and the surface is rough, and the coating property is deteriorated. Specific examples of the cyclic compound having a carbonyl group include the following compounds: i.e., r-butyrolactone, r-pentane Ester, <5-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone, etc. Among these, r-butyrolactone is preferred. These have a carbonyl group. The cyclic compound may be used alone or in combination of two or more. The compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used singly or in combination. When used in combination, the weight ratio thereof is not particularly limited. a compound having an alcoholic hydroxyl group / a cyclic compound having a carbonyl group = 99 to 50/1 to 50, more preferably 97 to 60/3 to 40. More than 99% by weight of a compound having an alcoholic hydroxyl group (having a ring of a carbonyl group) When the compound is less than i% by weight, the compatibility between the polyoxyalkylene oxide and the quinonediazide compound is poor, the cured film is whitened, and the transparency is poor. The compound having an alcoholic hydroxyl group is less than 50% by weight (the cyclic compound having a carbonyl group is large) 50% by weight of unreacted stanol in polyoxyalkylene It is easy to condense and has poor storage stability. The photosensitive composition of the present invention may contain other solvents as long as it does not impair the effects of the present invention. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. Esters such as isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate and the like. a ketone such as methyl isobutyl ketone, diisopropyl ketone or acetonitrile acetone; an ether such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether or diethylene glycol ethyl methyl ether. The amount of addition is not particularly limited, and is preferably 100 to 1000 parts by weight based on 100 parts by weight of the resin (polysiloxane/acrylic resin). -22- 200912544 The photosensitive composition of the present invention may contain a decane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution promoter, a dissolution inhibitor, a surfactant, and, if necessary, Additives such as stabilizers and defoamers. The photosensitive composition of the present invention may contain a decane coupling agent. Containing a decane affinity enhances adhesion to the substrate. Specific examples of the decane coupling agent include the following compounds. Namely, methyltrimethoxy decane, methyltriethoxy decane, dimethyldimethoxy decane, dimethyldiethoxy decane, ethyltrimethoxy decane, ethyltriethoxy decane, n-propyltrimethoxy decane , n-propyl triethoxy decane, n-butyl trimethoate, n-butyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy oxime, diphenyl dimethoxy decane, diphenyl Diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl propylene oxypropyl trimethoxy sand, 3-methyl propylene oxypropyl triethoxy decane, 3-methyl Propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene oxiranyl methyl diethoxy oxime, 3-propylene oxypropyl trimethoxy decane, 3-aminopropyl trimethoxy decane, 3 -Aminopropyltriethoxyoxane, 3-triethoxydecyl-N-(l,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxydecane' 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxane, 2-(3,4-epoxy Hexyl)ethyltriethoxydecane, [(3-ethyl-3-epoxypropyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-epoxypropyl)methoxy Propyl triethoxy decane, 3- propyl propyl trimethoxane, 3- propyl propyl dimethyl oxalate, 3-ureidopropyl triethoxy decane, 3-isocyanate propyl triethoxy decane, 3-trimethoxydecylpropyl succinic acid, N-tertiary butyl-3-(3-trimethoxydecylpropyl) amber imine or the like. -23- 200912544 The weight of the sand 丨/c affinity agent is not particularly limited. It is preferably 0.1 to 10 parts by weight based on 1 part by weight of the resin (polysiloxane/acrylic resin). When the amount is less than 0.1 part by weight, the adhesion improving effect is insufficient, and when it is more than 1 〇 by weight, the decane coupling agent is stored in a condensation reaction, resulting in insoluble residue at the time of development. The photosensitive composition of the present invention may also contain a crosslinking agent. When the crosslinking agent is thermally hardened, the polysiloxane or the acrylic resin is crosslinked, and the compound incorporated in the resin contains a degree of crosslinking of the cured film. Thereby, the chemical resistance of the cured film is increased, and the decrease in the pattern resolution due to the pattern collapse during heat hardening is suppressed. The crosslinking agent is not particularly limited, and preferably has two or more compounds selected from the group consisting of the general formula (3), an epoxy structure, and a propylene-propylene structure. The combination of the configurations is not particularly limited, and those having the same configuration are preferred. —(cH2~〇_r6) (3) (R6 represents hydrogen or any of the alkyl groups having 1 to 丨〇; the plural R6 in the compound may be the same or different) 2 groups having the general formula (3) In the above compound, R6 represents any one of hydrogen atoms having 1 'to 1 ' carbon number of carbon atoms. The plural R6 in the compound may be the same or different. Specific examples of the alkyl group are a methyl group, an ethyl group, a n-propyl group, an isopropyl 'n-butyl group, a tertiary butyl group, a n-hexyl group, and a n-decyl group. Specific examples of the compound having two or more groups of the general formula (3) include the following melamine derivatives and urea derivatives (trade names, manufactured by Sanwa Chemical Co., Ltd.). -24- 200912544

ηζο-ο-η2^ nch2-o-ch3 NIKALAC MW-30HM h3c-o-h2c、 H3C-0-H2C .CH2-0-CH3 N、 CH2O-CH3 ‘入财0,3 h3c-o-h2c、Ζζο-ο-η2^ nch2-o-ch3 NIKALAC MW-30HM h3c-o-h2c, H3C-0-H2C .CH2-0-CH3 N, CH2O-CH3 ‘Entering money 0,3 h3c-o-h2c,

NIKALAC MX-270NIKALAC MX-270

H3C-0 0-CH3 NIKALAC MX-280 H3C-O-H2C ,ch2-o-ch3 o=c、 VNH—CH2*〇—CH3 NH—CH/O—CH3 NIKALAC MX-290H3C-0 0-CH3 NIKALAC MX-280 H3C-O-H2C ,ch2-o-ch3 o=c, VNH—CH2*〇—CH3 NH—CH/O—CH3 NIKALAC MX-290

