TW200809412A - Positive colored radiation-sensitive resin composition - Google Patents

Positive colored radiation-sensitive resin composition Download PDF

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Publication number
TW200809412A
TW200809412A TW096122428A TW96122428A TW200809412A TW 200809412 A TW200809412 A TW 200809412A TW 096122428 A TW096122428 A TW 096122428A TW 96122428 A TW96122428 A TW 96122428A TW 200809412 A TW200809412 A TW 200809412A
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structural unit
resin
pattern
resin composition
compound
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TW096122428A
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Chinese (zh)
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Airi Yamada
Akira Yokota
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Sumitomo Chemical Co
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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
    • G03F7/022—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

A positive colored radiation-sensitive resin composition comprising (A) an alkali-soluble curable resin, (B) a quinonediazide compound and (C) a coloring agent, wherein (A) the alkali-soluble curable resin is a copolymer containing (a1) a constitutional unit derived from an unsaturated carboxylic acid and (a2) a constitutional unit derived from an unsaturated compound having an oxetanyl group other than the unsaturated carboxylic acid.

Description

200809412 九、發明說明.： 【舍明所屬之技術領域】 本發明係有關一種正型彩色輻射線感應樹脂組成物。 【先前技術】 已知使用含有藉由共聚合環氧化合物與其他成分所獲 得之共聚物，1，2_重氮醌化合物及黑色著色劑的輻射線感 應Μ月曰組成物以形成黑色矩陣（black matrix ;又稱為專 框）（專利文獻1)。 ” 亦已知’為了改善對比度，在黑色矩陣上形成彩色濾 光片用之光感應間隙材（photospacer)，造成變黑（例如，專 利文獻2)。 [專利文獻1]日本專利2001-343743號，實施例i [專利文獻2]日本專利第2002-174817號 然而’彩色濾光片用之光感應間隙材需具有進一步更 精細的構型，以改善液晶面板的輝度。 【發明内容】 本發明之目的係提供一種賦與高解析度之彩色硬化樹 脂圖樣的正型彩色輻射線感應樹脂組成物。 本發明人已進行研究以解決上述問題而發現含有（a2) 何生自具氧雜環丁基之不飽和化合物之結構單元之共聚物 的幸畜射線感應樹脂組成物可賦與高解析度之彩色硬化樹脂 圖樣。 亦即，本發明提供下述[1]至[9]: [1]· 一種正型彩色輻射線感應樹脂組成物，包括（A)鹼 319342 5 200809412 溶性可固化（alkali-soluble curable)樹脂，（B)重氮醌 ((}11丨1101^(^2丨(^)化合物及（(^)著色劑，其中（人）驗溶性可固 化树&係含有下述結構單元之共聚物··（a 1 )衍生自不飽和 羧酸之結構單元及（a2)衍生自具有不飽和羧酸以外之氧雜 環丁基之不飽和化合物之結構單元。 [2]·依據[1]之樹脂組成物，其中（A)鹼溶性可固化樹脂 進一步含有（a3)選自下述所成群組之至少一種結構單元·· (a31)衍生自具有碳-碳不飽和鍵之羧酸酯之結構單元，（a〕) 衍生自具有碳-碳不飽和鍵之芳香族化合物之結構單元， (a33)衍生自丙烯腈（νίηγι cyanide)化合物之結構單元，（u句 付生自在N位置視需要具有取代基之馬來醯亞胺化合物之 尨構單元及（a3 5)衍生自具有碳-碳不飽和鍵之環氧化合物 之結構單元。 " [3] ·依據[1]或[2]之樹脂組成物，其中著色劑（c)係選自 有機顏料及黑色無機顏料所組成群組之至少一種顏料。 [4] ·依據[1]至[3]任一者之樹脂組成物，進一步包括⑴） 有機溶劑。 ,[5]—種使用依據Π]至[4]任一者之樹脂組成物所形成 之彩色硬化樹脂圖樣。 7 Μ] —種彩色硬化樹脂圖樣之製造方法，包括在基板施 用依據[1]至[4]任—者之㈣組成物，移除溶劑，經由遮 以輻射線照射該樹脂組成物，然後以鹼性水溶液進行顯与 以形成圖樣。 ”、、、’7、/ [7]依據[6]之彩色硬化樹脂圖樣之製造方法，其中在囷 319342 6 200809412 樣形成之後，進一步加熱該圖樣。 [8] —種彩色硬化樹脂圖樣之製造方法，包括在基板施 用依據[1]至[4]任一者之正型彩色輻射線感應樹脂組成 物’移除溶劑，經由遮罩以輻射線照射該樹脂組成物，以 鹼性水溶液進行顯影以形成既定圖樣，然後以輻射線照射 基板之圖樣的整個表面或部份表面。 [9] 依據[8]之彩色硬化樹脂圖樣之製造方法，其中在以 輕射線照射基板之圖樣的整個表面或部份表面之後，進一 步加熱該圖樣。 【貫施方式】 (較佳實例之說明） (A)本發明中之鹼溶性可固化樹脂係含有下述結構單 7L之共聚物：（ai)衍生自不飽和羧酸之結構單元及（a2)衍生 自具有氧雜環丁基之不飽和化合物之結構單元。此處，欲 衍生至結構單元（a2)中之不飽和化合物非為不飽和致酸。 至於欲衍生至結構單元（al)中之不飽和羧酸，可提及 者，例如，分子中具有一個或多個羧基之不飽和羧酸等。 不飽和羧酸的特定實例包含丙烯酸、甲基丙烯酸、巴 丑酸、衣康酸、馬來酸、富馬酸、擰康酸、曱基富馬酸等。 本說明書中’（甲基）丙浠酸係表示選自丙浠酸及甲基 丙烯酸所成群組之至少一者，（甲基）丙烯酸酯係表示選自 丙細酸酯及甲基丙浠酸酯所成群組之至少一者，（甲基）丙 烯醯基係表示選自丙烯醯基及甲基丙烯醯基所成群組之至 少一者，以及（曱基）丙烯醯氧基係表示選自丙烯醯氧基及 319342 7 200809412 甲基丙烯醯氧基所成群組之至少一者。 上述欲衍生至結構單元⑷）中之具有氧雜環丁 實例包含H:基)丙稀酿氧基甲基氧:環丁 凡 土 -(甲基）丙烯酸氧基甲基氧雜環丁院、3 _3_(甲基）丙稀酿氧基甲基氧雜環丁烧、基^甲土 二稀:氧基]甲基氧雜環丁烧、3_乙基邮(甲： 基]甲基乳雜環丁统、3·甲基例甲基）丙稀酸氧基]乙^ ΓΓ:Γ3-乙基-物基)丙稀醯氧基]乙基氧雜環； -本基_3-(甲基）丙稀醯氧基甲基氧雜環丁院、2_ 甲土 _3-(甲基）丙婦酿氧基甲基氧雜環丁燒、2_五 _3-(甲基）丙烯醯氧基甲基氧雜環丁烷、夂甲基j t 烯醯氧基乙基氧雜環丁烷、3 二 土丙 ^ 〇丞j (甲基）丙烯醯氧基乙 ί、2"氟二2_苯基甲基)丙稀醯氧基乙基氧雜環丁 二氧 崎=雜丁=較者為一甲基丙 氧雜…Γ 甲基丙烯醯氧基甲基 产及3\1 m(1-甲基丙婦酿氧基）乙基氧雜環丁 乙：3甲其稀酿氧基氧雜環丁貌，*中，較佳使用、-广基丙烯酿氧基〒基氧雜環丁烷及」·甲 美 丙烯醯氧基甲基氧雜環丁烷。 土 製備=二==飽和化合物之鹼溶性樹脂所 衍生自呈^ 樹脂組成物相較下，使用含有 丁生自環丁基之不飽和化合物之結構單元㈣之驗 319342 8 200809412 眭树知所製備之正型彩色輻射線感應樹脂組 正型彩辛韧& a』 ^ ^ 竿田射線感應樹脂組成物之更優異的保存安定性呈 有較佳的傾向。 /、 ^在僅含結構單元（al)及結構單元（a2)之共聚物中，以共 二=:之所有結構單元之莫耳比率計之，結構單元⑷）的 一畺車乂彳土為5至50莫耳❻/。，更佳為15至40莫耳。/。，以乓 之所有結構單元之莫耳比率計之，結構單元（a⑽ 吞里車乂么為95至50莫耳0/〇，更佳為85至6〇莫耳％。 取由在顯影劑中適合的溶解速度及高硬性的觀點來看， /、♦物中之結構單元（al)及結構單元（a2)的含量較佳在上 述範圍内。 ^本發明中之（A)鹼溶性可固化樹脂可進一步含有（a3) 运自下述所成群組之至少一種結構單元：（a3”衍生自具有 f·碳不飽和鍵之羧酸酯之結構單元，（a32)衍生自具有碳_ 碳不飽和鍵之芳香族化合物之結構單元，（a33)衍生自丙 腈化合物之結構單元，（a34)衍生自在^^位置視需要具有取 代基之馬來醯亞胺化合物之結構單元及（a35)衍生自具有 碳-碳不飽和鍵之環氧化合物之結構單元。 欲衍生至結構單元（a31)之具有碳·碳不飽和鍵之羧酸 酯的實例包含不飽和羧酸酯如（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸2_羥基乙 酯、（甲基）丙烯酸苯子酯、（曱基）丙烯酸環己酯、（甲基）丙 烯酸異冰片醋、（甲基）丙烯酸二環戊醋、（甲基）丙婦酸苯 酯、馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等；不 319342 9 200809412 飽和羧酸胺基烷酯如（曱基）丙烯酸胺基乙酯等；羧酸乙晞 酯如乙酸乙烯酯、丙酸乙稀酯等。 ¥人竹生至結構早元（a3 2)之具有碳-碳不飽和鍵之芳香 族化合物的實例包含芳香族乙烯系化合物。芳香族乙稀系 化合物的實例包含苯乙烯、曱基苯乙烯、乙烯基曱苯等。 欲衍生至結構單元（a33)之丙烯腈化合物的實例包含 丙烯腈、曱基丙烯腈、α-氯（甲基）丙烯腈等。 欲衍生至結構單元（a34)之在Ν位置視需要具有取代 基之馬來醯亞胺化合物的實例包含馬來醯亞胺、N-甲基馬 來醯亞胺、N-乙基馬來醯亞胺、N-丁基馬來醯亞胺、1環 己基馬來酿亞胺、N-苯曱基馬來酸亞胺、N-苯基馬來酿亞 胺、N-(4-乙醯基苯基）馬來醯亞胺、N_(2,6_二乙基苯基）馬 來醯亞胺、N-(4-二甲基胺基_3,5_二硝基苯基）馬來醯亞 胺、N-號珀酿亞胺基-3-馬來醯亞胺苯甲酸酯、N-號珀醯亞 胺基-3-馬來醯亞胺丙酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺 丁酸i曰、N-坡亞胺基_6_馬來酿亞胺己酸醋、N-(l -苯 胺基萘基-4·>馬來醯亞胺、N-[4-(2-苯并噚唑基）苯基]馬來 醯亞胺、N-(9-吖啶基）馬來醯亞胺等。 欲衍生至結構單元（a35)之具有碳-碳不飽和鍵之環氧 化合物的實例包含（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸 冷-甲基縮水甘油酯、（甲基）丙烯酸々-乙基縮水甘油酯、（甲 基）丙烯酸3-曱基-3,4_環氧基丁酯、（甲基）丙烯酸乙基 •3，4-環氧基丁酯、（甲基）丙烯酸4-甲基-4,5-環氧基戊酯、 (甲基）丙烯酸2,3-環氧基環己基甲酯、（甲基）丙烯酸3,4- 10 319342 200809412 環氧基環己基甲酯、鄰-乙烯基苯甲基縮水甘油基醚、間_ 乙烯基苯曱基縮水甘油基醚、對-乙烯基苯甲基縮水甘油基 醚等。 土 。可使用衍生自一種或多種上述示例之化合物作為結構 單儿（al)，（a2)，（a31)，（a32)，（a33)，（a34)及（a35)。 (A)鹼溶性可固化樹脂除了結構單元（al)及結構單元 (a2)外，可含有結構單元（a3)。在除了結構單元（al)及結構 單元（a2)外又包含結構單元（a3)的情形下，以共聚物中之所 有、、、。構單元之莫耳比率計之，結構單元（al)的含量較佳為5 至莫耳/〇更佳為15至5 0莫耳％。以共聚物中之所、有 結構單元之莫耳比率計之，結構單元（a2)的含量較佳為9〇 至5莫耳％，更佳為乃至1〇莫耳％。以共聚物中之所有 、、、口構單7G之莫耳比率計之，結構單元（a3)的含量較佳為Μ 至5莫耳％，更佳為75至1〇莫耳％。 一含有結構單元（al)及結構單元（a2)之共聚物的實例包 含3-乙基甲基丙烯醯氧基甲基氧雜環丁烷/曱基丙烯酸 苯以旨/甲基丙埽酿酸共聚物、乙基I甲基丙烯酸氧基甲 基氧雜環丁烧/甲基丙稀酸苯甲醋/甲基丙稀酸/苯乙稀共聚 物+、3_^基_3_甲基丙稀酿氧基甲基氧雜環丁烧/甲基丙稀酸 /苯乙烯共水物、3_乙基曱基丙烯醯氧基甲基氧雜環丁烷 /甲基丙烯酸/甲基丙烯酸環己酯共聚物、％乙基冬甲基丙 烯醯氧基甲基氧雜環丁烧/甲基丙烯酸/曱基丙烯酸甲酯共 水物3乙基|甲基丙稀醯氧基甲基氧雜環丁烧/曱基丙稀 酸/甲基丙烯酸甲醋/苯乙烯共聚物、3-乙基-3-甲基丙浠酿 319342 11 200809412 氧基曱基氧雜環丁垸/甲基丙烯酸/曱基丙烯酸第三丁醋共 聚物、3-乙基_3_甲基丙烯酿氧基甲基氧雜環丁烧/甲基丙婦 酸/甲基丙烯酸異冰〇旨共聚物、3_乙基_3_甲基丙賴氧基 甲基氧雜環丁烧/甲基丙烯酸/丙稀酸苯甲§旨共聚物、3_乙基 -3-甲基丙烯醯氧基甲基氧雜環丁靖基丙烯酸/丙稀酸環 己酯共聚物、3-乙基_3_甲基丙烯醯氧基曱基氧雜環丁烷/ J基丙烯酸/丙烯酸異冰片酯共聚物、3_乙基_3_甲基丙烯醯 氧基甲基氧雜環丁烷/甲基丙烯酸/甲基丙烯酸二環戊酯共 聚物、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷/甲基丙稀 酸/丙烯酸第三丁酉旨共聚物、3_乙基_3_甲基丙婦酿氧基甲基 氧雜環丁烷/甲基丙烯酸/苯基馬來醯亞胺共聚物、3_乙基 -3-甲基丙稀醢氧基甲基氧雜環丁烷/甲基丙烯酸/環己基馬 來醯亞胺共聚物等。 例如，將欲衍生至結構單元（al)中之化合物與欲衍生 至結構單7G(a2)中之化合物，以及若需要時之欲衍生至結 構單元（a3)中之化合物，在觸媒存在或不存在下，在惰性 氣體氛圍或空氣氛圍中，於溶劑存在或不存在下混合，且 該混合物再予以加熱，通常於30至2〇(rc予以熱隔絕，以 引起其反應，再自所得之反應液體分離出欲使用於本發明 之驗溶固化性樹脂（A)，若有需要時，則予以純化。 藉由使用聚苯乙烯作為標準品之凝膠滲透層析術所測 付之含有結構單元（al)及結構單元（a2)之共聚物的重量平 均分子量較佳為2000至100000，更佳為2〇〇〇至5〇〇〇〇， 又更佳為3000至20000。重量平均分子量較佳在上述範圍 319342 12 200809412 雒持膜殘餘率 内，因而使其具有高顯影速度同時顯影令 (remaining ratio)的傾向。 以輪射線感應樹脂組成物的固含量計 ° < ’本發明中冬 有結構單元（al)及結構單元（a2)之共聚物的人曰土 Τ μ 3 1較佳為 50 至90重量％，更佳為60至90重量％。 ’ 此處，固含量係指自彩色感光樹脂組成物移除溶劑（D) 後的殘留部份。 欲使用於本發明之重氮醌化合物（Β)的實例包含i，2_ 笨并重氮職續酸鹽、1，2-萘并重氮職確酸鹽、丨，2_苯并重氕 酿磺酿胺、1，2-萘并重氮醌磺醯胺等。 