具有環氧構造2個以上之化合物的具體例可列舉以下 化合物。良卩，EPOLIGHT 40E、 EPOLIGHT 1 00E、 EP0LIGHT 200E、EPOLIGHT 400E、EPOLIGHT 70P、EPOLIGHT 200P、 EPOLIGHT 400P、EPOLIGHT 1 500NP、EPOLIGHT 80MF ' EPOLIGHT 4 000、EPOLIGHT 3002(以上商品名，共榮社化學 工業（股）製）、DENACOL EX-212L、DENACOL EX-214L、 DENACOL EX-216L 、 DENACOL EX-850L 、 DENACOL EX-321L(以上商品名，Nagase ChemteX(股）製）、GAN、C〇T、 EPPN5 02H、NC3 000、NC6000(以上商品名，日本化藥（股） 製）、EPIKOTE 8 2 8、EPIKOTE 1 002 ' EPIKOTE 1 7 5 0 ' EPIKOTE 1 007、YX8100-BH30、E 1 25 6、E425 0、E4275(以上商品名， JAPAN EPOXY RESIN(股）製）、EPICLON EXA- 9 5 8 3 'EPICLON HP403 2、EPICLON N 695 ' EPICLON HP7200(以上商品名， 大日本油墨化學工業（股）製）、TEPIC S、TEPIC G、TEPIC P (以上商品名，日產化學工業（股）製）、EPOTOHTO YH-434L(商品名，東都化成（股）製）、CELLOXIDE 2021P(商 品名，DAICEL 化學工業（股）製）、OGSOL PG-100、OGSOL EG-210 (以上商品名，Osaka Gas Chemicals(股）製）等。 -25- 200912544 具有環氧丙構造2個以上之化合物的具體例可列舉以 下化合物。即 ’ OXT-121、OXT-221、OX-SQ-H、OXT-191、 PNOX-1009、RSOX(以上商品名，東亞合成（股）製）、 ETANACOL 〇XBT、ETANACOL OXTP (以上商品名’宇咅G興 産（股）製）等。 該交聯劑可單獨或組合2種以上使用。 交聯劑之添加量無特殊限制，較佳者相對於樹脂（聚矽 氧烷+丙烯酸樹脂）1 〇〇重量份爲0.1 ~ 1 0重量份。交聯劑之 C 添加量小於〇.1重量份則樹脂的交聯不足，效果低。交聯 劑之添加量大於10重量份則硬化膜的無色透明度低，組成 物之儲存安定性差。 本發明之感光性組成物可含有交聯促進劑。交聯促進 劑係熱硬化時促進聚矽氧烷之交聯的化合物，熱硬化時係 使用產生酸之熱酸產生劑，而熱硬化前褪色曝光時係使用 產生酸之光酸產生劑。熱硬化時因膜中有酸存在，可促進 聚矽氧烷中之未反應矽烷醇基的縮合反應，而硬化膜之交 t 聯度提高。藉此，硬化膜之耐藥物性提升，熱硬化時圖案 崩壞所致之圖案解析度下降受抑制。 用於本發明之熱酸產生劑係熱硬化時產生酸之化合 物，以組成物塗布後預烘烤時不產生，或僅少量產生酸爲 佳。因此’以係於預烘烤溫度以上’例如1 0 〇 °c以上產生酸 之化合物爲佳。於預烘烤溫度以下產生酸則預烘烤時聚矽 氧烷易起父聯，感度下降，顯像時有不溶殘澄之產生等。 適用之熱酸產生劑的具體例可列舉以下熱酸產生劑。 即 ’ SI-60、SI-80、SI-100、SI-110、si-145、SI-150、SI-60L、 -26- 200912544 SI-80L、 SI-100L、 SI-110L、 SI-145L、 SI-150L、 SI-160L、 SI-180L(以上商品名，三新化學工業（股）製）三氟甲磺酸4-羥苯基二甲锍、三氟甲磺酸苯甲基-4-羥苯基甲毓、三氟甲 磺酸2-甲苯甲基-4-羥苯基甲锍、三氟甲磺酸4-乙醯苯基二 甲锍、三氟甲磺酸4-乙醯苯基苯甲基甲锍、三氟甲磺酸4-甲氧羰氧苯基二甲锍、三氟甲磺酸苯甲基-4-甲氧羰氧苯基 甲锍（以上商品名，三新化學工業（股）製）等。這些化合物可 單獨或組合2種以上使用。 用於本發明之光酸產生劑係褪色曝光時產生酸之化合 物，係藉曝光波長365nm(i線）、405nm(h線）、436nm(g線） 或這些之混合線照射而產生酸之化合物。因此，於使用同 樣光源之圖案曝光亦可能有酸產生。但是，圖案曝光因曝 光量小於褪色曝光，不會有僅產生少量酸之問題。所產生 之酸並係以全氟烷基磺酸、對甲苯磺酸等強酸爲佳。產生 羧酸之醌二疊氮化合物不具此所謂光酸產生劑之機能，在 本發明中有別於交聯促進劑。 適用之光酸產生劑的具體例可列舉以下光酸產生劑。 即，SI-100、 SI-101、 SI-105、 SI-106、 SI-109、 PI-105、 PI-106、 PI-109、NAI-100、NAI-1002、NAI-1003、NAI-1004、NAI-101、 NAI-105、NAI-106、NAI-109、NDI-1(H' NDI-105、NDI-106、 NDI-109、PAI-01、PAI-101、PAI-I06、ΡΑΙ-ΙΟΟΙ (以上商品 名，綠化學（股）製），SP-077 ' SP-082 (以上商品名，ADEKA(股） 製），TPS-PFBS(以上商品名，東洋合成工業（股）製）， WPAG-281、WPAG-336、WPAG-339、WPAG-342、WPAG-344、 -27- 200912544 WPAG-350、WPAG- 3 70、WPAG-372、WPAG-449、WPAG-469、 WPAG-505、WPAG-506(以上商品名，和光純藥工業（股）製）， CGI-MDT、 C GI - NIT (以上商品名，c i b a S p e c i a 11 y Chemicals (股）製）等。這些化合物可單獨或組合2種以上使 用。 亦可倂用該熱酸產生劑與光酸產生劑作爲交聯促進 劑。 交聯促進劑之添加量無特殊限制，較佳者相對於樹脂 (聚矽氧烷+丙烯酸樹脂）1〇〇重量份爲0.0丨~5重量份。添加 量小於0.01重量份則效果不足，大於5重量份則預烘烤 時、圖案曝光時聚矽氧烷起交聯。 本發明之感光性組成物亦可含有增感劑。含有增感劑 則感光劑醌二疊氮化合物之反應受促進而感度提升。含有 光酸產生劑作爲交聯促進劑則褪色曝光時之反應受到促 進，硬化膜之耐溶劑性與圖案解析度提升。 用於本發明之增感劑無特殊限制，較佳者爲因熱處理 而氣化，且/或因照光而褪色之增感劑。此增感劑必須對於 圖案曝光、褪色曝光時之光源波長365nm(i線）、405nm(h 線）、43 6nm(g線）有吸收。可是，直接殘留於硬化膜則於可 見光範圍有吸收，無色透明性變差。故因熱硬化等熱處® 而氣化之增感劑，及/或因褪色曝光等的照光而褪色之增感 劑較適用。 該因熱處理氣化，及/或因照射而褪色之增感劑的具體 例可列舉以下增感劑。即，3,3’ -羰雙（二乙胺薰草素）等薰 28- 200912544 草素，9,10-蒽醌等蒽醌，二苯基酮、4,4，-二甲氧二苯基 苯乙酮、4-甲氧苯乙酮、苯甲醛等芳酮，聯苯、i，4 —二^ 9_弗酮、莽、菲、聯三伸苯、芘、蒽、9-苯蒽、9_甲氧 9, 10-二苯蒽、9，10-雙（4-甲氧苯基）蒽、9, 10-雙（三苯砂1 蒽、9,10-二甲氧蒽、9,10-二乙氧蒽、9,10-二丙氧蒽、 二丁氧蒽、9,10-二戊氧蒽、2-三級丁 -9,10 -二丁氧恩、 雙（三甲矽烷基）蒽等縮合芳族等。 這些增感劑之中，係以因熱處理昇華、蒸發’熱 所產生之熱分解物昇華或蒸發之增感劑爲佳° 胃胃1 化溫度以130〜400t爲佳，150〜250 t更佳。增感劑之 溫度低於1 3 0。(：則有時增感劑於預烘烤中氣化’不存在 光過程中，感度無法提高。爲於預烘烤中極力抑制氣 增感劑之氣化溫度以1 5 0 r以上爲較佳。而增感齊1 $氣1 度高於4 0 0 °C則有時增感劑於熱硬化時不氣化’殘留# 膜中，無色透明性變差。爲使於熱硬化時完全氣化’ 劑之氣化溫度以250°C以下爲佳。 藉照光褪色之增感劑從透明性之觀點係以於可見 圍之吸收因照光而褪色之增感劑爲佳。更佳之因照光 的化合物係藉照光二聚化之化合物。因藉照光二聚化 子量增大而不溶化，可得耐藥物性提升，耐熱性提升 自透明硬化膜的萃取物減少等效果。 基於可達成高感度，基於藉照光二聚化而褪色， 劑係以蒽系化合物爲佳。因9，1 〇位係氫之蒽系化合物 熱不安定’尤以9，1 0-二取代蒽系化合物爲佳。從增感 :酮、 丨萘、 ，蒽、 完基） 9.10- 9.10- 分解 之氣 氣化 於曝 化， 化溫 硬化 增感 光範 褪色 ，分 ，來 增感 對於 劑之 -29- 200912544 溶解度提升與光二聚化反應的反應性之觀點’以一般式（4) 之9,10-二烷氧蒽系化合物爲較佳。Specific examples of the compound having two or more epoxy structures include the following compounds. Liangzhu, EPOLIGHT 40E, EPOLIGHT 1 00E, EP0LIGHT 200E, EPOLIGHT 400E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 400P, EPOLIGHT 1 500NP, EPOLIGHT 80MF ' EPOLIGHT 4 000, EPOLIGHT 3002 (above trade name, Gongrongshe Chemical Industry Co., Ltd. )), DENACOL EX-212L, DENACOL EX-214L, DENACOL EX-216L, DENACOL EX-850L, DENACOL EX-321L (trade names above, manufactured by Nagase ChemteX), GAN, C〇T, EPPN5 02H, NC3 000, NC6000 (above trade name, Nippon Kayaku Co., Ltd.), EPIKOTE 8 2 8, EPIKOTE 1 002 ' EPIKOTE 1 7 5 0 ' EPIKOTE 1 007, YX8100-BH30, E 1 25 6 , E425 0, E4275 (The above product name, JAPAN EPOXY RESIN (share) system), EPICLON EXA- 9 5 8 3 'EPICLON HP403 2, EPICLON N 695 ' EPICLON HP7200 (above trade name, Dainippon Ink Chemical Industry Co., Ltd.), TEPIC S , TEPIC G, TEPIC P (above trade name, Nissan Chemical Industry Co., Ltd.), EPOTOHTO YH-434L (trade name, Dongdu Chemical Co., Ltd.), CELLOXIDE 2021P (trade name, DAICEL Chemical Industry Co., Ltd.) , OGSOL PG-100, OGS OL EG-210 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd.). -25-200912544 Specific examples of the compound having two or more epoxidized structures include the following compounds. Namely 'OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (above trade name, East Asia Synthetic Co., Ltd.), ETANACOL 〇XBT, ETANACOL OXTP (above trade name '宇咅G production (shares) system, etc. These crosslinking agents can be used individually or in combination of 2 or more types. The amount of the crosslinking agent to be added is not particularly limited, and is preferably 0.1 to 10 parts by weight based on 1 part by weight of the resin (polysiloxane/acrylic resin). When the amount of C added to the crosslinking agent is less than 0.1 part by weight, the crosslinking of the resin is insufficient and the effect is low. When the amount of the crosslinking agent added is more than 10 parts by weight, the colorless transparency of the cured film is low, and the storage stability of the composition is poor. The photosensitive composition of the present invention may contain a crosslinking accelerator. The crosslinking accelerator is a compound which promotes crosslinking of polyoxyalkylene when it is thermally hardened, and uses a thermal acid generator which generates an acid when it is thermally cured, and a photoacid generator which generates an acid when it is exposed to fading before thermosetting. In the case of thermosetting, the presence of an acid in the film promotes the condensation reaction of the unreacted stanol group in the polyoxyalkylene, and the degree of crosslinking of the cured film is improved. Thereby, the chemical resistance of the cured film is improved, and the decrease in pattern resolution due to the collapse of the pattern during heat hardening is suppressed. The thermal acid generator used in the present invention is a compound which generates an acid upon thermal hardening, and is preferably produced when the composition is pre-baked after coating, or only a small amount of acid is produced. Therefore, it is preferred to use a compound which generates an acid at a temperature above the prebaking temperature, for example, 10 Torr. When acid is generated below the prebaking temperature, the polyoxyalkylene tends to act as a parent when pre-baking, and the sensitivity is lowered, and the insoluble residue is formed during the image formation. Specific examples of the suitable thermal acid generator include the following thermal acid generators. Namely 'SI-60, SI-80, SI-100, SI-110, si-145, SI-150, SI-60L, -26- 200912544 SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) 4-hydroxyphenyl dimethyl hydrazine trifluoromethanesulfonate, benzyl methyl trifluoromethanesulfonate Hydroxyphenylformamidine, 2-toluomethyl-4-hydroxyphenylformamidine trifluoromethanesulfonate, 4-ethyl phenyl dimethyl hydrazine trifluoromethanesulfonate, 4-ethyl fluorene trifluoromethanesulfonate Benzobenzylformamidine, 4-methoxycarbonyloxyphenyl dimethyl hydrazine trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenyl hydrazine trifluoromethanesulfonate (above trade name, Sanxin) Chemical industry (shares) system, etc. These compounds may be used alone or in combination of two or more. The photoacid generator used in the present invention is a compound which generates an acid upon fading exposure, and is a compound which generates an acid by irradiation with an exposure wavelength of 365 nm (i line), 405 nm (h line), 436 nm (g line) or a mixed line of these. . Therefore, acid exposure may occur in the pattern exposure using the same light source. However, since the pattern exposure is less than the fading exposure, there is no problem that only a small amount of acid is generated. The acid produced is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid. The quinone diazide compound which produces a carboxylic acid does not have the function of a so-called photoacid generator, and is different from the crosslinking accelerator in the present invention. Specific examples of the photoacid generator to be used include the following photoacid generators. That is, SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-1 (H' NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-I06, ΡΑΙ-ΙΟΟΙ ( The above product name, Green Chemical Co., Ltd., SP-077 'SP-082 (above trade name, ADEKA (share) system), TPS-PFBS (above trade name, Toyo Synthetic Industrial Co., Ltd.), WPAG- 281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, -27- 200912544 WPAG-350, WPAG- 3 70, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (The above trade name, Higashi Pure Chemical Industries Co., Ltd.), CGI-MDT, C GI - NIT (above trade name, ciba S pecia 11 y Chemicals Co., Ltd.), etc. These compounds may be used alone or in combination of two or more. The thermal acid generator and the photoacid generator may be used as a crosslinking accelerator. The amount of the crosslinking accelerator to be added is not particularly limited, and is preferably 1 相对 relative to the resin (polysiloxane/acrylic resin). 〇 Parts by weight are from 0.0丨 to 5 parts by weight. When the amount is less than 0.01 part by weight, the effect is insufficient. When the amount is more than 5 parts by weight, the polyoxyalkylene is crosslinked during prebaking or during pattern exposure. The photosensitive composition of the present invention may further contain a sensitizer. The reaction of the quinonediazide compound is promoted and the sensitivity is improved. When the photoacid generator is used as a crosslinking accelerator, the reaction at the time of fading exposure is promoted, and the solvent resistance and pattern resolution of the cured film are improved. The sensitizer is not particularly limited, and is preferably a sensitizer which is vaporized by heat treatment and/or which is discolored by light. The sensitizer must have a light source wavelength of 365 nm (i-line) and 405 nm for pattern exposure and fading exposure. (h) and 43 6nm (g line) are absorbed. However, the sensitizer which is directly absorbed in the cured film and absorbs in the visible light range, and the colorless transparency is deteriorated, so that it is vaporized by heat such as thermal hardening, And sensitizers which are discolored by illuminating exposure, etc., are suitable. The specific example of the sensitizer which is vaporized by heat treatment and/or discolored by irradiation may be exemplified by the following sensitizers. '-Carbohydrate (diethylamine oxacin), etc. 28- 200912544 Oxalate, 9,10-蒽醌, etc., diphenyl ketone, 4,4,-dimethoxydiphenylacetophenone, 4-methoxyacetophenone, benzaldehyde and other aryl ketones, Biphenyl, i, 4 — bis 9 — ketone, fluorene, phenanthrene, ternary benzene, hydrazine, hydrazine, 9-benzoquinone, 9-methoxy 9,10-diphenylhydrazine, 9,10-bis ( 4-methoxyphenyl)anthracene, 9,10-bis(triphenylene 1 蒽, 9,10-dimethoxy oxime, 9,10-diethoxy oxime, 9,10-dipropoxy oxime, dibutyl Oxidized aromatic groups such as oxonium, 9,10-dipentoxide, 2-tris-butyl-9,10-dibutoxide, bis(trimethyldecyl)anthracene, and the like. Among these sensitizers, it is preferable to use a sensitizer for sublimation by heat treatment, evaporation of thermal decomposition products generated by heat, or evaporation. The gastric and gastric tempering temperature is preferably 130 to 400 t, and more preferably 150 to 250 t. . The temperature of the sensitizer is below 130. (: Sometimes the sensitizer is vaporized in pre-baking.) In the absence of light, the sensitivity cannot be improved. In order to suppress the gasification temperature of the gas sensitizer in the prebaking, it is more than 150 rpm. Good. While the sensitization is 1 1 gas 1 degree higher than 4 0 0 °C, sometimes the sensitizer does not vaporize in the heat-hardening 'residue # film, the colorless transparency is worse. For the heat hardening completely The vaporization temperature of the gasification agent is preferably 250 ° C or less. The sensitizer by light fading is preferably a sensitizer which absorbs light which is fading due to illumination from the viewpoint of transparency. The compound is a compound which is photodimerized by light, and is insolubilized by the increase in the amount of photodimerization, thereby improving the drug resistance, improving the heat resistance and reducing the extract from the transparent cured film. It is based on photodimerization and fading, and the agent is preferably a lanthanide compound. The ruthenium compound of hydrogen at the 9,1 oxime is thermally unstable, especially the 9,1 0-disubstituted lanthanide compound. From sensitization: ketone, anthracene naphthalene, anthracene, ruthenium) 9.10- 9.10- decomposition gas is gasified in exposure, Warm hardening increases the sensitization of the sensitizer, fading, and sensitization for the agent -29- 200912544. The solubility improvement and the reactivity of the photodimerization reaction are based on the general formula (4) of 9,10-dialkyloxanium compound. Preferably.

一般式（4)之R7~R14各自獨立，表氫、碳原子數丨~2() 之烷基、烷氧基、烯基、芳基、醯基、及該等的經取代之 有機基。烷基之具體例有甲基、乙基、正丙基。烷氧基之 具體例有甲氧基、乙氧基、丙氧基、丁氧基、戊氧基。_ 基之具體例有乙烯基、丙烯醯氧丙基、甲基丙烯醯氧。 芳基之具體例有苯基、甲苯基、萘基。醯基之具體例有& 醯基。基於化合物之氣化性、光二聚化反應性，R\R14 & 係氫或碳原子數1~6之有機基爲佳。更佳者R7、Rl。、Rll> RM係氫。 一般式（4)之R15、R16表碳原子數1~20之院翁I Ή ^ # 判巻’及該 、: 等的經取代之有機基。烷氧基之具體例有甲氧甚 ^卜 丰、绝、乙氧基、 丙氧基、丁氧基、戊氧基。基於化合物之溶解度與藉光— 聚化之褪色，尤以丙氧基、丁氧基爲佳。 增感劑之添加量無特殊限制，較佳者相對& 1如樹脂（聚矽 氧烷+丙烯酸樹脂）100重量份爲0·01~5重量忪 ^ w。超出此範 圍則透明性低，感度差。 本發明之感光性組成物亦可含有熱自由甚& 產生劑。丙R7 to R14 of the general formula (4) are each independently represented by an alkyl group, an alkoxy group, an alkenyl group, an aryl group, a fluorenyl group, and the substituted organic groups having a carbon number of 丨~2(). Specific examples of the alkyl group are a methyl group, an ethyl group, and a n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Specific examples of the group include a vinyl group, an acryloxypropyl group, and a methacrylic acid. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. The specific example of 醯基 has & 醯 base. Based on the gasification property of the compound and the photodimerization reactivity, R\R14 & is preferably hydrogen or an organic group having 1 to 6 carbon atoms. Better R7, Rl. , Rll> RM is hydrogen. In the general formula (4), R15 and R16 have a carbon number of 1 to 20, and are substituted with an organic group such as: Specific examples of the alkoxy group are methoxyxanthene, aceto, ethoxy, propoxy, butoxy or pentyloxy. It is based on the solubility of the compound and the fading of the light-polymerization, especially the propoxy group and the butoxy group. The amount of the sensitizer to be added is not particularly limited, and is preferably from 0. 01 to 5 parts by weight based on 100 parts by weight of the resin (polysiloxane/acrylic resin). Beyond this range, transparency is low and sensitivity is poor. The photosensitive composition of the present invention may also contain a thermal free & generating agent. C