重氮i昆化合物（B)的實例包含三經基二苯甲酮之工,2_ 萘并重氮醌磺酸鹽，如2,3,4-三羥基二苯甲_β1，2_萘并重 ^醌-4-磺酸鹽、2,3,4_三羥基二苯曱酮'2_萘并重氮醌-% 石頁酸鹽、2,4,6-三羥基二苯曱酮'、萘并重氮醌_4_磺酸 鹽、2,4,6-二羥基二苯甲酮4,2-萘并重氮醌_5_磺酸鹽等； 四經基二苯甲酮之1，2_萘并重氮醌磺酸鹽，如 2,2’，4,4’-四羥基二苯甲酮_丨，2_萘并重氮醌_4_磺酸鹽、 2,2|，4,4'-四羥基二苯曱酮_1，2_萘并重氮醌_5_磺酸鹽、 2,2’，4,3’-四羥基二苯曱酮],2_萘并重氮醌_心磺酸鹽、 2,2’，4,3·-四羥基二苯甲酮_丨，2_萘并重氮醌_5_磺酸鹽、 2,3,4,4’-四羥基二苯曱酮_u_萘并重氮醌磺酸鹽、 2,3,4,4’-四羥基二苯曱酮_丨，2_萘并重氮醌_5_磺酸鹽、 2,3,4,2’-四羥基二苯曱酮·丨，2-萘并重氮醌磺酸鹽、 2,3,4,2’-四羥基二苯曱酮萘并重氮醌_5_磺酸鹽、 319342 13 200809412 2,3,4，f-四羥基-3’-甲氧基二苯甲酮-1,2-萘并重氮醌-4-磺 酸鹽、2,3,4,4’-四羥基-3f-甲氧基二苯甲酮-1，2-萘并重氮醌 ‘ -5-磺酸鹽等； 五羥基二苯曱酮之1，2-萘并重氮醌磺酸鹽，如2,3,4, 2’，6’-五羥基二苯甲酮-1,2-萘并重氮醌-4-磺酸鹽、2,3,4, 2、6f-五羥基二苯曱酮-1,2-萘并重氮醌-5-磺酸鹽等； 六羥基二苯曱酮之1，2-萘并重氮醌磺酸鹽如2,4,6, 3’， 4’，5f-六羥基二苯甲酮-1，2-萘并重氮醌-4-磺酸鹽、2,4,6, 3’， 4’,5’-六羥基二苯甲酮-1，2-萘并重氮醌-5-磺酸鹽、3,4,5, 3’， 4’，5f-六羥基二苯甲酮-1,2-萘并重氮醌-4-磺酸鹽、3,4,5, 3’， 4’，5’-六羥基二苯曱酮-1，2-萘并重氮醌-5-磺酸鹽等； (多羥基苯基）烷類之1，2-萘并重氮醌磺酸鹽，如雙 (2,4-二羥基苯基）甲烷-1，2-萘并重氮醌-4-磺酸鹽、雙（2,4-二羥基苯基）曱烷-1,2-萘并重氮醌-5-磺酸鹽、雙（對-羥基苯 基）曱烷-1,2-萘并重氮醌-4-磺酸鹽、雙（對-羥基苯基）曱烷 -1，2-萘并重氮醌-5-磺酸鹽、1，1，1-三（對-羥基苯基）乙烷 -1，2-萘并重氮醌-4-磺酸鹽、1，1，1-三（對-羥基苯基）乙烷 -1，2-萘并重氮醌-5·磺酸鹽、雙（2,3,4-三羥基苯基)甲烷-1，2-萘并重氮醌-4-磺酸鹽、雙（2,3,4-三羥基苯基）甲烷-1，2-萘并 重氮醌-5-磺酸鹽、2,2’-雙（2,3,4-三羥基苯基）丙烷-1，2-萘并 重氮醌-4_磺酸鹽、2,2’-雙（2,3,4-三羥基苯基）丙烷-1，2-萘并 重氮醌-5-磺酸鹽、1，1，3-叁（2,5-二甲基-4-羥基苯基）-3-苯基 丙烷-1，2-萘并重氮醌-4-磺酸鹽、1,1,3-叁（2,5-二曱基-4-羥 基苯基）-3-苯基丙烷-1，2-萘并重氮醌-5-磺酸鹽、 14 319342 200809412 4,4^[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚 -1,2 -秦弁重氮醒-4-石黃酸鹽、4,4f_[l-[4-[l-[4 -經基苯基]-1-曱基乙基]苯基]亞乙基]雙驗-1，2 -秦弁重氣S昆-5 -石黃酸鹽、雙 (2,5->一甲基-4-經基苯基）-2-輕基苯基甲烧_1，2 -秦弁重氣酉昆 -4-磺酸鹽、雙（2,5-二甲基-4-羥基苯基）-2-羥基苯基曱烷 -1，2-萘并重氮醌-5_磺酸鹽、3,3,3，，3，-四曱基-1，1，-螺茚 -5,6,7,5’，6f，7’-己醇 _1，2_萘并重氮醌-4-磺酸鹽、3,3,3，，3，·四 曱基-1，1’-螺茚-5,6,7,5，，6，J’-己醇-1，2·萘并重氮醌-5-磺酸 鹽、2,2,4-三甲基_7,2，，4，-三羥基黃烷-i，2·萘并重氮醌_4_磺 酸鹽、2,2,4-三甲基_7,2，，4’-三羥基黃烷-萘并重氮醌_5-磺酸鹽等。 明中重氮醌化合物（B)的含量較佳為2至5〇重量％，更佳 為至4〇重里/〇。重氮醌化合物的含量較佳在上述範圍 内口而使非曝光部份與曝光部份間之溶解速度的差異增 因此傾向於顯影中能夠維持高的膜殘餘率。 至於欲使用於本發明之著色200809412 IX. Invention Description: [Technical Field to which Sheming belongs] The present invention relates to a positive color radiation sensing resin composition. [Prior Art] It is known to use a radiation-containing cerium composition containing a copolymer obtained by copolymerizing an epoxy compound with other components, a 1,2 diazonium compound, and a black colorant to form a black matrix ( Black matrix; also known as a frame (Patent Document 1). It is also known that, in order to improve the contrast, a light-sensing gap spacer for a color filter is formed on a black matrix to cause blackening (for example, Patent Document 2). [Patent Document 1] Japanese Patent No. 2001-343743 Example i [Patent Document 2] Japanese Patent No. 2002-174817 However, the light-sensitive gap material for a color filter needs to have a further finer configuration to improve the luminance of the liquid crystal panel. The object of the present invention is to provide a positive color radiation sensing resin composition which imparts a high-resolution color hardening resin pattern. The present inventors have conducted research to solve the above problems and found that (a2) The photo-sensing resin composition of the copolymer of the structural unit of the ethylenically unsaturated compound can be imparted with a high-resolution color hardened resin pattern. That is, the present invention provides the following [1] to [9]: [1] · A positive color radiation sensing resin composition comprising (A) alkali 319342 5 200809412 alcohol-soluble curable resin, (B) diazonium hydrazine ((}11丨1101^(^2丨(^ Compounds and ((^) a coloring agent, wherein (human) a testable curable tree & is a copolymer containing the following structural unit: (a1) a structural unit derived from an unsaturated carboxylic acid and (a2) derived from having A structural unit of an unsaturated compound of an oxetanyl group other than a saturated carboxylic acid. [2] The resin composition according to [1], wherein the (A) alkali-soluble curable resin further contains (a3) selected from the group consisting of At least one structural unit in a group (a31) a structural unit derived from a carboxylate having a carbon-carbon unsaturated bond, (a) a structural unit derived from an aromatic compound having a carbon-carbon unsaturated bond (a33) a structural unit derived from a compound of acrylonitrile (νίηγι cyanide), which is derived from a carbon-containing unit of a maleimide compound having a substituent at the N position and (a3 5) derived from carbon a structural unit of an epoxy compound having a carbon unsaturated bond. [3] The resin composition according to [1] or [2], wherein the coloring agent (c) is selected from the group consisting of organic pigments and black inorganic pigments. At least one pigment of the group. [4] · Resin group according to any one of [1] to [3] Further, the method further comprises (1) an organic solvent. [5] A color hardening resin pattern formed by using a resin composition according to any one of Π] to [4]. 7 Μ] - a method for producing a color hardened resin pattern Including applying the composition of (4) according to any one of [1] to [4] on the substrate, removing the solvent, irradiating the resin composition with radiation, and then expressing it with an aqueous alkaline solution to form a pattern. [7], [7] The method for producing a color hardened resin pattern according to [6], wherein the pattern is further heated after the formation of 囷319342 6 200809412. [8] A method for producing a color hardened resin pattern, comprising: removing a solvent by applying a positive color radiation sensing resin composition according to any one of [1] to [4], irradiating a radiation through a mask The resin composition is developed with an aqueous alkaline solution to form a predetermined pattern, and then the entire surface or part of the surface of the pattern of the substrate is irradiated with radiation. [9] The method of producing a color hardened resin pattern according to [8], wherein the pattern is further heated after irradiating the entire surface or a part of the surface of the pattern of the substrate with light rays. [Comment] (Description of a preferred embodiment) (A) The alkali-soluble curable resin of the present invention contains a copolymer of the following structure 7L: (ai) a structural unit derived from an unsaturated carboxylic acid and (a2) a structural unit derived from an unsaturated compound having an oxetanyl group. Here, the unsaturated compound to be derivatized into the structural unit (a2) is not unsaturated to acid. As the unsaturated carboxylic acid to be derivatized into the structural unit (al), there may be mentioned, for example, an unsaturated carboxylic acid having one or more carboxyl groups in the molecule and the like. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, barley acid, itaconic acid, maleic acid, fumaric acid, thiconic acid, mercaptofumaric acid and the like. In the present specification, '(meth)propionic acid means at least one selected from the group consisting of propionic acid and methacrylic acid, and (meth) acrylate means selected from the group consisting of a propionate and a methyl propyl hydrazine. At least one of the groups in which the acid ester is grouped, the (meth) acrylonitrile group is at least one selected from the group consisting of an acryloyl group and a methacryl fluorenyl group, and a (mercapto) acryloxy group. Represents at least one selected from the group consisting of propylene decyloxy and 319342 7 200809412 methacryloxyloxy groups. Examples of the oxetane to be derivatized into the structural unit (4) include H: yl) acryloxymethyloxy: cyclobutane-(meth)acryloxymethyloxetane, 3 _3_(Methyl) propylene oxide oxymethyl oxetane, ketone di-carbamate: oxy] methyl oxetane, 3-ethyl-ethyl (meth) methyl milk Heterocyclic, 3, methyl, methyl) acrylic acid oxy] ethane Γ: Γ 3-ethyl- yl) acryloxy] ethyl oxo; Methyl) propylene methoxymethyl oxetane, 2_ 甲土_3-(methyl) propyl oxymethyl oxetane, 2_5-3-(methyl) propylene醯 methoxymethyl oxetane, fluorenylmethyl jt olefin ethoxyethyl oxetane, 3 dioxin 〇丞 j (meth) propylene methoxy ethoxy, 2 " fluorodi 2_Phenylmethyl) propylene oxiranoxyethyl oxetane dioxane = miscible = the first one is methyl propyl oxa... 甲基 methacryloxymethyl methylate and 3 \1 m (1-methylpropanoloxy)ethyloxetane: 3, its dilute oxyoxycyclobutene, *, preferably used, - broad-based acryloxycarbonyloxy Cyclobutane and "US-A-Bing Xixi methyl oxetane group. Soil preparation = two = = the alkali-soluble resin of the saturated compound is derived from the resin composition, and the structural unit (4) containing the unsaturated compound of butadiene-derived butyl group is used. 319342 8 200809412 Type color radiation sensing resin group positive color dying toughness & a』 ^ ^ The superior storage stability of the stalk radiation sensing resin composition tends to be better. /, ^ In the copolymer containing only the structural unit (al) and the structural unit (a2), the molar ratio of all structural units of the total two =:, the structural unit (4)) 5 to 50 moles /. More preferably 15 to 40 moles. /. In terms of the molar ratio of all the structural units of the pong, the structural unit (a(10) is immersed in the range of 95 to 50 m0/〇, more preferably 85 to 6 mol%. From the viewpoints of suitable dissolution rate and high hardness, the content of the structural unit (al) and the structural unit (a2) in /, ♦ is preferably within the above range. ^ (A) alkali soluble curable in the present invention The resin may further comprise (a3) at least one structural unit from the group consisting of: (a3) derived from a structural unit having a carboxylate having a f-carbon unsaturated bond, (a32) derived from having a carbon-carbon a structural unit of an aromatic compound having an unsaturated bond, (a33) is derived from a structural unit of a propionitrile compound, (a34) is derived from a structural unit of a maleimide compound having a substituent as required at the position of (^) and (a35) a structural unit derived from an epoxy compound having a carbon-carbon unsaturated bond. Examples of the carboxylic acid ester having a carbon-carbon unsaturated bond to be derivatized to the structural unit (a31) include an unsaturated carboxylic acid ester such as (meth) Methyl acrylate, ethyl (meth) acrylate, (methyl) propyl Butyrate, 2-hydroxyethyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate Vinegar, phenyl (meth) propyl acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; not 319342 9 200809412 Aminoalkyl ester of saturated carboxylic acid such as sulfhydryl Aminoethyl acrylate or the like; acetonitrile carboxylic acid ester such as vinyl acetate, ethyl propionate, etc. An example of an aromatic compound having a carbon-carbon unsaturated bond in the structure of the human element (a3 2) An aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, mercaptostyrene, vinyl anthracene, etc. Examples of the acrylonitrile compound to be derivatized to the structural unit (a33) include acrylonitrile and mercaptopropene. Nitrile, α-chloro(meth)acrylonitrile, etc. Examples of the maleimide compound to be derivatized to the structural unit (a34) at the oxime position, optionally having a substituent, include maleimide, N-methyl Maleic imine, N-ethyl maleimide, N-butyl maleimide 1 cyclohexylmaleimine, N-phenylmercaptomaleimide, N-phenylmaleimine, N-(4-ethylmercaptophenyl)maleimide, N_(2 , 6_diethylphenyl)maleimide, N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, N-type saponin -3-Maleic imide benzoate, N-type perinimido-3-maleimide propionate, N-succinimide-4-maleimide butyric acid i曰, N-poline imine _6_maleimine caproic acid vinegar, N-(l-anilinylnaphthyl-4·>maleimide, N-[4-(2-benzene And oxazolyl)phenyl]maleimide, N-(9-acridinyl)maleimide, etc. Epoxide compound having a carbon-carbon unsaturated bond to be derivatized to the structural unit (a35) Examples include glycidyl (meth)acrylate, cold-methyl glycidyl (meth)acrylate, fluorene-ethyl glycidyl (meth)acrylate, 3-mercapto-3 (meth)acrylate, 4_Epoxybutyl acrylate, ethyl (3) 4-butyloxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, (methyl) 2,3-epoxy ring of acrylic acid Hexylmethyl ester, (meth)acrylic acid 3,4- 10 319342 200809412 Epoxycyclohexyl methyl ester, o-vinyl benzyl glycidyl ether, m-vinylstyryl glycidyl ether, p- Vinyl benzyl glycidyl ether and the like. Earth. Compounds derived from one or more of the above examples can be used as structural units (al), (a2), (a31), (a32), (a33), (a34) and (a35). (A) The alkali-soluble curable resin may contain a structural unit (a3) in addition to the structural unit (al) and the structural unit (a2). In the case where the structural unit (a3) is contained in addition to the structural unit (al) and the structural unit (a2), all of the copolymers are included. The molar ratio of the structural unit is preferably from 5 to more than 15 to 50% by mole of the structural unit (al). The content of the structural unit (a2) is preferably from 9 Å to 5 mol%, more preferably even 1 〇 mol%, based on the molar ratio of the structural unit in the copolymer. The content of the structural unit (a3) is preferably from Μ to 5 mol%, more preferably from 75 to 1 mol%, based on the molar ratio of all of the copolymers in the copolymer, 7G. An example of a copolymer containing a structural unit (al) and a structural unit (a2) comprises 3-ethylmethacryloxymethyloxybutane/mercaptoacrylic acid benzene for the purpose of /methylpropionate Copolymer, ethyl I methacryloxymethyl oxetane / methyl acrylate benzyl acetate / methyl acrylate / styrene copolymer +, 3 _ base _3_ meth Dilute oxymethyloxetane/methacrylic acid/styrene hydrophile, 3_ethylmercaptopropenyloxymethyloxetane/methacrylic acid/methacrylic acid ring Hexyl Ester Copolymer, % Ethyl Methyl Ethyl Oxime Methyl Oxime Oxime / Methyl Acrylate / Methyl Methacrylate Co-Water 3 Ethyl | Methyl Acetyl Oxime Methoxy Cyclobutane/mercaptopropionic acid/methyl methacrylate/styrene copolymer, 3-ethyl-3-methylpropene broth 319342 11 200809412 Oxime oxirane/methacrylic acid/ Mercaptoacrylic acid third butane vinegar copolymer, 3-ethyl_3_methacrylic oxymethyloxetane/methylpropionic acid/methacrylic acid isobornyl copolymer, 3_B Base _3_methylpropoxymethyl oxetane / Acrylic