烯酸樹脂係用側鏈有乙烯式不飽和基加成之Μ X 〈界烯酸樹脂 時，尤其適用。含有熱自由基產生劑即可於執版 4硬化時產生 -30- 200912544 自由基物種。於是，丙烯酸樹脂中之乙烯式不飽和基藉自 由基互相結合而交聯，硬化膜之耐藥物性提升。 熱自由基產生劑之較佳者有，一般式（5)之有機過氧化 物。 R17_〇—〇—R18 (5) 一般式（5)之R”與R18可係相同或不同，表氫、碳原子 數1~30之烷基、碳原子數6〜30之芳基、碳原子數uo之 # 醯基、碳原子數2~30之酯基。一般式（5)中R17與R18之院 基、芳基、醯基、酯基皆可有取代基。並可係無取代基之 無取代體，可依組成物特性作選擇。 烷基之具體例可列舉以下基團。即，甲基、乙基、正 丙基、異丙基、正丁基、三級丁基、正己基、環己基、正 癸基、1,1-二甲丁基等。芳基之具體例可列舉以下基_。即， 苯基、甲苯基、對羥苯基、1-甲基-1-苯乙基、苯甲基、i 甲基-1-3-(1-三級丁過氧-卜甲乙基）苯乙基等。醯基之具體 i 例可列舉以下基團。即’乙醯基、2,2-二甲丙醯基、〗7 + 1 -乙戊 醯基、苯醯基、3 -甲戊醯基等。酯基之具體例可列舉以下 基團。即，甲酯基、乙酯基、正丙酯基、異丙酯基、正丁 酯基、三級丁酯基、s-丁酯基、三級丁環己酯基等。其中， 因分解溫度高，硬化時不產生二氧化碳等氣體，以燒基或 芳基爲佳。醯基、酯基者’會有分解後更經加熱所產生之 二氧化碳氣體殘留在膜中，膜變脆。 一般式（5)之有機過氧化物的具體例可列舉以卞 卜化s 物。即，1,1-二（三級丁過氧基）環己院、2,2 -二（4,4 -〜 ' * ( —* Hlr*p -31- 200912544 丁過氧基）環己基）丙烷、三級己過氧異丙基一碳酸醋、順 丁烯二酸過氧三級丁酯、3,5，5-三甲己酸過氧三級丁酯、月 桂酸過氧三級丁酯、三級丁過氧異丙基一碳酸酯' 苯甲酸 過氧三級己酯、2,5 -二甲-2,5 -二（苯甲醯過氧基）己院、乙酸 過氧三級丁酯、2,2 -二（三級丁過氧基）丁烷' 苯甲酸過氧三 級丁酯、正丁基4,4 -二（三級丁過氧基）戊酸酯、二（2 -三級 過氧異丙基）苯、二枯基過氧化物、過氧化二（三級己基）' 2,5-二甲基- 2,5 -二（三級丁過氧基）己烷、過氧化三級丁基枯 基、過氧化二（三級丁基）、對Μ過氧化氫、2,5·二甲基_2,5_ 二（三級丁過氧基）己炔-3·二異丙苯過氧化氫、Μ，3 ,3-四甲 丁基過氧化氫、異丙苯過氧化氫等。 茲說明使用本發明之感光性組成物形成硬化膜的方 法。將本發明之感光性組成物以旋塗、狹縫等習知方法塗 布於底材基板上，以熱板、烘箱等加熱裝置預烘烤。預烘 烤係於50-15 0°C進行30秒〜30分鐘，以使預烘烤後之膜厚 達 爲佳。 預烘烤後，使用步進機、鏡面投影光罩對準曝光器 (MPA)、平行光線光罩對準曝光器（pla)等紫外可見曝光 機’介著所欲之光罩作10~400(mm2左右（以波長365nm的 曝光量換算）之圖案曝光。 曝光後’顯像溶解曝光部，可得正型圖案。較佳顯像 方法係以淋洗、浸沾、浸置等方法浸泡5秒~ 1 0分鐘。顯像 液可用習知鹼顯像液。具體例有含鹼金屬之氫氧化物、碳 酸鹽、磷酸鹽、矽酸鹽、硼酸鹽等無機鹼，2_二乙胺乙醇、 一乙醇胺、二乙醇胺等胺類，氫氧化四甲銨、膽鹼等四級 -32- 200912544 銨鹽的1種或2種以上之水溶液等。顯像後以水淋洗爲佳， 必要時可藉熱板、烘箱等加熱裝置，於5 0 ~ 1 5 0 °C行脫水乾 燥烘烤。 然後，以進行褪色曝光爲佳。進行褪色曝光則殘留在 膜中之未反應醌二疊氮化合物起光分解，膜之光透明性更 提升。褪色曝光之方法係用PLA等紫外可見曝光機，作 100~20000〗/m2左右（以波長365nm的曝光量換算）之全面曝 光。 經褪色曝光之膜，必要時以熱板、烘箱等習知加熱裝 置，於5 0〜1 5 0 °C作軟烘烤3 0秒〜3 0分鐘。然後，以熱板' 烘箱等習知加熱裝置，於1 5 0 ~ 4 5 0 °C熟化1小時左右，形成 顯示元件之TFT用平坦化膜、半導體元件之層間絕緣膜、 或光波導之芯、覆材等硬化膜。 使用本發明之感光性組成物製作之硬化膜，於波長 400nm時膜厚3#m之透光率達90%以上，更佳者達92%以 上。透光率低於90 %則用作液晶顯示裝置之TFT用平坦化 膜時，背光透過時會變色，白色顯示偏黃。 該波長400nm時膜厚3#m之透光率係以如下方法求 出。使用旋塗機以任意轉數將組成物旋塗於TEMPAX玻璃 板，以熱板於1 〇(TC預烘烤2分鐘。然後，褪色曝光係用 PLA，膜全面以超高壓水銀燈作30001/m2 (以波長3 65 nm的 曝光量換算）之曝光，使用烘箱於空氣中以220°C熱硬化1 小時，製作膜厚3 m之硬化膜。使用島津製作所（股）製 “ MultiSpec- 1 5 00 ”測定得到之硬化膜的紫外可見吸收光 譜，求出波長400nm時之透過率。 -33- 200912544 此硬化膜適用於顯示元件中之TFT用平坦化膜、半導 體元件之層間絕緣膜、或光波導之芯、覆材等。 本發明中，元件指具有如上之高耐熱性、高透明性硬 化膜之顯示元件、半導體元件、或光波導材。使用於具有 TFT用平坦化膜之顯示元件，以及有機EL顯示元件特別有 效。 實施例 以下舉實施例更具體說明本發明，但本發明不限於這 些實施例。所用的化合物之中，使用簡稱者係指以下。 DAA :二丙酮醇 PGMEA ：丙二醇一甲醚乙酸酯 EAA :乙醯乙酸乙酯 GBL : r -丁內酯 聚矽氧烷溶液與丙烯酸樹脂溶液之固體成分濃度、聚 矽氧烷與丙烯酸樹脂的重量平均分子量（Mw)、及丙烯酸樹 脂的酸値係如下求出。 (1) 固體成分濃度 於鋁杯秤取聚矽氧烷（丙烯酸樹脂）溶液1 g，使用熱板 於25 0t加熱30分鐘，使液體成分蒸發。秤量殘留在加熱 後之鋁杯的固體成分，求出聚矽氧烷（丙烯酸樹脂）溶液之 固體成分濃度。 (2) 重量平均分子量 重量平均分子量係以GPC(Waters公司製996型偵測 器，展開溶劑四氫呋喃）經聚苯乙烯換算求出。 (3) 酸値 -34- 200912544 秤取相當於1 g丙烯酸樹脂的樹脂溶液，於此溶液滴入 0.1N之氫氧化鉀（κ〇Η)水溶液，由中和所需之K〇H量求出 酸値。 合成例1 聚矽氧烷溶液之合成 於 5 00ml之三口燒瓶饋入甲基三甲氧矽垸 40.86g(0.3mol)、苯基二甲氧砂院 118.98g(0.6mol)、2-(3,4· 環氧環己基）乙基三甲氧矽烷24.64g(〇.lm〇i)、二丙酮醇（以 下簡稱DAA)171.38g，室溫攪拌下以10分鐘添加溶解於水 54g之磷酸〇.〇92g(相對於饋入之單體的〇.〇5重量％)之磷酸 水溶液。之後，將燒瓶浸於40°C之油浴攪拌30分鐘後，以 油浴經3 0分鐘升溫至1 1 5 °C。開始升溫1小時後溶液內溫 達100°C，之後加熱攪拌2小時（內溫100〜1 10°C )，得聚矽 氧烷溶液（a)。加熱攪拌中以氮0.051升/nnn流過。反應中 餾出副產物甲醇、水合計1 20g。 得到之聚矽氧烷溶液（a)的固體成分濃度係40重量％， 聚矽氧烷之重量平均分子量係65 00。聚矽氧烷中苯基含有 率係相對於Si原子60莫耳％。 合成例2 聚矽氧烷溶液（b)之合成 於 500ml之三口燒瓶饋入甲基三甲氧矽烷 23.84g(0.175mol)、苯基三甲氧矽烷 99.15g(0.5mol)、2-(3,4-環氧環己基）乙基三.甲氧矽烷12.32g(0.05mol)、矽石粒子 DAA分散液Quartron PL-2L-DAAC扶桑化學工業（股）製’矽 石粒子濃度：25重量％)66.09g(以矽原子莫耳數計 0.275mol)、及DAA 63.04g，室溫攪拌下以10分鐘添加溶 解於水39.l5g之磷酸0.076g(相對於饋入之單體的0.05重 -35- 200912544 量％)之磷酸水溶液。然後將燒瓶浸於40°C之油浴攪拌30 分鐘後，藉油浴經3 0分鐘升溫至1 1 5 °C。開始升溫1小時 後溶液內溫達100°C，之後加熱攪拌2小時（內溫100〜1 1〇 °C )，得聚矽氧烷溶液（b)。加熱攪拌中以氮0.051升/min流 過。反應中餾出副產物甲醇、水合計85 g。 得到之聚矽氧烷溶液（b)的固體成分濃度係46重量％， 聚矽氧烷之重量平均分子量係8000。聚矽氧烷中苯基含有 率係相對於Si原子50莫耳％。 ί 合成例3 聚矽氧烷溶液（c)之合成 於 5 00ml之三口燒瓶饋入甲基三甲氧矽烷 8 8.5 3 g(0.65mol)、苯基三甲氧矽烷 49.5 8g(0.25mol)、2-(3,4-環氧環己基）乙基三甲氧矽烷 24.64g(0.1mol)、及 DAA 144.83g，室溫攪拌下以10分鐘添加溶解於水54g之磷酸 0.081g(相對於饋入之單體的0.05重量％)之磷酸水溶液。然 後將燒瓶浸於40°C之油浴攪拌30分鐘後，藉油浴經30分 鐘升溫至1 1 5 °C。開始升溫1小時後溶液內溫達1 〇〇 °C，之 〇 後加熱攪拌2小時（內溫100〜1 10°C ) ’得聚矽氧烷溶液（c)。 加熱攪拌中以氮0.051升/min流過。反應中餾出副產物甲 醇、水合計1 2 0 g。 得到之聚矽氧烷溶液（c)的固體成分濃度係4 0重量％， 聚矽氧烷之重量平均分子量係9 000。聚矽氧烷中酚基含有 率係相對於Si原子25莫耳％。 合成例4 聚矽氧烷溶液（d)之合成 於 500ml 之三口燒瓶饋入甲基三甲氧矽烷 20.43g(0.15mol)、苯基三甲氧矽烷 1 5 8.64g(0_8mol)、2-(3,4- -36- 200912544 環氧環己基）乙基三甲氧矽烷12.32g(0.05mol)、及 DAA 1 7 9.54g，室溫攪拌下以10分鐘添加溶解於水54g之磷酸 〇.3 8 3 g(相對於饋入之單體的0.2重量％)之磷酸水溶液。然 後將燒瓶浸於40°C之油浴攪拌30分鐘後，藉油浴經30分 鐘升溫至1 15°C。開始升溫1小時後溶液內溫達100°C，之 後加熱攪拌3小時（內溫100〜1 10°C )，得聚矽氧烷溶液（d)。 加熱攪拌中以氮0.051升/min流過。反應中餾出副產物甲 醇、水合計1 2 0 g。 得到之聚矽氧烷溶液（d)的固體成分濃度係40重量％， 聚矽氧烷之重量平均分子量係7000。聚矽氧烷中酚基含有 率係相對於Si原子80莫耳％。 合成例5 丙烯酸樹脂溶液（a)之合成 於500ml之三口燒瓶饋入2,2’-偶氮雙（異丁腈）5g、三 級十二硫醇 5 g、及丙二醇一甲醚乙酸酯（以下簡稱 PGMEA)150g。然後饋入甲基丙烯酸30g、甲基丙烯酸苯甲 酯35£、及甲基丙烯酸三環[5.2.1.02’6]癸-8-酯35£，室溫下 短暫攪拌，燒瓶內以氮取代後，於70°C加熱攪拌5小時。 其次，於得到之溶液添加甲基丙烯酸環氧丙酯15g、二甲基 苯甲胺U、及對甲氧酚0.2g，於90°C加熱攪拌4小時，得 丙烯酸樹脂溶液（a)。 得到之丙烯酸樹脂溶液（a)的固體成分濃度係43重量 %，丙烯酸樹脂的重量平均分子量係 10600，酸値 118mgKOH/g，不飽和當量 1 090。 合成例6 丙烯酸樹脂溶液（b)之合成 於500ml之三口燒瓶饋入2,2’-偶氮雙（異丁腈）5g、及 -37- 200912544 PGMEA 150g。然後饋入甲基丙烯酸27g、甲基丙烯酸苯甲 酯38§、及甲基丙烯酸三環[5.2.1.02’6]癸-8-酯352，室溫下 短暫攪拌，燒瓶內以氮取代後，於7 0 °C加熱攪拌5小時。 其次’於得到之溶液添加甲基丙烯酸環氧丙酯15g、二甲基 苯甲胺1 g、及對甲氧酚0,2 g，於9 0 °C加熱攪拌4小時，得 丙烯酸樹脂溶液（b)。 得到之丙烯酸樹脂溶液（b)的固體成分濃度係43重量 %，丙烯酸樹脂的重量平均分子量係 31400，酸値 105mgKOH/g > 不飽和當量 1〇9〇。 合成例7 丙烯酸樹脂溶液（c)之合成 於500ml之二口燒瓶饋入2,2’-偶氮雙（異丁腈）5g、及 PGMEA 150g。然後饋入甲基丙烯酸15g、甲基丙烯酸甲酯 45g、及苯乙烯40g’室溫下短暫攪拌，燒瓶內以氮取代後， 於7 0°C加熱攪拌5小時，得丙烯酸樹脂溶液（c )。 得到之丙烯酸樹脂溶液（c)的固體成分濃度係43重量 %，丙烯酸樹脂的重量平均分子量係 20000，酸値 97mgK〇H/g，不飽和當量〇。 合成例8 丙烯酸樹脂溶液（d)之合成 於500 ml之三口燒瓶饋入2,2，-偶氮雙（異丁腈）3g、及 PGMEA 50g。然後饋入甲基丙稀酸30g、甲基丙烯酸苯甲酯 35g、及甲基丙烯酸三環[5.2.1.02.6]癸-8-酯35g，室溫下短 暫攪拌’燒瓶內以氮取代後，於7 0 °C加熱攪拌5小時。其 次，於得到之溶液添加甲基丙烯酸環氧丙酯1 5 g、二甲基苯 甲胺lg、及對甲氧酚0.2g、及PGMEA 100g，於90°C加熱 攪拌4小時，得丙稀酸樹脂溶液（d)。 -38- 200912544 得到之丙烯酸樹脂溶液（d)的固體成分濃度係43重量 %，丙烯酸樹脂的重量平均分子量 65000 ’酸値 118mgKOH/g，不飽和當量 1 090。 合成例9 丙烯酸樹脂溶液（e)之合成 於500ml之三口燒瓶饋入2，2，-偶氮雙（異丁腈）5g、三 級十二硫醇20g、及PGMEA 200g。然後饋入甲基丙烯酸 30g、甲基丙烯酸苯甲酯35g、及甲基丙烯酸三環[5.2.1.02’6] 癸-8 -酯3 5 g，室溫下短暫攪拌’燒瓶內以氮取代後’於7 0 °C加熱攪拌5小時。其次’於得到之溶液添加甲基丙'嫌酸 環氧丙酯15g、二甲基苯甲胺lg、及對甲氧酚〇_2g，於90 °C加熱攪持4小時，得丙烯酸樹脂溶液（e)。 得到之丙烯酸樹脂溶液（e)的固體成分濃度係43重量 %，丙烯酸樹脂的重量平均分子量4500,酸値118mgKOH/g， 不飽和當量1 090。 合成例10 醌二疊氮化合物U)之合成 乾燥氮氣流下，溶解TrisP-PA(商品名，本州化學工業 (股）製）21.23g(0.05mol)與 5-醌二疊氮磺酸氯 37.62g(0.14mol)於1,4-二烷450g，保持於室溫。於此，滴 入與1,4 - — D萼院50g混合之二乙fe 15.58g(0.154mol)但不使 系內溫度達3 5 °C以上。滴完後於3 0 °C攪拌2小時。將三乙 胺鹽過濾，將濾液注入水中。然後濾取析出之沈澱物。以 真空乾燥機乾燥此沈澱物’得下述構造之醌二疊氮化合物 (a) 〇 -39- 200912544The olefinic resin is particularly useful when the side chain has an ethylenically unsaturated group addition Μ X 〈 olefinic acid resin. Containing a thermal free radical generator can produce -30-200912544 free radical species when plate 4 is hardened. Thus, the ethylenically unsaturated groups in the acrylic resin are crosslinked by the mutual bonding of the radicals, and the chemical resistance of the cured film is improved. The thermal radical generating agent is preferably an organic peroxide of the general formula (5). R17_〇—〇—R18 (5) R′ and R18 of the general formula (5) may be the same or different, and represent hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and carbon. Atomic number uo# thiol, an ester group having 2 to 30 carbon atoms. In general formula (5), the substituents, aryl, sulfhydryl and ester groups of R17 and R18 may have a substituent. The unsubstituted body may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, N-hexyl, cyclohexyl, n-decyl, 1,1-dimethylbutyl, etc. Specific examples of the aryl group include the following groups: phenyl, tolyl, p-hydroxyphenyl, 1-methyl-1 - phenethyl, benzyl, i methyl-1-3-(1-tert-butylperoxy-bromoethyl)phenethyl, etc. The specific examples of the fluorenyl group include the following groups: a mercapto group, a 2,2-dimethylpropenyl group, a 7+1-ethylpentyl group, a benzoinyl group, a 3-methylpentanyl group, etc. Specific examples of the ester group include the following groups: Base, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, tertiary butyl ester, s- Ester group, tertiary butylcyclohexyl ester group, etc. Among them, because of high decomposition temperature, no gas such as carbon dioxide is generated during hardening, and a base or an aryl group is preferred. The sulfhydryl group and the ester group may be decomposed and heated. The carbon dioxide gas generated remains in the film, and the film becomes brittle. Specific examples of the organic peroxide of the formula (5) include s objects, that is, 1,1-di(tertiary butylperoxy).环环院, 2,2 - 2 (4,4 -~ ' * ( —* Hlr*p -31- 200912544 Butoxy)cyclohexyl)propane, tertiary hexylperoxyisopropyl acetonate, Maleic acid peroxytributyl butyl ester, 3,5,5-trimethylhexanoic acid peroxytributyl butyl ester, lauric acid peroxy tertiary butyl ester, tertiary butyl peroxyisopropyl monocarbonate benzene Peroxytrihexyl formate, 2,5-dimethyl-2,5-bis(benzhydrylperoxy)hexyl, peroxybutylation of butyl, 2,2 -di (tertiary butanoperoxy Butane' benzoic acid tert-butyl butyl ester, n-butyl 4,4-di(tri-tert-butoxy) valerate, di(2-tri-peroxyisopropyl)benzene, dicumin Base peroxide, bis(tri-hexyl)peroxide 2,5-dimethyl-2,5- Di(tertiary butylperoxy)hexane, tertiary butyl cumyl peroxide, di(tertiary butyl peroxide), p-hydrazine hydroperoxide, 2,5·dimethyl-2,5_di ( Tertiary butylperoxy)hexyne-3·diisopropylbenzene hydrogen peroxide, hydrazine, 3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. A method of forming a cured film of the composition. The photosensitive composition of the present invention is applied onto a substrate substrate by a conventional method such as spin coating or slit, and is prebaked by a heating device such as a hot plate or an oven. 50-15 0 ° C for 30 seconds ~ 30 minutes, so that the film thickness after prebaking is better. After pre-baking, use a stepper, mirror projection aligner (MPA), parallel light ray aligner (pla), etc. UV-visible exposure machine to make the desired mask for 10~400 (The pattern is exposed to about mm2 (converted by the exposure amount of 365 nm). After exposure, the image is dissolved and exposed to obtain a positive pattern. The preferred method of development is immersion, dipping, dipping, etc. Seconds to 10 minutes. The developing solution can be a conventional alkali imaging solution. Specific examples include alkali metal hydroxides, carbonates, phosphates, citrates, borate and other inorganic bases, 2-diethylamine ethanol. , amines such as monoethanolamine and diethanolamine, tetramethylammonium hydroxide, choline, etc. -32-200912544 Ammonium salt, one or more aqueous solutions, etc. It is preferred to rinse with water after development, if necessary It can be dehydrated and dried and baked at 50 to 150 °C by means of a heating device such as a hot plate or an oven. Then, it is preferably subjected to fading exposure. The unreacted quinonediazide compound remaining in the film by fading exposure is carried out. When the light is decomposed, the transparency of the film is improved. The method of fading exposure is UV-visible using PLA or the like. The optical machine is used for the overall exposure of 100~20000〗/m2 (converted by the exposure of wavelength 365nm). The film is exposed by fading, if necessary, it is a hot plate, an oven, etc., at 50 to 1 50. °C for soft baking for 30 seconds to 30 minutes. Then, using a conventional heating device such as a hot plate oven, it is aged at 150 to 450 °C for about 1 hour to form a flattening TFT for display elements. A cured film such as an interlayer insulating film of a film or a semiconductor element, or a core or a cladding of an optical waveguide. The cured film produced by using the photosensitive composition of the present invention has a light transmittance of 90% at a wavelength of 400 nm at a film thickness of 3 #m. When the light transmittance is less than 90%, it is used as a flattening film for a TFT of a liquid crystal display device, and when the backlight passes through, it changes color, and the white color is yellowish. The film thickness at the wavelength of 400 nm is 3#. The light transmittance of m was determined by the following method: The composition was spin-coated on a TEMPAX glass plate at a random number of revolutions using a spin coater, and pre-baked for 2 minutes on a hot plate at 1 Torr. Then, the fading exposure system was used. PLA, the film is fully exposed to an ultra-high pressure mercury lamp for 30001/m2 (converted at a wavelength of 3 65 nm). The film was thermally cured at 220 ° C for 1 hour in an oven to prepare a cured film having a thickness of 3 m. The ultraviolet visible absorption spectrum of the cured film obtained by "MultiSpec- 1 500" manufactured by Shimadzu Corporation was determined. Transmittance at a wavelength of 400 nm -33- 200912544 This cured film is suitable for a planarizing film for a TFT, an interlayer insulating film for a semiconductor element, a core of an optical waveguide, a cladding material, and the like in a display element. A display element, a semiconductor element, or an optical waveguide material having a high heat resistance and a high transparency cured film as described above. It is particularly effective for use in a display element having a planarizing film for TFT, and an organic EL display element. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. Among the compounds used, the term "abbreviation" means the following. DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate EAA: ethyl acetate ethyl acetate GBL: r-butyrolactone polyoxane solution and solid content concentration of acrylic resin solution, polyoxyalkylene and acrylic resin The weight average molecular weight (Mw) and the acid hydrazine of the acrylic resin were determined as follows. (1) Solid content concentration 1 g of a polyoxyalkylene (acrylic resin) solution was weighed in an aluminum cup, and heated at 25 ° C for 30 minutes using a hot plate to evaporate the liquid component. The solid content of the heated aluminum cup was weighed to determine the solid content concentration of the polyoxyalkylene (acrylic resin) solution. (2) Weight average molecular weight The weight average molecular weight was determined by polystyrene conversion using GPC (Model 996 detector manufactured by Waters Co., Ltd., developing solvent tetrahydrofuran). (3) Acid bismuth-34- 200912544 A resin solution equivalent to 1 g of acrylic resin is weighed, and 0.1N potassium hydroxide (κ〇Η) aqueous solution is added dropwise to the solution, and the amount of K〇H required for neutralization is determined. Sour. Synthesis Example 1 Synthesis of Polyoxane Solution A three-necked flask of 500 ml was fed with methyltrimethoate 40.86 g (0.3 mol), phenyl dimethicone 118.98 g (0.6 mol), 2-(3, 4·epoxycyclohexyl)ethyltrimethoxy oxime 24.64g (〇.lm〇i), diacetone alcohol (hereinafter referred to as DAA) 171.38g, and added to a solution of 54g of cesium phosphate in water for 10 minutes under stirring at room temperature. 92 g (with respect to 5% by weight of the fed monomer) aqueous phosphoric acid solution. Thereafter, the flask was immersed in an oil bath at 40 ° C for 30 minutes, and then heated to 1 15 ° C in an oil bath over 30 minutes. After the temperature was raised for 1 hour, the temperature in the solution reached 100 ° C, and then the mixture was heated and stirred for 2 hours (internal temperature: 100 to 1 10 ° C) to obtain a polyoxane solution (a). Under heating and stirring, nitrogen was passed through 0.051 liter/nnn. In the reaction, by-product methanol and a total of 12 g of a water were distilled off. The solid concentration of the obtained polyoxane solution (a) was 40% by weight, and the weight average molecular weight of polyoxyalkylene was 65 00. The phenyl group content in the polyoxyalkylene is 60 mol% relative to the Si atom. Synthesis Example 2 Synthesis of Polyoxane Solution (b) A 500 ml three-necked flask was fed with 23.84 g (0.175 mol) of methyltrimethoxydecane, 99.15 g (0.5 mol) of phenyltrimethoxydecane, and 2-(3,4). -Epoxycyclohexyl)ethyltrimethoxysilane 12.32g (0.05mol), vermiculite particle DAA dispersion Quartron PL-2L-DAAC Fusang Chemical Industry Co., Ltd. 'Vermiculite particle concentration: 25% by weight) 66.09 g (0.275 mol based on the molar atom molar number), and DAA 63.04 g, and added 0.076 g of phosphoric acid dissolved in water 39.1 g in 10 minutes under stirring at room temperature (0.05-35 relative to the monomer fed in) 200912544 quantity %) aqueous phosphoric acid solution. The flask was then immersed in an oil bath at 40 ° C for 30 minutes and then warmed to 1 15 ° C over 30 minutes in an oil bath. After the temperature was raised for 1 hour, the internal temperature of the solution reached 100 ° C, and then the mixture was heated and stirred for 2 hours (internal temperature 100 to 1 1 ° C) to obtain a polyoxane solution (b). The mixture was heated to a flow of 0.051 L/min of nitrogen. In the reaction, methanol as a by-product and 85 g of a water mixture were distilled off. The solid concentration of the obtained polyoxane solution (b) was 46% by weight, and the weight average molecular weight of polyoxyalkylene was 8,000. The phenyl group content in the polyoxyalkylene is 50 mol% relative to the Si atom.合成 Synthesis Example 3 Synthesis of Polyoxane Solution (c) A three-necked flask of 500 ml was fed with methyltrimethoxyoxane 8 8.5 3 g (0.65 mol), phenyltrimethoxydecane 49.5 8 g (0.25 mol), 2- (3,4-epoxycyclohexyl)ethyltrimethoxy oxime 24.64g (0.1mol), and DAA 144.83g, added 0.081g of phosphoric acid dissolved in 54g of water in 10 minutes under stirring at room temperature (relative to the feed order) 0.05% by weight of aqueous phosphoric acid solution. The flask was then immersed in an oil bath at 40 ° C for 30 minutes and then warmed to 1 15 ° C over 30 minutes in an oil bath. After the temperature was raised for 1 hour, the temperature in the solution reached 1 〇〇 ° C, and then the mixture was heated and stirred for 2 hours (internal temperature 100 to 1 10 ° C) to obtain a polyoxane solution (c). The mixture was flowed with nitrogen at 0.051 liter/min under heating and stirring. In the reaction, by-product methanol and a total of 1,200 g of water were distilled off. The solid concentration of the obtained polyoxane solution (c) was 40% by weight, and the weight average molecular weight of polyoxyalkylene was 9 000. The phenol group content in the polyoxyalkylene is 25 mol% relative to the Si atom. Synthesis Example 4 Synthesis of Polyoxane Solution (d) A 500 ml three-necked flask was fed with 20.43 g (0.15 mol) of methyltrimethoxyoxane, phenyltrimethoxydecane 1 5 8.64 g (0-8 mol), 2-(3, 4--36- 200912544 Epoxy cyclohexyl)ethyltrimethoxy decane 12.32g (0.05mol), and DAA 1 7 9.54g, added with 54g of cesium phosphate dissolved in water for 10 minutes at room temperature. 3 8 3 g An aqueous solution of phosphoric acid (0.2% by weight relative to the monomer fed). The flask was then immersed in an oil bath at 40 ° C for 30 minutes and then warmed to 1 15 ° C over 30 minutes in an oil bath. After the temperature was raised for 1 hour, the internal temperature of the solution reached 100 ° C, and then the mixture was heated and stirred for 3 hours (internal temperature of 100 to 10 ° C) to obtain a polyoxane solution (d). The mixture was flowed with nitrogen at 0.051 liter/min under heating and stirring. In the reaction, by-product methanol and a total of 1,200 g of water were distilled off. The solid concentration of the obtained polyoxyalkylene solution (d) was 40% by weight, and the weight average molecular weight of polyoxyalkylene was 7,000. The phenol group content in the polyoxyalkylene is 80 mol% with respect to the Si atom. Synthesis Example 5 Synthesis of Acrylic Resin Solution (a) A 500 ml three-necked flask was fed with 2,2'-azobis(isobutyronitrile) 5 g, tertiary tricaptanol 5 g, and propylene glycol monomethyl ether acetate. (hereinafter referred to as PGMEA) 150g. Then, 30 g of methacrylic acid, 35 mg of benzyl methacrylate, and 35 tons of tricyclo [5.2.1.0''6] fluorene-8-ester methacrylate were fed, and the mixture was briefly stirred at room temperature, and the flask was replaced with nitrogen. The mixture was heated and stirred at 70 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, dimethylbenzylamine U and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 °C for 4 hours to obtain an acrylic resin solution (a). The obtained acrylic resin solution (a) had a solid content concentration of 43% by weight, and the acrylic resin had a weight average molecular weight of 10,600, acid hydride of 118 mgKOH/g, and an unsaturated equivalent of 1,090. Synthesis Example 6 Synthesis of Acrylic Resin Solution (b) A 500 ml three-necked flask was fed with 5 g of 2,2'-azobis(isobutyronitrile) and -37-200912544 PGMEA 150 g. Then, 27 g of methacrylic acid, benzyl methacrylate 38 §, and tricyclo [5.2.1.02'6] fluorene-8-ester 352 of methacrylic acid were fed, and the mixture was briefly stirred at room temperature, and then replaced with nitrogen in the flask. The mixture was stirred under heating at 70 ° C for 5 hours. Next, '15 g of methacrylic acid methacrylate, 1 g of dimethylbenzylamine, and 0,2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 ° C for 4 hours to obtain an acrylic resin solution ( b). The obtained acrylic resin solution (b) had a solid content concentration of 43% by weight, and the acrylic resin had a weight average molecular weight of 31,400, acid hydrate of 105 mgKOH/g > unsaturated equivalent of 1〇9〇. Synthesis Example 7 Synthesis of Acrylic Resin Solution (c) A 500 ml two-necked flask was fed with 5 g of 2,2'-azobis(isobutyronitrile) and 150 g of PGMEA. Then, 15 g of methacrylic acid, 45 g of methyl methacrylate, and 40 g of styrene were stirred at room temperature for a short period of time. After the flask was replaced with nitrogen, the mixture was heated and stirred at 70 ° C for 5 hours to obtain an acrylic resin solution (c). . The obtained acrylic resin solution (c) had a solid content concentration of 43% by weight, and the acrylic resin had a weight average molecular weight of 20,000, yttrium acid 97 mg K 〇 H / g, and an unsaturated equivalent 〇. Synthesis Example 8 Synthesis of Acrylic Resin Solution (d) A 500 ml three-necked flask was fed with 2 g of 2,2,-azobis(isobutyronitrile) and 50 g of PGMEA. Then, 30 g of methyl acrylate, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.02.6] 癸-8-ester methacrylate were added, and the mixture was stirred at room temperature for a short period of time. The mixture was heated and stirred at 70 ° C for 5 hours. Next, 15 g of propylene glycol methacrylate, lg of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C for 4 hours to obtain propylene. Acid resin solution (d). -38- 200912544 The obtained acrylic resin solution (d) had a solid content concentration of 43% by weight, an acrylic resin having a weight average molecular weight of 65,000' acid strontium 118 mgKOH/g, and an unsaturated equivalent of 1 090. Synthesis Example 9 Synthesis of Acrylic Resin Solution (e) A 500 ml three-necked flask was fed with 5 g of 2,2,-azobis(isobutyronitrile), 20 g of tridecahydrofuran, and 200 g of PGMEA. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.02'6] dec-8-ester of methacrylic acid were fed, and the flask was briefly stirred at room temperature, and then replaced with nitrogen. 'The mixture was heated and stirred at 70 ° C for 5 hours. Next, 'the obtained solution was added with methyl propyl sulfonate 15 g, dimethyl benzylamine lg, and p-methoxyphenol oxime 2 g, and heated at 90 ° C for 4 hours to obtain an acrylic resin solution. (e). The obtained acrylic resin solution (e) had a solid content concentration of 43% by weight, an acrylic resin having a weight average molecular weight of 4500, a strontium acid of 118 mgKOH/g, and an unsaturated equivalent of 1,090. Synthesis Example 10 Synthesis of quinonediazide compound U) 21.13 g (0.05 mol) of trisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g of 5-quinonediazidesulfonic acid chloride were dissolved under a dry nitrogen stream. (0.14 mol) was 450 g in 1,4-dioxane and kept at room temperature. Here, 15.58 g (0.154 mol) of a dife fe blended with 50 g of 1,4 - D broth was dropped, but the internal temperature was not more than 35 °C. After the completion of the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate which precipitated was then collected by filtration. The precipitate was dried by a vacuum dryer to obtain a quinonediazide compound of the following structure (a) 〇 -39- 200912544

合成例11 醌二疊氮化合物（b)之合成 乾燥氮氣流下，溶解TnsP-HAP(商品名’本州化學工 業（股）製）15.32g(0.05mol)與 5-醌二疊氮磺酸氯 26.87g(0.1mol)於1，4-二噚烷450g，保持於室溫。於此，滴 入與1，4-二曙烷50g混合之三乙胺11.13g(0.11mol)但不使 系內溫度達35°C以上。滴完後於30°C攪拌2小時。將三乙 胺鹽過濾，將濾液注入水中。然後濾取析出之沈澱物。以 真空乾燥機乾燥此沈澱物，得下述構造之醌二疊氮化合物 (b)。Synthesis Example 11 Synthesis of quinonediazide compound (b) Under dry nitrogen gas flow, dissolved in TnsP-HAP (trade name: manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-quinonediazidesulfonic acid chloride 26.87 g (0.1 mol) in 450 g of 1,4-dioxane was kept at room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, but the internal temperature was not higher than 35 °C. After the completion of the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate which precipitated was then collected by filtration. The precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (b) having the following structure.

-pdrN2H S〇2-pdrN2H S〇2

I 2.0 1.0 醌二疊氮材料（b) 合成例12 聚矽氧烷溶液（e)之合成 於 5 00ml之三口燒瓶饋入甲基三甲氧矽烷 54_48g(0.4mol)、苯基三甲氧矽烷 99.15g(0,5mol)、2-(3,4-I 2.0 1.0 醌Diazide material (b) Synthesis Example 12 Synthesis of polyoxane solution (e) In a 500 ml three-necked flask, methyltrimethoxyoxane 54-48 g (0.4 mol) and phenyltrimethoxydecane 99.15 g were fed. (0,5mol), 2-(3,4-