acid/acrylic acid benzoic acid copolymer, 3_ethyl-3-methylpropenyloxymethyloxebutanylacrylic acid/cyclohexyl acrylate copolymer, 3-ethyl_3 _Methyl propylene fluorenyl fluorenyl oxetane / J-based acrylic acid / isobornyl acrylate copolymer, 3 - ethyl - 3 - methacryloxymethyl oxetane / methacrylic acid /Dicyclopentyl methacrylate copolymer, 3-ethyl-3-methylpropenyloxymethyloxetane/methacrylic acid/acrylic acid terpene copolymer, 3-ethyl _3_methyl propyl oxymethyloxetane/methacrylic acid/phenylmaleimide copolymer, 3-ethyl-3-methyl propyl methoxymethyl oxalate Cyclobutane/methacrylic acid/cyclohexylmaleimide copolymer and the like. For example, a compound to be derivatized into the structural unit (al) and a compound to be derivatized into the structural single 7G (a2), and if desired, a compound to be derivatized into the structural unit (a3), exist in a catalyst or In the absence of inert gas or air, mixed in the presence or absence of a solvent, and the mixture is heated again, usually at 30 to 2 Torr (rc is thermally insulated to cause its reaction, and then self-generated The reaction liquid is used to separate the test-curable resin (A) to be used in the present invention, and if necessary, it is purified. The structure containing the gel is determined by gel permeation chromatography using polystyrene as a standard. The weight average molecular weight of the copolymer of the unit (al) and the structural unit (a2) is preferably from 2,000 to 100,000, more preferably from 2 to 5 Torr, still more preferably from 3,000 to 20,000. Preferably, in the above range 319342 12 200809412, the film retention ratio is such that it has a high development speed and a tendency to maintain the ratio. The solid content of the composition of the wheel-ray sensing resin is < The human 曰 3 μ 3 1 of the copolymer of the structural unit (al) and the structural unit (a2) in winter is preferably from 50 to 90% by weight, more preferably from 60 to 90% by weight. ' Here, the solid content means The residual portion after removing the solvent (D) from the color photosensitive resin composition. Examples of the diazonium compound (Β) to be used in the present invention include i, 2_ stupid and diazonium salt, 1,2-naphthalene And diazonium salt, bismuth, 2_benzene, heavy sulfonamide, 1,2-naphthodiazepine sulfonamide, etc. Examples of diazo i quinone compound (B) include tris-based benzophenone Work, 2_ naphthodiazepine sulfonate, such as 2,3,4-trihydroxydiphenyl-β1,2-naphthylquinone-4-sulfonate, 2,3,4-trihydroxydiphenyl Anthrone '2_naphthodiazepine-% sulphate, 2,4,6-trihydroxybenzophenone', naphthodiazepine _4_sulfonate, 2,4,6-dihydroxy Benzophenone 4,2-naphthodiazepine_5_sulfonate, etc.; 1,2-naphthodiazepine sulfonate of tetracarboxylic benzophenone, such as 2,2',4,4'- Tetrahydroxybenzophenone 丨, 2_naphthyldiazonium _4_sulfonate, 2,2|,4,4'-tetrahydroxydibenzophenone-1,2-naphthodiazepine_5_ Sulfonate 2,2',4,3'-tetrahydroxydibenzophenone], 2_naphthodiazepine_heart sulfonate, 2,2',4,3·-tetrahydroxybenzophenone 丨, 2 _Naphthodiazepine 醌_5_ sulfonate, 2,3,4,4'-tetrahydroxydibenzophenone _u_naphthodiazepine sulfonate, 2,3,4,4'-tetrahydroxy Phenyl fluorenone 丨, 2_naphthyldiazepine _5_ sulfonate, 2,3,4,2'-tetrahydroxybenzophenone oxime, 2-naphthodiazepine sulfonate, 2,3 , 4,2'-tetrahydroxydibenzophenone naphthodiazepine_5_sulfonate, 319342 13 200809412 2,3,4,f-tetrahydroxy-3'-methoxybenzophenone-1, 2-naphthodiazepine-4-sulfonate, 2,3,4,4'-tetrahydroxy-3f-methoxybenzophenone-1,2-naphthodiazepine'-5-sulfonate 1,2-naphthodiazepine sulfonate of pentahydroxydibenzophenone, such as 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthodiazepine- 4-sulfonate, 2,3,4,2,6f-pentahydroxydibenzophenone-1,2-naphthodiazepine-5-sulfonate; hexahydroxydibenzophenone 1,2- Naphthodiazepine sulfonate such as 2,4,6,3',4',5f-hexahydroxybenzophenone-1,2-naphthodiazepine-4-sulfonate, 2,4,6, 3', 4', 5'-hexahydroxydi Ketone-1,2-naphthodiazepine-5-sulfonate, 3,4,5,3',4',5f-hexahydroxybenzophenone-1,2-naphthodiazepine-4- Sulfonate, 3,4,5,3',4',5'-hexahydroxydibenzophenone-1,2-naphthodiazepine-5-sulfonate; (polyhydroxyphenyl)alkane 1,2-naphthodiazepine sulfonate, such as bis(2,4-dihydroxyphenyl)methane-1,2-naphthodiazepine-4-sulfonate, bis(2,4-dihydroxyl) Phenyl)decane-1,2-naphthodiazepine-5-sulfonate, bis(p-hydroxyphenyl)decane-1,2-naphthodiazepine-4-sulfonate, double (pair) -hydroxyphenyl)decane-1,2-naphthodiazepine-5-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthodiazepine-4 -sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthodiazepine-5-sulfonate, bis(2,3,4-trihydroxyphenyl) Methane-1,2-naphthodiazepine-4-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthodiazepine-5-sulfonate, 2,2 '-Bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthodiazepine-4_sulfonate, 2,2'-bis(2,3,4-trihydroxyphenyl) Propane-1,2-naphthalene醌-5-sulfonate, 1,1,3-叁(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthodiazepine-4-sulfonic acid Salt, 1,1,3-anthracene (2,5-dimercapto-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthodiazepine-5-sulfonate, 14 319342 200809412 4 ,4^[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-Qinda Diazo Xing-4-Shi Xanthate, 4,4f_[l-[4-[l-[4-]-phenylphenyl]-1-indolylethyl]phenyl]ethylidene] double-test-1,2-Qinqin heavy gas S Kun-5 - sulphate, bis (2,5-> monomethyl-4-phenylphenyl)-2-light phenyl ketone _1,2 -Qin 弁 heavy gas 酉 - - 4-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenyldecane-1,2-naphthodiazepine-5-sulfonate, 3,3, 3,3,-tetradecyl-1,1,-spiro-5,6,7,5',6f,7'-hexanol_1,2-naphthyldiazepine-4-sulfonate, 3,3,3,,3,·tetradecyl-1,1'-spiro-5,6,7,5,6,J'-hexanol-1,2.naphthyldiazepine-5- Sulfonate, 2,2,4-trimethyl-7,2,4,3-trihydroxyflavan-i,2.naphthyldiazepine_4_sulfonate, 2,2,4-trimethyl Base _7,2,,4'-trihydroxyl Flavan-naphthyldiazolium_5-sulfonate and the like. The content of the diazonium compound (B) in the present invention is preferably from 2 to 5 % by weight, more preferably up to 4 % by weight. The content of the diazonium compound is preferably within the above range to increase the difference in the dissolution rate between the non-exposed portion and the exposed portion, so that a high film residual ratio can be maintained in development. As for the coloring to be used in the present invention

上述之重氮醌化合物（B)可各單獨或者兩種或更多種 口併使用。以輻射線感應樹脂組成物的固含量計之，本發 ，可述及染料及顏料 而且該等可單獨或以The above diazonium compound (B) may be used singly or in combination of two or more kinds. Based on the solid content of the radiation-inducing resin composition, the present invention may describe dyes and pigments and these may be used alone or in