環氧環己基）乙基三甲氧矽烷24.64g(0.1mol)、及DAA -40- 200912544 16 3.35g，室溫攪拌下以10分鐘添加溶解於水54g之磷酸 0.5 3 5 g(相對於饋入之單體的0.3重量％)之磷酸水溶液。然 後將燒瓶浸於40°C之油浴攪拌30分鐘後，藉油浴經30分 鐘升溫至115°C。開始升溫1小時後溶液內溫達l〇〇°C，之 後加熱攪拌2小時（內溫100〜110 °C )，得聚矽氧烷溶液（e)。 加熱攪拌中以氮0.051升/min流過。反應中餾出副產物甲 醇、水合計1 2 0 g。 得到之聚矽氧烷溶液（e)的固體成分濃度係40重量％> ’ 聚矽氧烷之重量平均分子量6000。聚矽氧烷中苯基含有率 係相對於Si原子50莫耳％。 合成例13 聚矽氧烷溶液（f)之合成 於 5 00ml 之三口燒瓶饋入甲基三甲氧矽烷 54.48g(0.4mol)、苯基三甲氧矽院 99.15g(0.5mol)、2-(3,4-環氧環己基）乙基三甲氧矽烷 24.64g(0.1mol)、及 DAA 1 63.80g，室溫攪拌下以10分鐘添加溶解於水54g之磷酸 0.089g(相對於饋入之單體的〇.〇5重量％)之磷酸水溶液。然 後將燒瓶浸於4 0 °C之油浴攪持3 0分鐘後，藉油浴經3 0分 鐘升溫至1 1 5 °C。開始升溫1小時後溶液內溫達1 0 0 °C，之 後加熱攪拌2小時（內溫1〇〇~1 l〇°C ) ’得聚矽氧烷溶液（f)。 加熱攪拌中以氮0.05 1升/nun流過。反應中餾出副產物甲 醇 '水合計丨1 〇 g。 得到之聚矽氧烷溶液（0的固體成分濃度係42重量％， 聚矽氧烷之重量平均分子量4 0 00。聚矽氧烷中苯基含有率 係相對於S1原子5 0莫耳％。 合成例1 4 聚砂氧院溶液（g)之合成 -41- 200912544Epoxycyclohexyl)ethyltrimethoxy oxime 24.64g (0.1mol), and DAA-40-200912544 16 3.35g, added 0.5g 5 g of phosphoric acid dissolved in water 54g (with respect to feeding) in 10 minutes with stirring at room temperature A 0.3% by weight aqueous solution of phosphoric acid of the monomer. Then, the flask was immersed in an oil bath of 40 ° C for 30 minutes, and then heated to 115 ° C in an oil bath for 30 minutes. After the temperature was raised for 1 hour, the internal temperature of the solution reached 10 ° C, and then the mixture was heated and stirred for 2 hours (internal temperature of 100 to 110 ° C) to obtain a polyoxane solution (e). The mixture was flowed with nitrogen at 0.051 liter/min under heating and stirring. In the reaction, by-product methanol and a total of 1,200 g of water were distilled off. The solid concentration of the obtained polyoxane solution (e) was 40% by weight > The weight average molecular weight of the polyoxyalkylene was 6000. The phenyl content in the polyoxyalkylene is 50 mol% relative to the Si atom. Synthesis Example 13 Synthesis of Polyoxane Solution (f) In a 500 ml three-necked flask, 54.48 g (0.4 mol) of methyltrimethoxyoxane, 99.15 g (0.5 mol) of phenyltrimethoxysulfonate, and 2-(3) were fed. , 4-epoxycyclohexyl)ethyltrimethoxy oxime 24.64g (0.1mol), and DAA 1 63.80g, added 0.089g of phosphoric acid dissolved in 54g of water in 10 minutes under stirring at room temperature (relative to the monomer fed in) 〇.〇5 wt%) aqueous phosphoric acid solution. Then, the flask was immersed in an oil bath at 40 ° C for 30 minutes, and then heated to 1 15 ° C by means of an oil bath for 30 minutes. After the temperature was raised for 1 hour, the temperature in the solution reached 100 ° C, and then the mixture was heated and stirred for 2 hours (internal temperature: 1 〇〇 to 1 l 〇 ° C) to obtain a polyoxane solution (f). Under heating and stirring, nitrogen was passed through 0.05 1 liter/nun. In the reaction, the by-product methanol 'Hydration 丨 1 〇 g was distilled off. The obtained polyoxane solution (0 has a solid content concentration of 42% by weight, and polypyrene has a weight average molecular weight of 400%. The polyoxyalkylene has a phenyl content of 50% by mole relative to the S1 atom. Synthesis Example 1 Synthesis of polyoxalate solution (g) -41- 200912544

於 500ml之三口燒瓶饋入甲基三甲氧5夕烷 68.10g(0.5mol)、苯基二甲氧砂院 99.15g(0.5mol)、及 DAA 14 9.9U，室溫攪拌下以1〇分鐘添加溶解於水54§之磷酸 0.502g(相對於饋入之單體的0.3重量％)之磷酸水溶液。然 後將燒瓶浸於40 r之油浴攪拌30分鐘後，藉油浴經30分 鐘升溫至1 1 5 t。開始升溫1小時後溶液內溫達1 00°c ’之 後加熱攪拌2小時（內溫1 00~ 1 1 0°C ) ’得聚矽氧烷溶液（S)。 加熱攪拌中以氮〇.〇5 1升/min流過。反應中餾出副產物甲 、 醇、水合計1 2 0 g。 得到之聚矽氧烷溶液（g)的固體成分濃度係40重量％ ’ 聚矽氧烷之重量平均分子量6500。聚矽氧烷中酚基含有率 係相對於S i原子5 0莫耳％。 合成例15醌二疊氮化合物（c)之合成 乾燥氮氣流下，溶解Ph-cc-AP-MF(商品名’本州化學 工業（股）製）15.32g(0.05mol)與 5-醌二疊氮磺酸氯 3 7.62g(0.14mol)於1，4-二噚烷450g，保持於室溫。於此， 滴入與1,4-二嗶烷50g混合之三乙胺15.58g(0.154mol)但不 使系內溫度達35°C以上。滴完後於30°C攪拌2小時。將三 乙胺鹽過濾，將濾液注入水中。然後濾取析出之沈澱物。 以真空乾燥機乾燥此沈澱物，得下述構造之醌二疊氮化合 物（c)。 -42- 200912544The 500 ml three-necked flask was fed with methyltrimethoxy-5-pentane 68.10 g (0.5 mol), phenyl dimethicone 99.15 g (0.5 mol), and DAA 14 9.9 U, and added at room temperature for 1 minute. An aqueous phosphoric acid solution dissolved in 0.502 g of phosphoric acid (0.3% by weight relative to the fed monomer) was dissolved in water. The flask was then immersed in a 40 r oil bath for 30 minutes and then warmed to 1 15 t by means of an oil bath over 30 minutes. After the temperature was raised for 1 hour, the internal temperature of the solution reached 100 °c', and the mixture was heated and stirred for 2 hours (internal temperature of 00 to 110 °C) to obtain a polyoxane solution (S). The mixture was heated and stirred with nitrogen 〇.〇5 1 liter/min. In the reaction, by-products of methanol, alcohol and water were distilled off to 120 g. The solid concentration of the obtained polyoxane solution (g) was 40% by weight of the polyoxyalkylene having a weight average molecular weight of 6,500. The phenol group content in the polyoxyalkylene is 50% by mole relative to the S i atom. Synthesis Example 15 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, 15.32 g (0.05 mol) of Ph-cc-AP-MF (trade name: manufactured by Honshu Chemical Industry Co., Ltd.) and 5-quinonediazide were dissolved. Sulfonic acid chloride 3 7.62 g (0.14 mol) in 450 g of 1,4-dioxane was kept at room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, but the internal temperature was not higher than 35 °C. After the completion of the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate which precipitated was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide (c) of the following constitution. -42- 200912544

醌二疊氮材料Bismuth azide material

Η 2 0· 實施例1 於黃燈下混合合成例1中得之聚矽氧烷溶液 (a)19.62g、合成例6中得之丙烯酸樹脂溶液（b) 7 8 2 g、合成 例1 0中得之醌二疊氮化合物（a) 1 · 0 1 g、矽烷耦合劑 KBM202ss(二苯基二甲氧矽烷，商品名，信越化學工業（股） 製）0.11g、KBM303(2-(3,4-環氧環己基）乙基三甲氧矽烷，商 品名’信越化學工業（股）製）〇.llg、N-三級丁基-3-(3-三甲 氧丙基）琥珀醯亞胺〇.〇6g、溶劑DAA 5.10g、及PGMEA 16. 17g ’攪拌成均勻溶液後，以0.45 // m之濾器過濾，得組 成物丨。聚矽氧烷與丙烯酸樹脂的混合比率係聚矽氧烷/丙 烯酸樹脂=70/3 0。 組成物1使用旋塗機（MIKASA(股）製1H- 3 60S)以任意 轉數旋塗於TEMPAX玻璃板（旭技玻璃板（股）製）、矽晶圓、 及成膜有氮化矽l〇〇nm左右之OA-10玻璃板（日本電氣硝子 (股）製）基板（以下簡稱SiN基板）後，使用熱板（大日本製網 (股）製SCW-636)以100°C預烘烤2分鐘’製作膜厚3/zm之 膜。所製作之膜使用平行光線光罩對準曝光器（以下簡稱 PLAHCANON(股）製PLA-5 0 1 F) ’以超高壓水銀燈介著感度 測定用之灰階光罩作圖案曝光後’使用自動顯像裝置（滝沢 -43- 200912544 產業（股）製AD-2000)以2.38重量％氫氧化四甲銨水溶液 ELM-D(商品名，三菱瓦斯化學（股）製）淋洗顯像80秒’其 次以水淋洗3 0秒。然後’褪色曝光，使用P L A (C A Ν Ο N (股） 製 P L A - 5 0 1 F)於膜全面以超高壓水銀燈作 3 0 0 (H / m2 (波長 3 65 nm的曝光量換算）之曝光。然後，使用熱板於11CTC軟 烘烤2分鐘，其次使用烘箱（TABAI ESPEC (股）製IHPS-222) 於空氣中以220°C熟化1小時製作硬化膜。 感光特性及硬化膜特性之評估結果如表2。表中之評 估係以如下方法進行。下述 （4)、（5)、（6)、（7)、（11)之評 估係用矽晶圓，（9)之評估係用TEMPAX玻璃板，（10)之評 估係用SiN基板。 (4) 膜厚測定 使用Lambda Ace STM-602(商品名，大曰本SCREEN製） 以折射率1 . 5 0作測定。 (5) 殘膜率之算出 殘膜率係由下式算出。 殘膜率（％)=顯像後之未曝光部膜厚+預烘烤後之膜厚χ1〇〇。 (6) 感度之算出 曝光、顯像後，以1對1之寬度形成1 0 V m的線條及 間隔圖案之曝光量（下稱最適曝光量）爲感度。 (7) 解析度之算出 以最適曝光量下顯像後之最小圖案尺寸爲顯像後解丰斤 度，熟化後之最小圖案尺寸爲熟化後解析度。 (8) 減重率 將組成物約100mg放入鋁池，使用熱重量測定裝置 -44- 200912544 (TGA-50，島津製作所（股）製）’在氮氛圍中以升溫速度10 °C /分鐘加熱至3 00°C，如此加熱硬化1小時’然後以升溫 速度l〇r /分鐘加熱至400°C時’測定減重率。測定達300 r時之重量，並測定達400°C時之重量’求出與300 °C時的 重量之差，求出減少之重量分率，爲減重率。 (9)透光率之測定 使用M u 11 i S P e c - 1 5 0 0 (商品名，島津製作所（股）製），首 先僅以Τ Ε Μ P A X玻璃板測定，以其紫外可見吸收光譜爲參 考基準。其次於TEMPAX玻璃板上形成組成物之硬化膜（不 作圖案曝光），此樣本以單光束測定，求出每3 // m之波長 4 OOnm的透光率，以與參考基準之差異爲透光率。 (1 0)密著性之評估 於SiN基板上形成組成物之硬化膜（不作圖案曝光）， 於此硬化膜上垂直豎立附環氧樹脂的短鋁棒（QUAD GROUP 公司製），使用烘箱在空氣中以20 0°C加熱30分鐘使短鋁棒 黏著於硬化膜。然後，使用TENSIRON RTM-100(商品名， 0 r i e n t e c公司（股）製），以拉伸速度5 m m / m i η相對於硬化膜 垂直拉伸短鋁棒，測定硬化膜/基板界面剝離時之強度。 (1 1)耐藥物性之評估（TO Κ-106處理之膜減量評估） 於矽晶圓上形成組成物之硬化膜，將此樣本浸於加熱 至70°C的TOK-106(商品名，東京應化工業（股）製）10分鐘 後，以水淋洗5分鐘。由此處理之膜厚減量評估耐藥物性。 實施例2〜1 2，比較例1 ~ 4 依表1之組成，如同組成物1製造組成物2 ~ 1 6。用作 丙烯酸樹脂的Ripoxy SPCR-10XC商品名，昭和高分子（股） -45- 200912544 製）係甲基丙烯酸/甲基丙烯酸苯甲酯/甲基丙烯酸三環癸酯 共聚物之甲基丙烯酸環氧丙酯加成物（重量平均分子量： 1 73 00，酸値：109mgKOH/g)，Ri p ox y S PC R - 6 X (商品名，B召 和高分子（股）製）係甲基丙烯酸/甲基丙烯酸苯甲酯/甲基丙 烯酸三環癸酯共聚物之甲基丙烯酸環氧丙酯加成物（重量 平均分子量：10700，酸値：127mgKOH/g)。用作矽烷耦合 劑之KBM403 (商品名，信越化學工業（股）製），用作交聯劑 之 EPIKOTE 828 (商品名，JAPAN EPOXY RESIN(股）製）’ NIKALAC MX-270、NIKALAC MW-30HM(商品名，Sanwa Chemical (股）製）係構造如下之化合物。用作交聯促進劑之 MC〇PDMS-TFMS(三新化學工業（股）製）係三氟甲院擴酸4-甲氧羰氧苯基二甲銃’ WPAG-469(商品名，和光純藥工業（股） 製）係全氟丁烷磺酸4-甲苯基二苯鏑之20%PGMEA溶液，用 作增感劑之DPA(商品名，川崎化成工業（股）製）係9, ίο-二 丙蒽。Η 2 0· Example 1 19.62 g of the polyoxoxane solution (a) obtained in Synthesis Example 1 and the acrylic resin solution (b) 7 8 2 g obtained in Synthesis Example 6 were synthesized under a yellow lamp, Synthesis Example 1 0得中醌醌 azide compound (a) 1 · 0 1 g, decane coupling agent KBM202ss (diphenyl dimethoxy decane, trade name, Shin-Etsu Chemical Co., Ltd.) 0.11g, KBM303 (2-(3) , 4-epoxycyclohexyl)ethyltrimethoxy decane, trade name 'Shin-Etsu Chemical Co., Ltd.') 〇.llg, N-tertiary butyl-3-(3-trimethoxypropyl) succinimide 〇.〇6g, solvent DAA 5.10g, and PGMEA 16.17g ' After stirring into a homogeneous solution, it was filtered through a 0.45 // m filter to obtain a composition 丨. The mixing ratio of polyoxyalkylene to acrylic resin is polyoxyalkylene/acrylic resin = 70/30. The composition 1 was spin-coated on a TEMPAX glass plate (manufactured by Asahi Glass Co., Ltd.) using a spin coater (manufactured by MIKASA Co., Ltd., 1H-360S), a tantalum wafer, and a tantalum nitride film. l OA-10 glass plate (made by Nippon Electric Glass Co., Ltd.) substrate (hereinafter referred to as SiN substrate), using a hot plate (SCW-636 manufactured by Dainippon Co., Ltd.) at 100 ° C Bake for 2 minutes' to make a film with a film thickness of 3/zm. The film produced is a parallel light ray aligning exposer (hereinafter referred to as PLAAHCANON (PLA-5 0 1 F). 'Using a high-pressure mercury lamp for pattern exposure with a gray scale mask for sensitivity measurement' The developing device (AD-2000 manufactured by 滝沢-43-200912544, Ltd.) was washed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 80 seconds. Next, rinse with water for 30 seconds. Then 'faded exposure, using PLA (CA Ν Ο N (share) PLA - 5 0 1 F) in the membrane full of ultra-high pressure mercury lamp for 300 (H / m2 (wavelength 3 65 nm exposure conversion) exposure Then, it was soft baked at 11 CTC for 2 minutes using a hot plate, and then a cured film was formed by curing in air at 220 ° C for 1 hour in an oven (TABAI ESPEC (IHPS-222).) Evaluation of photosensitivity and properties of the cured film The results are shown in Table 2. The evaluation in the table was carried out as follows. The evaluations of (4), (5), (6), (7), and (11) below were used for the evaluation of the wafer, (9) The TEMPAX glass plate and the evaluation of (10) were made of SiN substrate. (4) The film thickness was measured using Lambda Ace STM-602 (trade name, manufactured by Otsuka SCREEN) with a refractive index of 1.50. The residual film ratio is calculated by the following formula: Residual film rate (%) = film thickness of unexposed portion after development + film thickness after prebaking χ 1 〇〇 (6) Calculation of sensitivity, exposure After the development, the exposure amount (hereinafter referred to as the optimum exposure amount) of the line and the interval pattern of 10 V m formed by the width of one to one is the sensitivity. (7) The calculation of the resolution is optimal. The minimum pattern size after development under light quantity is the resolution after development, and the minimum pattern size after aging is the resolution after aging. (8) Weight loss rate: About 100 mg of the composition is placed in an aluminum bath, using thermogravimetry Device-44- 200912544 (TGA-50, manufactured by Shimadzu Corporation) "heated to 300 °C at a heating rate of 10 °C / min in a nitrogen atmosphere, so heat hardened for 1 hour" and then at a heating rate l〇r When the temperature is heated to 400 ° C, the weight loss rate is measured. The weight at 300 r is measured, and the weight at 400 ° C is measured to determine the difference from the weight at 300 ° C. The rate is the weight loss rate. (9) The transmittance is measured using M u 11 i SP ec - 1 5 0 0 (trade name, manufactured by Shimadzu Corporation), and is first measured only on the Τ Ε Μ PAX glass plate. The UV-visible absorption spectrum was used as a reference. Secondly, the cured film of the composition was formed on the TEMPAX glass plate (no pattern exposure). The sample was measured by a single beam to obtain a transmittance of 4 OOnm per 3 // m wavelength. , the difference from the reference datum is the transmittance. (10) Evaluation of the adhesion to the SiN base A cured film of the composition (without pattern exposure) is formed thereon, and a short aluminum bar (manufactured by QUAD GROUP Co., Ltd.) with an epoxy resin vertically erected on the cured film is heated in an air at 20 ° C for 30 minutes in an oven to make it short. The aluminum rod was adhered to the cured film, and then a short aluminum rod was drawn perpendicularly to the cured film at a tensile speed of 5 mm / mi η using a TENSIRON RTM-100 (trade name, manufactured by 0 rientec Co., Ltd.) to measure the cured film. / Strength at the time of peeling off the substrate interface. (1 1) Evaluation of drug resistance (film reduction evaluation by TO Κ-106 treatment) A cured film of a composition was formed on a wafer, and the sample was immersed in TOK-106 (trade name, heated to 70 ° C, After 10 minutes, the Tokyo Chemical Industry Co., Ltd. was rinsed with water for 5 minutes. The film thickness reduction thus treated was evaluated for drug resistance. Examples 2 to 1 2, Comparative Examples 1 to 4 According to the composition of Table 1, compositions 2 to 16 were produced as in Composition 1. Ripoxy SPCR-10XC, which is used as an acrylic resin, is a methacrylic acid ring of methacrylic acid/benzyl methacrylate/tricyclodecyl methacrylate copolymer. Oxypropyl acrylate adduct (weight average molecular weight: 1 73 00, acid hydrazine: 109 mg KOH/g), Ri p ox y S PC R - 6 X (trade name, B-call and polymer) Acrylic acid/methacrylic acid methacrylate/trimethyl methacrylate methacrylate propylene glycol methacrylate adduct (weight average molecular weight: 10700, acid hydrazine: 127 mg KOH/g). KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) used as a decane coupling agent, and EPIKOTE 828 (trade name, manufactured by JAPAN EPOXY RESIN Co., Ltd.) used as a crosslinking agent. NIKALAC MX-270, NIKALAC MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) is a compound having the following structure. MC〇PDMS-TFMS (made by Sanshin Chemical Industry Co., Ltd.) used as cross-linking accelerator is a trifluoromethyl-acid-extended 4-methoxycarbonyloxyphenyl dimethyl hydrazine' WPAG-469 (trade name, and light pure) Pharmaceutical Industry Co., Ltd. is a 20% PGMEA solution of 4-tolyldiphenyl sulfonate perfluorobutanesulfonate, and is used as a sensitizer DPA (trade name, manufactured by Kawasaki Chemical Industry Co., Ltd.) 9, ίο - Dipropene.

-46- 200912544 〇〇 蘅 〇 m m 聆 蝴 a 瞇 皿 1 1 銳 U 豳 增感劑 DPA ·· 0.04g _1 DPA 0.04g DPA : 0.05g DPA ： 0.06g DPA ： 0.05g 蘅 S ο οα 0-67g _1 0.66g aa 〇 CO ).〇Bg ).16g ).14g m m 1 8 $ •«a- 2 Η Η Q 1 ο ϊ ό i ό < % Q υ s s S ο i 0 Γ·) I .AC MX 0.22g ^ ou S P s -Ξ? ο 〇 υ fN 5 α. ω m m m m 爾 矽烷耦合劑 ^ »#S 00 Ού 3 M ο -： ffi- 〇 ·. "J ^ 爸〇gB Is^I = i；|s Ο 5 B- ° 二…".丨狴 gsr：^ 產5 bs 乂 α鸾辉 ，a KBM403 ： O.Olg οβ ο Ί： ffi- ° s〇〇s § 2二嫿 戔 sfc·® Ο ^ ffi- ° ·· .. Hi <w 3 S ό w Ρ亡s μ 乂鸾饀 KBM202ss ： 0. KBM303 ： 0.2 ο ΓΛ i ΚΒΜ303 ： 0.1 KBM202ss ： 0. KBM303 · 0.1 KBM202ss ： 0. ΚΒΜ303 : 0.1 KBM202ss ： 0. ΚΒΜ303 ： 0.1 |scl |Ιη| 2 ^輩s KBM202ss 0. KBM303 : 0.1 KBM202ss ： 0.. KBM303 ： 0.3' KBM303 : 0.2 III ^ U1 ^ HI ^ II] * lit ® z. z. z z 槭 1? a 1? 1? 1? Ί5 1? 1? 3· 1 ϊ f I I Μ S f I I I 4η in <□ <η . <!α <|D 4U An <u <η 4c <1〇 <Ja <a <D <0 氮化 l.Olg mz： m — 氮化 l.OOg 氮化 1.32g 氮化 l.OOg 氮化 1.10g 氮化 1.41g m 2 氮化 0.80g 氣化 t.Olg 氮化. 1.60g 氮化· 1.95g 氣化· 1.42g m^· m m _ m 豳 m 豳 m 幽 m 豳 m i 1 m 1 1 m l I m ι! I ! m 1 1 m Μ 鼷 1 1 m 11 m 11 鼷 ι 1 m l 1 鼷 1 1 m i 1 m tl m 11 魅 蘅 5.10g ：16.i7g 8.83g ：11.64g 1.88g 11.98g ：8.66g 1.88g 5.85g ：14.32g 3.75g 6.78g :10.53g 3.75g 5.22g :15.68g | 5.32g :15.72g S.76g , :ll.58g 1.88g ! 8.83g :9.62S 1.88g 12.80g 1 :3.75g ! 7.50g 1.74g :19.1½ 15.27g ·· 6.00g 1.88g :27.15g lllg 7.86g 7.69g ：11.69g 1.88g 8.48g :5.34g DAA ： PGMHA DAA ： PGMEA EAA ： DAA ： PGMEA EAA ： DAA ： PGMEA GBL : DAA ： PGMEA GBL ： DAA ： PGMEA DAA : PGMEA DAA PGMEA EAA ： DAA ： PGMEA EAA : DAA : PGMEA GBL : DAA : PGMEA 1 DAA : PGMHA 丨 EAA : PGMEA 1 DAA : .PGMEA DAA ： PGMHA EAA : DAA : PGMEA Μ 趑 雲 o 8 8 嘁 B o O O o 3 § δ g 0 δ 1? -75 m bW 鋰屮 魅5Γ 樂 — 1 8 n 瘈S dm 〇〇 〇 靈g $ 癭S' i -§ UCC σ' O ISI 瘍S Slr^l 髮 - i^I m - m 8 1 s 抑 s Iff 1 e t M§ ΰπ OO W~i U~i ag 〇j m 觸脂溶液( I4.50g lw=4500) % 8 m is s y 柴 - S 8 Ϊ5 ^ 3 |3! ySPCR-]〇； 6.97g w= 17300) cy SPCR-6> 14.2¾ w=10700) ipoxySPCR-10： 10.99g (Mw= 17300) 歧A 趙 s 发 一 趙 s 发 一 寧 2 褰 — 趙 s 发 w 魅 s 逻 - 魅 2 趙 s 发 - 魅 2 发β 瞄 2 链 2 趙 s 想 2 逻 一· § S .a. — 1 1 r r IE E E： E： E ίΕ： E r E： ai 1?冢 3 1 3 1 £ 妥 S I 3 g @ g s 1 c 茨 1» ψ 1爷 s对稱· 塔沒哔 - <ro ^ ¥ 逆2胼 hi 嘁00邻 f ? -¾ ? 锭3褂 •g< S "t J|E 铤哭# 铵，褂 -¾ «ι 链s肼 樂 s id % m 您 iA m ? g占蘇 ·)= 11 疫泛褂 |s 1¾ 减一如 祕一如 igp 挪: lif. Sg ]r ilifr — Hfi? — <r〇 逻5俾: 减〜<ra 贼〜<r〇 1» ~ 40 蹈5腺 嘁〜如 给蝴 诠 m P _ 訟蝴 訟 n % 域 诠 m 洽蝴 訟 m 訟 η 洽蝴 訟 m 跋 % 踩 u 踩 % 联 % 嵌 % 跋 % tv 货 — (N f*~l Ό v~ oo CK 〇 二 «r Ό m 芻 链 链 链 琮 m 璀 200912544-46- 200912544 〇〇蘅〇mm Listening a dish 1 1 Sharp U 豳 sensitizer DPA ·· 0.04g _1 DPA 0.04g DPA : 0.05g DPA : 0.06g DPA : 0.05g 蘅S ο οα 0-67g _1 0.66g aa 〇CO ).〇Bg ).16g ).14g mm 1 8 $ •«a- 2 Η Η Q 1 ο ϊ ό i ό < % Q υ ss S ο i 0 Γ·) I .AC MX 0.22g ^ ou SP s -Ξ? ο 〇υ fN 5 α. ω mmmm 矽 耦合 coupling agent ^ »#S 00 Ού 3 M ο -: ffi- 〇·. "J ^ 爸〇gB Is^I = i;|s Ο 5 B- ° two...".丨狴gsr:^ 5 bs 乂α鸾辉, a KBM403 : O.Olg οβ ο Ί: ffi- ° s〇〇s § 2 二婳戋sfc ·® Ο ^ ffi- ° ·· .. Hi <w 3 S ό w Ρ s μ 乂鸾饀KBM202ss : 0. KBM303 : 0.2 ο ΓΛ i ΚΒΜ303 : 0.1 KBM202ss : 0 KBM303 · 0.1 KBM202ss : 0. ΚΒΜ303 : 0.1 KBM202ss : 0. ΚΒΜ303 : 0.1 |scl |Ιη| 2 ^ s KBM202ss 0. KBM303 : 0.1 KBM202ss : 0.. KBM303 : 0.3' KBM303 : 0.2 III ^ U1 ^ HI ^ II] * lit ® zz zz Maple 1? a 1? 1? 1? Ί5 1? 1? 3· 1 ϊ f II Μ S f III 4η in <□ <η . <!α <|D 4U An <u <η 4c <1〇<Ja <a <D <0 nitriding l.Olg mz: m - nitriding l.OOg nitriding 1.32g nitriding l.OOg nitriding 1.10g Nitriding 1.41gm 2 Nitriding 0.80g Gasification t.Olg Nitriding. 1.60g Nitriding · 1.95g Gasification · 1.42gm^· mm _ m 豳m 豳m 幽m 豳mi 1 m 1 1 ml I m ι! I ! m 1 1 m Μ 鼷1 1 m 11 m 11 鼷ι 1 ml 1 鼷1 1 mi 1 m tl m 11 Charm 5.10g :16.i7g 8.83g :11.64g 1.88g 11.98g :8.66 g 1.88g 5.85g : 14.32g 3.75g 6.78g : 10.53g 3.75g 5.22g : 15.68g | 5.32g : 15.72g S.76g , :ll.58g 1.88g ! 8.83g : 9.62S 1.88g 12.80g 1 : 3.75g ! 7.50g 1.74g : 19.11⁄2 15.27g ·· 6.00g 1.88g :27.15g lllg 7.86g 7.69g :11.69g 1.88g 8. 48g : 5.34g DAA : PGMHA DAA : PGMEA EAA : DAA : PGMEA EAA : DAA : PGMEA GBL : DAA : PGMEA GBL : DAA : PGMEA DAA : PGMEA DAA PGMEA EAA : DAA : PGMEA EAA : DAA : PGMEA GBL : DAA : PGMEA 1 DAA : PGMHA 丨EAA : PGMEA 1 DAA : .PGMEA DAA : PGMHA EAA : DAA : PGMEA 趑 趑 cloud o 8 8 嘁B o OO o 3 § δ g 0 δ 1? -75 m bW Lithium enchantment 5Γ Le — 1 8 n 瘈S dm 〇〇〇灵g $ 瘿S' i -§ UCC σ' O ISI SS Slr^l hair - i^I m - m 8 1 s s Iff 1 et M§ ΰπ OO W~ i U~i ag 〇jm lipophobic solution ( I4.50g lw=4500) % 8 m is sy Chai - S 8 Ϊ5 ^ 3 |3! ySPCR-]〇; 6.97gw= 17300) cy SPCR-6> 14.23⁄4 w=10700) ipoxySPCR-10: 10.99g (Mw= 17300) AA Zhao s 发一赵 s 发一宁2 褰— Zhao s hair w charm s Logic - Charm 2 Zhao s hair - Charm 2 hair β aim 2 chain 2 Zhao s want 2 Logic 1 § S .a. — 1 1 rr IE EE: E: E ίΕ: E r E: ai 1?冢3 1 3 1 £ Pro SI 3 g @ gs 1 c 茨1» ψ 1 s symmetry · tower no - <ro ^ ¥ Reverse 2胼hi 嘁00邻 f ? -3⁄4 ? Ingot 3褂•g< S "t J|E 铤哭# Ammonium, 褂-3⁄4 «ι Chain 肼 s s id % m iA m ? g占苏·)= 11 泛泛褂|s 13⁄4 minus one as secret as igp: lif. Sg ]r ilifr — Hfi? — <r〇 俾 5俾: minus ~<ra thief~ <r〇1» ~ 40 5 嘁 嘁 如 如 如 如 如 如 m m m m m m m m m m % % % % % % % % % 蝴 洽 洽 洽 洽 蝴 洽 蝴 蝴 蝴 蝴 蝴 蝴 蝴 蝴 蝴 蝴 洽 洽 洽 蝴 蝴 蝴Tv goods — (N f*~l Ό v~ oo CK 〇二«r Ό m 刍 chain chain 琮m 璀200912544