色热機顏料所成群 貢料’較佳為顯示高彩色顯影性 更it為頒示而耐熱分解性的彦員 319342 200809412 料，尤其較佳為碳黑與兩種或更多種有機顏料的組合。 視所需之吸收光譜而定’可使用選自碳黑及有機顏料 之兩種或更多種的組合。更明確地說，較佳使用碳黑與一 種或多種有機顏料的組合，或者兩種或更多種有機顏料的 組合。 至於及黑，可述及者有C.I·顏料黑6、C.I·顏料黑7等。 明確地示例為爐黑如SAF、SAF-HS、ISAF、ISAF-LS、 ISAF-HS、HAF、HAF-LS、HAF-HS、NAF、FEF、FEF-HS、 SRF、SRF-LM、SRF-LS ' GPF、ECF、N-339、N-351 等； 熱解黑（thermal black)如FT、MT等；乙炔黑等。這些碳黑 可單獨或以兩種或更多種之混合物使用之。 本發明中碳黑以外之無機顏料的實例包含金屬氧化物 如鈦黑、Cu-Fe_Mn氧化物、合成鐵黑等。這些無機顏料可 單獨或以兩種或更多種之混合物使用之。 本發明中之有機顏料的實例包含分類成色彩索引 (C.I·，染工與著色師學會出版）之顏料的化合物，明確地 說，如下述之那些賦予色彩索弓丨（C L)號碼者。 C.I·顏料黃12、C.I·顏料黃13、c丄顏料黃Η、C.I·顏 料頁17、C.I·顏料黃20、C.I·顏料黃24、C.I·顏料黃31、 C.I·顏料黃55、C.I·顏料黃83、C.I.顏料黃93、C.I·顏料黃 109、c.l·顏料黃110、C I顏料黃138、C I•顏料黃139、 C.I·顏料黃15〇、C·;[•顏料黃1S3、C·〗·顏料黃154、C.I.顏 料貝155、C.I·顏料黃166、C.I·顏料黃168 ; C.I·顏料橘36、C.I·顏料橘43、C.I.顏料橘51、C.I·顏 16 319342 200809412 料橘61、C.I.顏料橘71 ; c · I ·顏料么π • 、 、 9、C.I·顏料紅 97、C.I·顏料紅 122、c I 荈 料紅123、c Τ鉍w 顏 . ••顔料紅顏料紅168、C.I·顏料紅176、 C · I ·顏料红17 7、 • C.I·顏料紅1⑽、c.l·顏料紅209、C I鴻 料紅215、C I祐刹^ ， ·顔 ，丄顏枓紅224、C.I·顏料紅242、C.I·顏料紅254; CJ·顏料紫19、C.I·顏料紫23、C.I·顏料紫29 ; CJ·顏料藍15、C.I·顏料藍60、C.I·顏料藍15:3、cx 顏料監15 ·· 4、ρ τ紅λ丨4 β C.I·顏料藍 15:6 ; C.1.顏料綠7、C.I.顏料綠36 ; C.1.顏料棕23、C.I.顏料棕25 ; C.I·顏料黑^ ^也‘擇及使用這些有機顏料以獲得所要的色調。 、料視^形可與體質顏料（body pigment)—起使用。體 質彥員 / 、焉例包含硫酸鋇、碳酸鋇、碳酸鈣、二氧化矽、 驗式石炭酸H # ^ 、、 恭土白、光澤白、緞光白、水滑石等。這些 體貝顏料可單獨或以兩種或更多種之混合物使用之。以 B重星伤黑色顏料計之，該體質顏料的用量較佳為1⑽ 重里知或更少’更佳為50重量份或更少，又更佳為40重 量份或更少。 _ 本發明之正型彩色輻射線感應樹脂組成物較佳進一步 含有①)有機溶劑。 有機溶劑（D)的實例包含乙二醇單烷基醚，如乙二醇單 土…乙二醇單乙基醚、乙二醇單丙基謎、乙二醇單丁 基醚箄·一 ^ 、，一乙二醇二炫基鱗，如二乙二醇二甲基鱗、二乙 319342 17 200809412 二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基峻、 二乙二醇甲基乙基醚、二乙二醇甲基異丙基醚等；乙二醇 炫基趟乙酸酯，如甲基溶纖素乙酸酯、乙基溶纖素乙酸駿 專，丙一醇烧基乙酸醋，如丙二醇單甲基_乙酸酯、丙 一醇單乙基醚乙酸酯、丙二醇單丙基_乙酸酯等；芳香族 烴類，如苯、甲苯、二曱苯等；酮類，如曱基乙基酮:= 酮、甲基戊基酮、曱基異丁基酮、環己酮等；醇類，如乙 醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等；酯類， 如3-乙氧基丙酸乙酯、3-曱氧基丙酸甲酯、乳酸甲酯、乳 酸乙酯、乳酸丙酯、乳酸丁酯、2_羥基異丁酸甲酯、乙酸 丁酯、乙酸戊酯、乙酸異戊酯、丙酮酸甲酯等；環狀酯類， 如r -丁内酯等。 '' 可混合並使用兩種或更多種有機溶劑作為有機溶 ⑼。 蜊 有機溶劑（D)之較佳組合的實例包含下述組合：二乙一 醇二甲基醚與乳酸了 g旨、：乙：醇乙基甲基㈣與乳酸丁 酯、丙二醇單甲基醚乙酸酯與二乙二醇二甲基醚、丙二 單甲基醚乙酸醋與乳酸丁酯、％乙氧基丙酸乙酿與乳酸丁 酯、3-乙氧基丙酸乙酯與丙二醇單甲基醚乙酸酯、二乙二 醇甲^乙基醚與3_乙氧基丙酸乙醋、二乙二醇甲基:基: 與^酸I酉曰、二!^二醇甲基乙基趟與3·乙氧基丙酸乙酉旨與 礼I 丁酯、3-乙氧基丙酸乙酯與乙酸丁酯與乳酸丁酯等。 以正型彩色幸畐射線感應樹脂組成物計之，該有^溶: ⑼的含量較佳為50至95重量％，更佳為65至9q重量^ 319342 18 200809412 該有機溶劑（D)的含量較佳在上述範圍内，因而有能夠形成 優異平坦性膜的傾向。 本發明之正型彩色輻射線感應樹脂組成物除了（A)鹼 溶性固化樹脂，（B)重氮醒化合物，（C)著色劑及（D)有機溶 劑外，亦可含有（E)聚合反應起始劑，（F)多價酚化合物，（G) 交聯劑，及（H)可聚合化合物。 至於上述之聚合反應起始劑（E)，可述及者有作為陽離 子聚合反應起始劑之鏽鹽。上述鑌鹽係由鑌陽離子與源自 路易士酸之陰離子所構成。 上述鏽陽離子的特定實例包含二苯基碘鏽、雙（對-曱 苯基)碘鏽、雙（對-第三丁基苯基）碘鏽、雙（對-辛基苯基） 碘鏽、雙（對-十八烷基苯基）碘鏽、雙（對-辛氧基苯基）碘 鏽、雙（對-十八烷基苯基）碘鏽、雙（對-十八烷氧基苯基）碘 鏽、（對-甲苯基）（對-異丙基苯基）碘鏽、三苯基銃、叁（對-曱苯基）銃、叁（對-異丙基苯基）锍、叁（2,6-二曱基苯基）锍、 叁（對-第三丁基苯基）鏟、叁（對-氰基苯基）锍、叁（對-氯苯 基）锍、二曱基（甲氧基苯基）銃、二曱基（乙氧基苯基）銃、 二甲基（丙氧基苯基）锍、二曱基（丁氧基苯基）鎞、二甲基（辛 氧基苯基）锍、二曱基（十八烷氧苯基）銃、二曱基（異丙氧基 苯基）銃、二甲基（第三丁氧基苯基）銕、二曱基（環戊氧基苯 基）锍、二甲基（環己氧基苯基）銃、二曱基（氟曱氧基苯基） 鏟、二曱基（2-氯乙氧基苯基）锍、二甲基（3-溴丙氧基苯基） 锍、二曱基（4-氰基丁氧基苯基）锍、二曱基（8-硝基辛氧基 苯基）锍、二甲基（18-三氟曱基十八烷氧苯基）锍、二曱基（2- 19 319342 200809412 羥基異丙氧基苯基）鏟、二曱基（叁（三氯曱基）甲基）锍等。 較佳之鑌陽離子可述及者有雙（對-曱苯基）碘鑌、（對-曱苯基）（對-異丙基苯基）碘鏽、雙（對-第三丁基苯基）碘 鏽、三苯基銃、叁（對-第三丁基苯基）銃等。 上述源自路易士酸之陰離子的特定實例包含六氟填酸 鹽、六氟砷酸鹽、六氟銻酸鹽、肆（五氟苯基）硼酸鹽等。 至於較佳之源自路易士酸之陰離子可述及者有六氟銻酸鹽 及肆（五氟苯基）硼酸鹽。 上述之鑌陽離子與源自路易士酸之陰離子可任意組 合。 陽離子聚合反應起始劑（E)的特定實例包含六氟磷酸 二苯基碘鏽、六氟磷酸雙（對-曱苯基）碘鏽、六氟磷酸雙（對 -第三丁基苯基）碘鏽、六氟磷酸雙（對-辛基苯基）碘鑌、六 氟磷酸雙（對-十八烷基苯基）碘鏽、六氟磷酸雙（對-辛氧基 本基）破麵、六氣填酸雙（對-十八烧氧基苯基）蛾麵、六氣石粦 酸苯基（對-十八烷氧基苯基）碘鑌、六氟磷酸（對-甲苯基） (對-異丙基苯基）碘鏽、六氟磷酸曱基萘基碘鏽、六氟磷酸 乙基萘基碘鏽、六氟磷酸三苯基鎞、六氟磷酸叁（對-甲苯基） 疏、六氣填酸卷（對-異丙基苯基）疏、六氣構酸卷（2，6-二曱 基苯基）锍、六氟磷酸叁（對-第三丁基苯基）銃、六氟磷酸叁 (對-氣基苯基）疏、六氟構酸卷（對-氯苯基）锍、六氟鱗酸二 甲基萘基锍、六氟磷酸二乙基萘基銃、六氟磷酸二曱基（曱 氧基苯基）锍、六氟磷酸二甲基（乙氧基苯基）銕、六氟磷酸 二曱基（丙氧基苯基）锍、六氟磷酸二甲基（丁氧基苯基）锍、 20 319342 200809412 六氟磷酸二甲基（辛氧基苯基）鏟、六氟磷酸二曱基（十八烷 氧基苯基）銃、六氟磷酸二甲基（異丙氧基苯基）銕、六氟磷 酸二甲基（第三丁氧基苯基）锍、六氟磷酸二曱基（環戊氧基 苯基）鏟、六氟磷酸二曱基（環己氧基苯基）銃、六氟磷酸二 曱基（氟甲氧基）銃、六氟磷酸二甲基（2-氯乙氧基苯基）銃、 六氟磷酸二曱基（3-溴丙氧基苯基）锍、六氟磷酸二曱基（4-氰基丁氧基苯基）锍、六氟磷酸二甲基（8-硝基辛氧基苯基) 鏟、六氟磷酸二曱基（18-三氟曱基十八烷氧基苯基）銃、六 氟磷酸二曱基（2-羥基異丙氧基苯基）锍、六氟磷酸二曱基 (叁（三氯甲基）曱基）锍； 六氟砷酸二苯基碘鏽、六氟砷酸雙（對-曱苯基）碘鏽、 六氟砷酸雙（對-第三丁基苯基）碘鏽、六氟砷酸雙（對-辛基 苯基）硤鑌、六氟神酸雙（對-十八烧基苯基）蛾鏽、六氟珅酸 雙（對-辛氧基苯基）碘鏽、六氟砷酸雙（對-十八烷氧基苯基） 碘鏽、六氟砷酸苯基（對-十八烷氧基苯基）磺鏽、六氟砷酸 (對-甲苯基）（對-異丙基苯基）碘鏽、六氟珅酸曱基萘基碘 鑌、六氟砷酸乙基萘基碘鏽、六氟砷酸三苯基銃、六氟砷 酸卷（對-曱苯基）録L、六氟珅酸卷（對-異丙基苯基）疏、六氟 砷酸叁（2,6-二甲基苯基）銃、六氟砷酸叁（對-第三丁基苯基） 锍、六氟砷酸叁（對-氰基苯基）锍、六氟砷酸叁（對-氯苯基） 锍、六氟砷酸二曱基萘基銃、六氟砷酸二乙基萘基鎞、六 氟砷酸二甲基（曱氧基苯基）銃、六氟砷酸二甲基（乙氧基苯 基）録L、六氟神酸二甲基（丙氧基苯基）疏、六氟石申酸二曱基 (丁氧基苯基）疏、六氟珅酸二甲基（辛氧基苯基）鍈、六氟石申 21 319342 200809412 酸二甲基（十八烷氧基苯基）銃、六氟珅酸二曱基（異丙氧基 苯基）銃、六氟砷酸二曱基（第三丁氧基苯基）锍、六氟砷酸 二甲基（環戊氧基苯基）锍、六氟砷酸二曱基（環己氧基苯基) 録L、六氟珅酸二曱基（氟甲氧基苯基）疏、六氟坤酸二曱基 (2-氯乙氧基苯基）锍、六氟砷酸二甲基（3-溴丙氧基苯基） 録L、六氟砷酸二甲基（4-氰基丁氧基苯基）锍、六氟砷酸二 曱基（8-硝基辛氧基苯基）銃、六氟砷酸二曱基（18-三氟曱基 十八烷氧基笨基）銃、六氟砷酸二曱基（2-羥基異丙氧基苯 基）銃、六氟砷酸二曱基（叁（三氯甲基）曱基）銃； 六氟銻酸二苯基碘鑌、六氟銻酸雙（對-曱苯基）碘鏽、 六氟銻酸雙（對-第三丁基苯基）碘鏽、六氟銻酸雙（對-辛基 苯基）碘鏽、六氟銻酸雙（對-十八烷基苯基）碘鏽、六氟銻酸 雙（對-辛氧基苯基）碘鏽、六氟銻酸雙（對-十八烷氧基苯基） 碘鑌、六氟録酸苯基（對-十八烷氧基苯基）碘鑌、六氟銻酸 (對-甲苯基）（對-異丙基苯基）碘鏽、六氟銻酸曱基萘基碘 鏽、六氟銻酸乙基萘基碘鏽、六氟銻酸三苯基銃、六氟銻 酸卷（對-曱苯基）疏、六氟銻酸卷（對-異丙基苯基）録L、六氣 銻酸叁（2,6-二甲基苯基）锍、六氟銻酸叁（對-第三丁基苯基） 銃、六氟銻酸叁（對-氰基苯基）鑪、六氟銻酸叁（對-氯苯基） 銃、六氟銻酸二甲基萘基鏟、六氟銻酸二乙基萘基锍、六 氟銻酸二曱基（曱氧基苯基）銃、六氟銻酸二甲基（乙氧基苯 基）鏟、六氟銻酸二甲基（丙氧基苯基）锍、六氟銻酸二曱基 (丁氧基苯基）锍、六氟銻酸二甲基（辛氧基苯基）銃、六氟銻 酸二甲基（十八烷氧基苯基）銃、六氟銻酸二甲基（異丙氧基 22 319342 200809412 苯基）疏、六氟銻酸二曱基（第三丁氧基苯基）锍、六氟銻酸 二甲基（環戊氧基苯基）銃、六氟銻酸二T基（環己氧基苯基) 録L、六氟銻酸二甲基（氟曱氧基苯基）疏、六氟録酸二甲基 (2-氯乙氧基苯基）锍、六氟銻酸二曱基（3-溴丙氧基苯基） 疏、六氟録酸二甲基（4-氰基丁氧基苯基）锍、六氟銻酸二 曱基（8 -石肖基辛乳基苯基）録l、六氣録酸二甲基（18-三氣甲基 十八烷氧基苯基）銃、六氟銻酸二曱基（2-羥基異丙氧基苯 基）锍、六氟銻酸二曱基（叁（三氯甲基）曱基）銃； 肆（五氟苯基）硼酸二苯基碘鏽、肆（五氟苯基）獨酸雙 (對-曱苯基）碘鏽、肆（五氟苯基）硼酸雙（對-第三丁基苯基） 碘鏽、肆（五氟苯基）硼酸雙（對-辛基苯基）碘鏽、肆（五氟苯 基）硼酸雙（對-十八烷基苯基）碘鏽、肆（五氟苯基）硼酸雙 (對-辛氧基苯基）碘鏽、肆（五氟苯基）硼酸雙（對-十八烷氧 基苯基）碘鏽、肆（五氟苯基）硼酸苯基（對-十八烷氧基苯基） 碘鏽、肆（五氟苯基）硼酸（對-曱苯基）（對-異丙基苯基）碘 鏽、肆（五氟苯基）硼酸曱基萘基碘鏽、肆（五氟苯基）硼酸乙 基萘基碘鏽、肆（五氟苯基）酸三苯基锍、肆（五氟苯基） 硼酸叁（對-曱苯基）銃、肆（五氟苯基）硼酸叁（對-異丙基苯 基）锍、肆（五氟苯基）硼酸叁（2,6-二曱基苯基）锍、肆（五氟 苯基）硼酸叁（對-第三丁基苯基）銃、肆（五氟苯基）硼酸叁 (對-氰基苯基）锍、肆（五氟苯基）硼酸叁（對-氯苯基）銃、肆 (五氟苯基）硼酸二甲基萘基銕、肆（五氟苯基）硼酸二乙基萘 基銃、肆（五氟苯基）硼酸二曱基（甲氧基苯基）銕、肆（五氟 苯基）硼酸二曱基（乙氧基苯基）鈒、肆（五氟苯基）硼酸二甲 23 319342 200809412 % 基（丙氧基苯基）锍、肆（五氟苯基）硼酸二甲基（丁氧基苯基） 銃、肆（五氟苯基）硼酸二甲基（辛氧基苯基）銃、肆（五氟苯 基）硼酸二甲基（十八烷氧基苯基）銃、肆（五氟苯基）硼酸二 曱基（異丙氧基苯基）锍、肆（五氟苯基）硼酸二甲基（第三丁 氧基苯基）锍、肆（五氟苯基）硼酸二甲基（環戊氧基苯基） 銃、肆（五氟苯基）硼酸二甲基（環己氧基苯基）锍、肆（五氟 苯基）石朋酸二曱基（氟曱氧基苯基）銃、肆（五氟苯基）硼酸二 曱基（2-氯乙氧基苯基）锍、肆（五氟苯基）酸二曱基（3-溴 丙氧基苯基)銃、肆（五氟苯基）酸二甲基（4-氰基丁氧基苯 基）銃、肆（五氟苯基）酸二甲基（8-硝基辛氧基苯基）銃、 肆（五氟苯基）硼酸二甲基（18-三氟曱基十八烷氧基苯基） 銕、肆（五氟苯基）硼酸二曱基（2-羥基異丙氧基苯基）銕、肆 (五氟苯基）硼酸二曱基（叁（三氯甲基）甲基）毓等。 其中，較佳為六氟磷酸雙（對-曱苯基）碘鏽、六氟磷酸 (對-甲苯基）（對-異丙基苯基）碘鑌、六氟磷酸雙（對-第三丁 基苯基）碘鑌、六氟磷酸三苯基銃、六氟磷酸叁（對-第三丁 基苯基）銃、六氟砷酸雙（對-曱苯基）碘鏽、六氟砷酸（對-曱 苯基）（對-異丙基苯基）碘鑌、六氟砷酸雙（對-第三丁基苯基) 碘鏽、六氟砷酸三苯基銃、六氟砷酸叁（對-第三丁基苯基） 锍、六氟銻酸雙（對-曱苯基）碘鏽、六氟銻酸（對-曱苯基）（對 -異丙基苯基）碘鏽、六氟銻酸雙（對-第三丁基苯基）碘鏽、 六氟銻酸三苯基鏽、六氟銻酸叁（對-第三丁基苯基）銃、肆 (五氟苯基）硼酸雙（對-曱苯基）碘鑌、肆（五氟苯基）硼酸（對-甲苯基）（對-異丙基苯基）碘鑌、肆（五氟苯基）硼酸雙（對- 24 319342 200809412 f三丁基苯基）碘鏽、肆（五氟苯基）硼酸三苯基毓及肆（五氟 苯蝴酸卷（對.第三丁基苯基）疏，更佳為六說録酸雙（對- 1苯基^錐、六氟録酸（對-甲苯基）（對-異丙基苯基）峨 /、氟銻心雙（對·第二丁基苯基）填鏽、六氟銻酸三苯基 銃、六氟銻酸卷（對-第三丁基苯基）鎮、肆（五氣苯基㈣ς 雙（對甲苯基）蛾鑌、肆（五氟苯基）硼酸（對_甲苯基^對-異 1基苯基)硬鏽、肆（五敦苯基）賴雙（對_第三丁基苯基）峨 11 $(五氟苯基）硼酸二苯基銃及肆（五氟苯基）硼酸叁（對_ 第三丁基苯基）銃。 — 當含有聚合反應起始劑⑹時，以正型彩色輕射線感應 樹脂組成物之固含量的重量分率計之，其含量較佳為〇 〇1 至10曰重量％，更佳為（U至5重量％。聚合反應起始劑⑻ 々έ里車又it在上述範圍0 ’因❿可提升熱硬化時的硬化速 度’因此熱硬化時之解析度的下降受到抑制，再者，易於 改善硬化膜的耐溶劑性。 上述之多價紛化合物（F)包含分子中具有兩個或更多 ，性經基之化合物、經由至少使㈣基苯乙料為原料 單體所得到之聚合物、及酚醛樹脂等。 —上述之分子中具有兩個或更多個酚性羥基之化合物的 貫例包含三經基二苯甲酮類、四經基二苯甲_、五經基 、六經基二苯甲綱類、（多絲苯基）燒類及重 氮醌化合物說明中所示例者等。 