H2 H2CH H3-CHH3 CLCο1,01o -o C3 H C I H2cH2 H2CH H3-CHH3 CLCο1,01o -o C3 H C I H2c

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KBM403 h3c-o-h2%An，ch2-o-ch3 H3C-O-H2C Y ch2-o-ch3 ' o NIKALAC MX-270 EPICOAT 828 h3c-o-h2c、 ，ch2-o-ch3 ,N N N、 h3c-o-h2c γ if ch2-o-ch3 ΝγΝKBM403 h3c-o-h2%An,ch2-o-ch3 H3C-O-H2C Y ch2-o-ch3 ' o NIKALAC MX-270 EPICOAT 828 h3c-o-h2c, ,ch2-o-ch3 ,NNN, h3c- O-h2c γ if ch2-o-ch3 ΝγΝ

AA

H3C-O-H2C CH2-O-CH3 NIKALAC MW-30HM 使用得到之各組成物，如同實施例1評估各組成物。 唯於實施例2、3、5、8、9、1 1及比較例3、4之評估，顯 像係以0.4重量％氫氧化四甲銨水溶液（ELM-D以水稀釋者） 淋洗顯像80秒爲之。 結果如表2。 -48- 200912544H3C-O-H2C CH2-O-CH3 NIKALAC MW-30HM The respective compositions were evaluated as in Example 1 using the obtained compositions. Only in the evaluation of Examples 2, 3, 5, 8, 9, 11 and Comparative Examples 3 and 4, the imaging system was eluted with 0.4% by weight aqueous solution of tetramethylammonium hydroxide (ELM-D diluted with water). Like 80 seconds. The results are shown in Table 2. -48- 200912544

rrn 1 I； (I S驚6 Ο g s 〇 S 〇 〇 s 〇 〇 Ο 〇 〇 ί〇 s ^ψ, 5 Ο ^ o ο 〇 Ο ώ o o 密著性 (Mpa) cn C<1 υη CS1 CNl ON 1 < CNl C<1 〇〇 1 ( CO CSI 〇\ 1 < OO Csl 1 1 1 < MD a ON Os σ\ vo VO 〇\ CN CTn 〇\ \〇 〇\ cn σ> OO a\ OO σ\ ON OO OO OO 鰥 •Sf _ _ 1 < Cs) CN > < r—i 1 _ < CO 1 < c<\ 1' 1 '< T- "H i i 寸 卜 与忘1 wo vn 寸 寸 VO wo OO cn v〇 寸 寸 v〇 »J〇 v〇 添邀w 熟化後 膜厚 (#m) r- cs \〇 c^i VO \〇 c^* csi Ό ir- CN Γ-* r- oi OO OO r^j 毖S 蹯 感光特性 感度 (J/m2) o OO o o\ 〇 r- o O O o r- Ο OO o o o 1 '< 1 < 0 CO 1 1 i if _ m ^ 没 cn cr\ CO o CO ON CO On in 〇\ Os cn crs 〇\ OO ON a\ g m w 預烘烤 後膜厚 (//m) m CO m cn m cn m cn cn cn CO m cn cn CO 組成物 »~< cn 寸 υη Ό OO 〇\ M 寸 r _、 m 1 < \〇 ψ < 鬆 〇 1 < r—H 1 < 鬆 CNl 1 < cn 1 痛 m 枭 t -H csl cn m 寸 m νη S Ό OO m o\ m 〇 ί < 1 i τ — ^ 匡 CnI 1 i m 1 * m C<1 CO 寸 S 辑 辑 辑 辑 辑 辑 習 辑 辑 習 辑 鎰 鎰 鎰 鎰 {_( _ί u ®ι; IK IK IK IK 卹 Κ {_; |K j_j J-Λ J_J J-4 J_j J-A 200912544 產業上之利用可能性 本發明可利用作，用以形成液晶顯示元件、有機EL 顯示元件等之薄膜電晶體（TFT)基板用平坦化膜，半導體元 件之層間絕緣膜，或光波導之芯、覆材的材料。 【圖式簡單說明】 Μ 。 y \ \\ 【主要元件符號說明】 並。 j\ \\ -50-Rrn 1 I; (IS 惊 6 Ο gs 〇S 〇〇s 〇〇Ο 〇〇ί〇s ^ψ, 5 Ο ^ o ο 〇Ο oo oo Adhesion (Mpa) cn C<1 υη CS1 CNl ON 1 < CNl C<1 〇〇1 (CO CSI 〇\ 1 < OO Csl 1 1 1 < MD a ON Os σ\ vo VO 〇\ CN CTn 〇\ \〇〇\ cn σ> OO a\ OO σ \ ON OO OO OO 鳏•Sf _ _ 1 < Cs) CN >< r-i 1 _ < CO 1 <c<\ 1' 1 '< T- "H ii Inch and forget 1 wo vn inch VO wo OO cn v〇 inch inch v〇»J〇v〇添 invite w After curing film thickness (#m) r- cs \〇c^i VO \〇c^* csi Ό ir- CN Γ- * r- oi OO OO r^j 毖S 蹯 Sensitivity characteristic sensitivity (J/m2) o OO oo\ 〇r- o OO o r- Ο OO ooo 1 '< 1 < 0 CO 1 1 i if _ m ^ no cn cr\ CO o CO ON CO On in 〇 \ Os cn crs 〇\ OO ON a\ gmw Pre-baking film thickness (//m) m CO m cn m cn m cn cn cn CO m cn cn CO composition »~< cn inchυη Ό OO 〇\ M inch r _, m 1 < \〇ψ < 松〇1 < r-H 1 < 松 CNl 1 < cn 1 痛m 枭t -H csl cn m 寸 m νη S Ό OO mo\ m 〇ί < 1 i τ — ^ 匡CnI 1 im 1 * m C<1 CO 寸 S Edit Collection 习 _ { _ ( _ ί u ® ι; IK IK IK IK Shirt Κ {_; |K j_j J-Λ J_J J-4 J_j JA 200912544 Industrial Applicability The present invention can be used for forming a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element. A planarizing film, an interlayer insulating film of a semiconductor element, or a material of a core or a cladding of an optical waveguide. [Simple description of the diagram] Μ . y \ \\ [Main component symbol description] and. j\ \\ -50-

Claims (1)

200912544 十、申請專利範圍： 1. 一種感光性組成物，係含有（a)聚矽氧烷、（b)丙烯酸樹脂 、（c) _二疊氮化合物、（d)溶劑之感光性組成物，其中（a) 聚砍氧院/(b)丙烯酸樹脂之混合比率爲重量比20/80以上 80/20以下’且（a)聚矽氧烷係由使一般式（1)所表之有機 砂院的1種以上反應所合成之聚矽氧烷， (R七Si<〇R2)4_n . (1) 1' (式中，Rl表氫、碳原子數1~10之烷基、碳原子數2~10 之烯基、碳原子數6~15之芳基中任一者，複數之R1可各 係相同或不同；R2表氫、碳原子數1〜6之烷基、碳原子 數2〜6之醯基、碳原子數6~15之芳基中任一者，複數之 R2可各係相同或不同；η表〇至3之整數）。 2. 如申請專利範圍第1項之感光性組成物，其中（a)於聚矽 氧烷，聚矽氧烷中之苯基之含有率係相對於Si原子爲 30〜70吴耳％ 〇 I 3.如申請專利範圍第1或2項之感光性組成物，其中（b)丙 烯酸樹脂於側鏈有乙烯式不飽和基。 4.如申請專利範圍第丨至3項中任一項之感光性組成物， 其中（b)丙烯酸樹脂之重量平均分子量係在5000〜50000之 範圍內。 5 . —種硬化膜，係由如申請專利範圍第1至4項中任一項 之感光性組成物所形成之硬化膜，其中於波長400nm的 每3//m膜厚之透光率係90%以上。 6. —種元件，其中具備如申請專利範圍第5項之硬化膜。 -51- 200912544 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： Μ 〇 j\ \\ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 。 /\\\200912544 X. Patent application scope: 1. A photosensitive composition comprising (a) polydecane, (b) acrylic resin, (c) _diazide compound, (d) solvent photosensitive composition, Wherein (a) polycauterine/(b) acrylic resin is blended at a weight ratio of 20/80 or more and 80/20 or less' and (a) polyoxyalkylene is derived from the organic sand of the general formula (1) Polyoxane synthesized by one or more kinds of reactions in the hospital, (R7 Si<〇R2)4_n. (1) 1' (wherein, R1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, and the number of carbon atoms Any one of 2 to 10 alkenyl groups and 6 to 15 aryl groups, the plural R1 may be the same or different; R 2 represents hydrogen, 1 to 6 carbon atoms, carbon number 2~ Any one of 6 fluorenyl groups and aryl groups having 6 to 15 carbon atoms, the plural R2 may be the same or different; η represents 整数 to an integer of 3). 2. The photosensitive composition of claim 1, wherein (a) the polyphenylene oxide, the polyphenylene oxide has a phenyl group content of 30 to 70 mil% relative to the Si atom. 3. The photosensitive composition of claim 1 or 2, wherein (b) the acrylic resin has an ethylenically unsaturated group in the side chain. 4. The photosensitive composition according to any one of claims 3 to 3, wherein (b) the acrylic resin has a weight average molecular weight of from 5,000 to 50,000. A hardened film formed by a photosensitive composition according to any one of claims 1 to 4, wherein a light transmittance per 3/m film thickness at a wavelength of 400 nm is used. more than 90 percent. 6. A component having a cured film as in claim 5 of the patent application. -51- 200912544 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: /\\\
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