經由至少使用經基苯乙烯作為原料單體所得到之聚合 物的特定實例包含藉由聚合經基苯乙稀所得到之樹脂，如 319342 25 200809412 基笨乙、歸經基苯乙烯/甲基丙稀酸甲酿共聚物、芦某 本乙烯/f基丙婦酸環己酯共聚物、經基苯 ^The tribute of the color heat machine pigments is preferably a high-color developability, which is a heat-decomposable 319342 200809412 material, especially preferably carbon black and two or more organic pigments. combination. Depending on the desired absorption spectrum, a combination of two or more selected from the group consisting of carbon black and organic pigment can be used. More specifically, it is preferred to use a combination of carbon black and one or more organic pigments, or a combination of two or more organic pigments. As for black, there are C.I. Pigment Black 6, C.I. Pigment Black 7, and the like. Specifically exemplified by furnace black such as SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRF, SRF-LM, SRF-LS 'GPF, ECF, N-339, N-351, etc.; thermal black such as FT, MT, etc.; acetylene black. These carbon blacks may be used singly or in combination of two or more. Examples of the inorganic pigment other than carbon black in the present invention include metal oxides such as titanium black, Cu-Fe_Mn oxide, synthetic iron black and the like. These inorganic pigments may be used singly or in combination of two or more. Examples of the organic pigment in the present invention include a compound classified into a pigment of a color index (C.I., published by the Society of Colorists and Colorists), specifically, those given the color cable (C L) number as described below. CI·Pigment Yellow 12, CI·Pigment Yellow 13, c丄Pigment Yellow, CI·Pig Sheet 17, CI·Pig Yellow 20, CI·Pig Yellow 24, CI·Pig Yellow 31, CI·Pig Yellow 55, CI· Pigment Yellow 83, CI Pigment Yellow 93, CI·Pigment Yellow 109, cl·Pig Yellow 110, CI Pigment Yellow 138, CI•Pigment Yellow 139, CI·Pig Yellow 15〇, C·; [• Pigment Yellow 1S3, C· 〗 〖Pigment Yellow 154, CI Pigment Shell 155, CI·Pigment Yellow 166, CI·Pigment Yellow 168; CI·Pigment Orange 36, CI·Pigment Orange 43, CI Pigment Orange 51, CI·Yan 16 319342 200809412 CI Pigment Orange 71; c · I · Pigment π • , , 9, CI·Pigment Red 97, CI·Pigment Red 122, c I 荈 Red 123, c Τ铋w 颜. ••Pigment Red Pigment Red 168, CI·Pigment Red 176, C · I · Pigment Red 17 7、• CI·Pigment Red 1 (10), cl·Pigment Red 209, CI Hongqihong 215, CI Youzhan ^, ·Yan, Yan Yanhong 224, CI·Pigment Red 242, CI·Pigment Red 254; CJ·Pigment Violet 19, CI·Pigment Violet 23, CI·Pigment Violet 29; CJ·Pigment Blue 15, CI·Pigment Blue 60, CI·Pigment Blue 15:3, cx Pigment Super 15 ·· 4, ρ τ red λ丨4 β CI·Pigment Blue 15:6 ; C.1. Pigment Green 7, CI Pigment Green 36; C.1. Pigment Brown 23, CI Pigment Brown 25; CI·Pigment Black ^ ^ Also use these organic pigments Get the desired color tone. The material can be used together with body pigment. Body fate / , examples include barium sulphate, barium carbonate, calcium carbonate, cerium oxide, test charcoal H # ^,, Gongbai white, glossy white, satin white, hydrotalcite and so on. These body shell pigments may be used singly or in combination of two or more. The amount of the extender pigment is preferably 1 (10) by weight or less, more preferably 50 parts by weight or less, still more preferably 40 parts by weight or less, based on the B heavy star black pigment. The positive color radiation sensing resin composition of the present invention preferably further contains 1) an organic solvent. Examples of the organic solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethane...ethylene glycol monoethyl ether, ethylene glycol monopropyl mystery, ethylene glycol monobutyl ether 箄·一^ ,, ethylene glycol dimercaptoscale, such as diethylene glycol dimethyl scale, diethylene 319342 17 200809412 diol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl sulphate, two Ethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, etc.; ethylene glycol dahuryl acetate, such as methyl fibrin acetate, ethyl fibrin acetate, Propylene alcohol-based acetic acid vinegar, such as propylene glycol monomethyl-acetate, propanol monoethyl ether acetate, propylene glycol monopropyl acetate, etc.; aromatic hydrocarbons, such as benzene, toluene, two Alkene or the like; ketones such as mercaptoethyl ketone: = ketone, methyl amyl ketone, decyl isobutyl ketone, cyclohexanone, etc.; alcohols such as ethanol, propanol, butanol, hexanol, Cyclohexanol, ethylene glycol, glycerin, etc.; esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate , 2-hydroxyisobutyric acid methyl ester, acetic acid Acetate, amyl acetate, isoamyl acetate, methyl pyruvate and the like; cyclic esters, such as r - butyrolactone. '' It is possible to mix and use two or more organic solvents as organic solvents (9). Examples of preferred combinations of the hydrazine organic solvent (D) include the following combinations: diethyl dimethyl ether and lactic acid, and: ethyl: alcohol ethyl methyl (tetra) with butyl lactate, propylene glycol monomethyl ether Acid esters with diethylene glycol dimethyl ether, propylene dimethicone acetic acid vinegar and butyl lactate, % ethoxy propionate ethyl and butyl lactate, 3-ethoxypropionate ethyl ester and propylene glycol single Methyl ether acetate, diethylene glycol methyl ethyl ether and 3_ethoxy propionic acid ethyl acetate, diethylene glycol methyl: base: with acid I酉曰, di! Ethyl hydrazine and ethoxylated acetoacetate are intended to be butyl butyl ester, ethyl 3-ethoxypropionate, butyl acetate and butyl lactate. The content of the (9) is preferably from 50 to 95% by weight, more preferably from 65 to 9% by weight, based on the composition of the positive color ray-sensing resin composition. 319342 18 200809412 The content of the organic solvent (D) It is preferable to be in the above range, and thus there is a tendency that an excellent flat film can be formed. The positive color radiation sensing resin composition of the present invention may contain (E) a polymerization reaction in addition to (A) an alkali-soluble curing resin, (B) a diazo awakening compound, (C) a coloring agent, and (D) an organic solvent. The initiator, (F) a polyvalent phenol compound, (G) a crosslinking agent, and (H) a polymerizable compound. As the above polymerization initiator (E), there may be mentioned a rust salt as a cationic polymerization initiator. The onium salt is composed of a phosphonium cation and an anion derived from Lewis acid. Specific examples of the above rust cation include diphenyl iodine rust, bis(p-nonylphenyl) iodine rust, bis(p-tert-butylphenyl) iodine rust, bis(p-octylphenyl) iodine rust, Bis(p-octadecylphenyl) iodine, bis(p-octyloxyphenyl) iodine, bis(p-octadecylphenyl) iodine, bis(p-octadecyloxy) Phenyl) iodine rust, (p-tolyl) (p-isopropylphenyl) iodine, triphenyl sulfonium, fluorene (p-quinophenyl) fluorene, fluorene (p-isopropylphenyl) fluorene , 叁 (2,6-dimercaptophenyl) fluorene, hydrazine (p-tert-butylphenyl) shovel, hydrazine (p-cyanophenyl) fluorene, hydrazine (p-chlorophenyl) fluorene, two Mercapto (methoxyphenyl) fluorene, dimercapto (ethoxyphenyl) hydrazine, dimethyl (propoxyphenyl) fluorene, dimercapto (butoxyphenyl) fluorene, dimethyl (octyloxyphenyl) fluorene, didecyl (octadecyloxyphenyl) fluorene, diindolyl (isopropoxyphenyl) fluorene, dimethyl (tert-butoxyphenyl) fluorene, two Indenyl (cyclopentyloxyphenyl) fluorene, dimethyl (cyclohexyloxyphenyl) fluorene, dinonyl (fluorononyloxyphenyl) Shovel, dimercapto (2-chloroethoxyphenyl) hydrazine, dimethyl (3-bromopropyloxyphenyl) fluorene, dimercapto (4-cyanobutoxyphenyl) fluorene, diterpenes (8-Nitrooctyloxyphenyl) fluorene, dimethyl (18-trifluorodecyl octadecyloxyphenyl) fluorene, dimercapto (2- 19 319342 200809412 hydroxyisopropoxyphenyl) Shovel, dimercapto (indenyl (trichloroindenyl) methyl) hydrazine, etc. Preferred ruthenium cations are bis(p-nonylphenyl)iodonium, (p-nonylphenyl)(p-isopropylphenyl) iodine, bis(p-tert-butylphenyl). Iodine rust, triphenyl hydrazine, hydrazine (p-tert-butylphenyl) hydrazine, and the like. Specific examples of the above anion derived from Lewis acid include hexafluoride acid salt, hexafluoroarsenate salt, hexafluoroantimonate salt, ruthenium (pentafluorophenyl) borate salt, and the like. As the preferred anion derived from Lewis acid, there may be mentioned hexafluoroantimonate and quinone (pentafluorophenyl) borate. The above ruthenium cation and the anion derived from Lewis acid may be arbitrarily combined. Specific examples of the cationic polymerization initiator (E) include diphenyl iodine hexafluorophosphate, bis(p-nonylphenyl) iodine hexafluorophosphate, and bis(p-tert-butylphenyl) hexafluorophosphate. Iodine rust, bis(p-octylphenyl) iodonium hexafluorophosphate, bis(p-octadecylphenyl) iodine hexafluorophosphate, bis(p-octyloxy) hexafluorophosphate, Hexahydrate filled bis(p-octadecyloxyphenyl) moth face, hexachlor phthalate phenyl (p-octadecyloxyphenyl) iodonium, hexafluorophosphate (p-tolyl) ( P-isopropylphenyl) iodine rust, decylnaphthyl iodine hexafluorophosphate, ethylnaphthyl iodine hexafluorophosphate, triphenyl sulfonium hexafluorophosphate, bismuth hexafluorophosphate (p-tolyl) , six gas filled acid coil (p-isopropylphenyl) sparse, six-gas acid acid coil (2,6-dimercaptophenyl) fluorene, hexafluorophosphate (p-tert-butylphenyl) hydrazine , bismuth hexafluorophosphate (p-phenylphenyl), hexafluoroacid (p-chlorophenyl) fluorene, dimethylnaphthyl hexafluoroantimonate, diethylnaphthyl hexafluorophosphate, Dinonyl hexafluorophosphate (decyloxyphenyl) ruthenium, hexafluorophosphorus Dimethyl(ethoxyphenyl)anthracene, dinonyl (propoxyphenyl)phosphonium hexafluorophosphate, dimethyl(butoxyphenyl)phosphonium hexafluorophosphate, 20 319342 200809412 hexafluorophosphate Sodium (octyloxyphenyl) shovel, diamyl hexafluorophosphate (octadecyloxyphenyl) fluorene, dimethyl (isopropoxyphenyl) hexafluorophosphate, dimethyl hexafluorophosphate Tert-butoxyphenyl)anthracene, diamyl hexafluorophosphate (cyclopentyloxyphenyl) shovel, dinonyl hexafluorophosphate (cyclohexyloxyphenyl) fluorene, difluorol hexafluorophosphate (fluorine Methoxy)anthracene, dimethyl(2-chloroethoxyphenyl)phosphonium hexafluorophosphate, dinonyl (3-bromopropoxyphenyl)phosphonium hexafluorophosphate, diindolyl hexafluorophosphate (4 -Cyanobutoxyphenyl)anthracene, dimethyl hexafluorophosphate (8-nitrooctyloxyphenyl) shovel, dinonyl hexafluorophosphate (18-trifluorodecyl octadecyloxyphenyl)铳, dinonyl hexafluorophosphate (2-hydroxyisopropoxyphenyl) fluorene, dimercapto hexafluorophosphate (phosphonium (trichloromethyl) fluorenyl) hydrazine; hexafluoroarsenic acid diphenyl iodine rust , hexafluoroarsenic acid bis(p-nonylphenyl) iodine rust, six Bis(p-tert-butylphenyl) iodine arsenate, bis(p-octylphenyl)phosphonium hexafluoroarsenate, bis(p-octadecanylphenyl) moth rust, Bis(p-octyloxyphenyl) iodine hexafluoroantimonate, bis(p-octadecyloxyphenyl) iodine hexafluoroarsenate, phenyl hexafluoroarsenate (p-octadecyloxy) Phenyl) sulfonate, hexafluoroarsenic acid (p-tolyl) (p-isopropylphenyl) iodine, decylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodine hexafluoroarsenate, Triphenylsulfonium hexafluoroarsenate, hexafluoroarsenic acid coil (p-nonylphenyl) recorded L, hexafluoroantimonic acid (p-isopropylphenyl) sparse, bismuth hexafluoroarsenate (2,6- Dimethylphenyl)anthracene, ruthenium hexafluoroarsenate (p-tert-butylphenyl) ruthenium, ruthenium hexafluoroarsenate (p-cyanophenyl) ruthenium, ruthenium hexafluoroarsenate (p-chlorobenzene) Base, bismuthylnaphthyl ruthenium hexafluoroarsenate, diethylnaphthyl ruthenium hexafluoroarsenate, dimethyl (decyloxyphenyl) ruthenium hexafluoroarsenate, dimethyl hexafluoroarsenate Ethoxyphenyl) is recorded as L, hexafluoroantimonic acid dimethyl (propoxyphenyl) sparse, hexafluorolithic acid dimercapto (butoxyphenyl), Dimethyl(octyloxyphenyl)phosphonium hexafluoroantimonate, hexafluorite 21 319342 200809412 Dimethyl (octadecyloxyphenyl) sulfonate, dinonyl hexafluoroantimonate (isopropoxy) Phenyl)anthracene, dinonyl (t-butoxyphenyl) ruthenium hexafluoroarsenate, dimethyl (cyclopentyloxyphenyl) ruthenium hexafluoroarsenate, dinonyl hexafluoroarsenate (cyclohexane) Oxyphenyl) L, hexafluoroantimonate difluoro (fluoromethoxyphenyl), hexafluoro-nonyl (dichloroethoxyphenyl) fluorene, hexafluoroarsenate (3-bromopropyloxyphenyl) L, hexafluoroarsenic acid dimethyl (4-cyanobutoxyphenyl) fluorene, hexafluoroarsenate dimercapto (8-nitrooctyloxybenzene) Bismuth, ruthenium hexafluoroarsenate (18-trifluorodecyl octadecyloxy) fluorene, hexafluoroarsenate dinonyl (2-hydroxyisopropoxyphenyl) fluorene, hexafluoro Di-decyl arsenate (decyl (trichloromethyl) decyl) hydrazine; diphenyl iodonium hexafluoroantimonate, bis(p-nonylphenyl) iodine hexafluoroantimonate, hexafluoroantimonic acid bis (pair) -T-butylphenyl)iodine rust, bis(p-octylphenyl) iodine hexafluoroantimonate, hexafluoroantimonic acid double (p-eighteen Phenyl phenyl) iodine rust, bis(p-octyloxyphenyl) iodine hexafluoroantimonate, bis(p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl hexafluoroantimonate P-octadecyloxyphenyl)iodonium, hexafluoroantimonic acid (p-tolyl) (p-isopropylphenyl) iodine, decylnaphthyl iodine hexafluoroantimonate, hexafluoroantimonic acid Ethylnaphthyl iodide rust, triphenyl sulfonium hexafluoroantimonate, hexafluoroantimonic acid (p-phenylene), hexafluoroantimonic acid (p-isopropylphenyl), L, six gas Barium (2,6-dimethylphenyl)anthracene, ruthenium hexafluoroantimonate (p-tert-butylphenyl) ruthenium, ruthenium hexafluoroantimonate (p-cyanophenyl) furnace, hexafluoroantimony Barium (p-chlorophenyl) hydrazine, dimethylnaphthyl hexafluoroantimonate, diethylnaphthyl hexafluoroantimonate, dinonyl hexafluoroantimonate (decyloxyphenyl) fluorene, six Dimethyl(ethoxyphenyl) shovel fluoroantimonate, dimethyl(propoxyphenyl)phosphonium hexafluoroantimonate, dinonyl (butoxyphenyl)phosphonium hexafluoroantimonate, hexafluoroantimony Acid dimethyl (octyloxyphenyl) hydrazine, hexafluoroantimonate dimethyl (octadecyloxyphenyl) fluorene, hexafluoroantimonate dimethyl ( Propyloxy 22 319342 200809412 Phenyl), diamyl hexafluoroantimonate (t-butoxyphenyl) hydrazine, hexafluoroantimonate dimethyl (cyclopentyloxyphenyl) fluorene, hexafluoroantimonic acid Di-T-based (cyclohexyloxyphenyl) L, hexafluoroantimonate dimethyl (fluorodecyloxyphenyl), hexafluoroanthenic acid dimethyl (2-chloroethoxyphenyl) hydrazine, Dimethyl hexafluoroantimonate (3-bromopropyloxyphenyl), hexafluoroantimony dimethyl (4-cyanobutoxyphenyl) fluorene, hexafluoroantimonate dimercapto (8 - Shi Xiaoji Octyl phenyl), l, hexahydrate, dimethyl (18-trimethylmethyloctadecyloxyphenyl) hydrazine, hexafluoroantimonate dinonyl (2-hydroxyisopropoxyphenyl)锍, bismuth hexafluorodecanoate (叁 (trichloromethyl) fluorenyl) 铳; 肆 (pentafluorophenyl) borate diphenyl iodine, bismuth (pentafluorophenyl) monoacid bis (pair - Phenyl phenyl) iodine rust, bismuth (pentafluorophenyl) borate bis(p-tert-butylphenyl) iodine rust, bismuth (pentafluorophenyl) borate bis(p-octylphenyl) iodine, ruthenium (pentafluorophenyl)boronic acid bis(p-octadecylphenyl) iodine rust, quinone (pentafluorophenyl)boronic acid bis ( -octyloxyphenyl) iodine rust, bis(p-octadecyloxyphenyl) iodine ruthenium, pentium (pentafluorophenyl)boronic acid phenyl (p-octadecyloxy) Phenyl phenyl) iodine rust, ruthenium (pentafluorophenyl) boric acid (p-nonylphenyl) (p-isopropylphenyl) iodine, ruthenium (pentafluorophenyl) borate decylnaphthyl iodine, ruthenium (Pentafluorophenyl)boronic acid ethylnaphthyl iodide rust, quinone (pentafluorophenyl) acid triphenyl sulfonium, hydrazine (pentafluorophenyl) borohydride (p-quinone phenyl) fluorene, quinone (pentafluorobenzene) Base) bismuth borate (p-isopropylphenyl) ruthenium, osmium (pentafluorophenyl) borate bismuth (2,6-dimercaptophenyl) ruthenium, osmium (pentafluorophenyl) borate bismuth (p-the Tributylphenyl) ruthenium, osmium (pentafluorophenyl) borate bismuth (p-cyanophenyl) ruthenium, osmium (pentafluorophenyl) borate bismuth (p-chlorophenyl) ruthenium, iridium (pentafluorobenzene) Dimethylnaphthyl boron borate, diethyl naphthyl anthracene (pentafluorophenyl)borate, dimercapto (methoxyphenyl) fluorene, ruthenium (pentafluorobenzene) Dialkyl bis(ethoxyphenyl) ruthenium, osmium (pentafluorophenyl) boric acid A 23 319342 200809412 % propyl (propoxyphenyl) ruthenium, ruthenium (pentafluorophenyl) borate dimethyl (butoxyphenyl) ruthenium, osmium (pentafluorophenyl) borate dimethyl (octyloxy) Phenyl) hydrazine, hydrazine (pentafluorophenyl)boronic acid dimethyl (octadecyloxyphenyl) fluorene, hydrazine (pentafluorophenyl) borate didecyl (isopropoxyphenyl) fluorene, hydrazine ( Pentafluorophenyl)boronic acid dimethyl(t-butoxyphenyl)anthracene, quinone (pentafluorophenyl)boronic acid dimethyl (cyclopentyloxyphenyl) ruthenium, osmium (pentafluorophenyl)borate Methyl (cyclohexyloxyphenyl) ruthenium, osmium (pentafluorophenyl) sphaphonic acid dinonyl (fluorononyloxyphenyl) ruthenium, ruthenium (pentafluorophenyl) borate dinonyl (2-chloro Ethoxyphenyl) ruthenium, osmium (pentafluorophenyl) acid di-decyl (3-bromopropyloxyphenyl) ruthenium, ruthenium (pentafluorophenyl) acid dimethyl (4-cyanobutoxyl) Phenyl) hydrazine, hydrazine (pentafluorophenyl) acid dimethyl (8-nitrooctyloxyphenyl) fluorene, hydrazine (pentafluorophenyl) borate dimethyl (18-trifluorodecyl octadecane) Oxyphenyl) ruthenium, osmium (pentafluorophenyl) borate dinonyl (2-hydroxyiso) Propyloxyphenyl) hydrazine, hydrazine (pentafluorophenyl)boronic acid dimercapto (phosphonium (trichloromethyl)methyl) hydrazine, and the like. Among them, preferred is bis(p-nonylphenyl) iodine hexafluorophosphate, hexafluorophosphoric acid (p-tolyl) (p-isopropylphenyl) iodonium, hexafluorophosphate bis (p-butadiene) Phenyl phenyl) iodonium, triphenyl sulfonium hexafluorophosphate, bismuth hexafluorophosphate (p-tert-butylphenyl) fluorene, bis(p-nonylphenyl) iodine hexafluoroarsenate, hexafluoroarsenic acid (p-phenylphenyl)(p-isopropylphenyl)iodonium, bis(p-tert-butylphenyl) hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, hexafluoroarsenic acid叁(p-tert-butylphenyl) hydrazine, bis(p-nonylphenyl) iodine hexafluoroantimonate, hexafluoroantimonic acid (p-nonylphenyl) (p-isopropylphenyl) iodine , hexafluoroantimonic acid bis(p-tert-butylphenyl) iodine rust, hexafluoroantimonate triphenyl rust, hexafluoroantimonate bismuth (p-tert-butylphenyl) ruthenium, iridium (pentafluorobenzene) Bis(bis-p-indolephenyl) iodonium, hydrazine (pentafluorophenyl)boronic acid (p-tolyl) (p-isopropylphenyl) iodonium, quinone (pentafluorophenyl)boronic acid bis ( -24 319342 200809412 f Tributylphenyl) iodine rust, triphenyl sulfonium quinone (pentafluorophenyl) borate and hydrazine Pentafluorobenzene acid acid coil (p. tert-butylphenyl) sparse, more preferably six said acid double (p-phenylene cone, hexafluoro acid (p-tolyl) (p-isopropyl) Phenyl) fluorene, fluorinated bismuth (p-butyl phenyl) rust, triphenyl sulfonium hexafluoroantimonate, hexafluoroantimonic acid (p-tert-butylphenyl),肆(five-pure phenyl(tetra)phosphonium bis(p-tolyl) moth, quinone (pentafluorophenyl)boronic acid (p-tolyl^p-iso-1-ylphenyl) hard rust, bismuth (five phenyl) lysine (p-tert-butylphenyl) 峨11 $ (pentafluorophenyl)boronic acid diphenyl hydrazine and hydrazine (pentafluorophenyl) borate bismuth (p-tert-butylphenyl) hydrazine. The reaction initiator (6) is preferably 〇〇1 to 10% by weight, more preferably (U to 5% by weight) based on the weight fraction of the solid content of the positive color light ray-sensitive resin composition. The polymerization initiator (8) is also in the above range 0 'Because it can increase the hardening rate at the time of thermal hardening', so the decrease in the resolution at the time of heat hardening is suppressed, and further, it is easy to improve the resistance of the cured film. Solvent. The polyvalent compound (F) comprises a polymer having two or more compounds in the molecule, a polymer obtained by using at least a (tetra)phenylbenzene as a raw material monomer, a phenol resin, etc. - the above Examples of compounds having two or more phenolic hydroxyl groups in the molecule include tris-based benzophenones, tetra-based benzophenones, penta-based groups, hexa-based diphenylmethyls, (multifilaments) Phenyl) and diazonium compounds are exemplified in the description. Specific examples of the polymer obtained by using at least styrene-based styrene as a raw material monomer include a resin obtained by polymerizing styrene-butadiene, Such as 319342 25 200809412 base stupid, styrene-based styrene / methyl acrylate acid copolymer, a certain ethylene / f-based propylene cyclohexyl ester copolymer, benzene

聚物、絲苯乙频氧基苯乙稀共聚物等。本乙L 至於上述之紛酸樹脂，可述及者，例如，藉 類、甲驗類及兒茶_所成群組之一種或多種化合物鱼選 自㈣㈣類所成群組之—種或多種化合物的 觸 得到之樹脂。 ％ 田3有上述之多價紛化合物（F)時，以正型彩色輕射線 感應樹脂組成物之固含量的重量分率計之，其含量較佳為 0.01至40重量％，更佳為〇.1至25重量％。 至於上述之交聯劑⑹，可述及者有經甲基化合物等。 至於上述之經甲基化合物，可述及者有烧氧基甲基化 胺基樹脂，如絲基甲基化蜜胺樹脂、絲基曱基化服樹 脂等。烧氧基甲基化蜜胺樹脂的實例包含甲氧基曱基化蜜 胺树月曰6氧基甲基化蜜胺樹脂、丙氧基甲基化蜜胺樹脂、 丁氧基甲基化蜜胺樹月旨等。烧氧基甲基化脲樹脂的實例包 含曱氧基甲基化脲樹脂、乙氧基甲基化脲樹脂、丙氧基甲 基化脲樹脂、丁氧基曱基化脲樹脂等。上述之交聯劑（g) 可各單獨使用或者兩種或更多種合併使用。 當含有交聯劑（G)時’以正型彩色輻射線感應樹脂組成 物之固含量的重量分率計之，其含量較佳 1至15重 %。交聯劑的含量較佳在上述範圍内，因而可改善如硬化 樹脂圖樣之性能。 至於上述之可聚合化合物，例如，可述及者有可藉 319342 26 200809412 由1…、予以自由基聚合之可聚合化合物或可陽離子聚合之 可水卞:匕合物等。至於較佳之可聚合化合物⑻，可述及者 有可陽離子聚合之可聚合化合物。 、、至於上述之可自由基聚合之可聚合化合物，例如，可 L及者有具有可聚合之碳·碳不飽和鍵之化合物等。具有可 聚合之碳-碳不飽和鍵之化合物可為單官能可聚合化合 物又g月b可合化合物、或多官能^三或更多官能）可聚 合化合物。 ^皁官能可聚合化合物的實例包含丙烯酸壬基苯基卡必 2醋、甲基丙埽酸壬基苯基卡必醇酯、丙烯酸2_經基_3_ 苯氧基丙酯、甲基丙烯酸2_羥基_3_苯氧基丙酯、丙烯酸 2乙基己基卡必醇酯、曱基丙烯酸2_乙基己基卡必醇酯、 丙烯酉夂2-每基乙g旨、曱基丙烯酸2_經基乙酯、Ν·乙烯基吡 咯烷酮等。 雙官能可聚合化合物的實例包含二丙烯酸丨，^己二醇 酯、二（甲基丙烯酸）1，6_己二醇酯、二丙烯酸乙二醇酯、二 (曱基丙稀酸）乙二醇酯、二丙晞酸新戊二醇酯、二（甲基丙 烯酸）新戊二醇酯、二丙烯酸三乙二醇酯、二（甲基丙烯酸) 三乙二醇酯、雙酚A之雙（丙烯醯氧基乙基）醚、二丙烯酸 3-甲基戊二醇、二（甲基丙烯酸）3-甲基戊二醇等。 夕B月b可聚合化合物的實例包含三丙烯酸三經甲基丙 烷酯、三（曱基丙烯酸）三羥甲基丙烷酯、三丙烯酸季戊四 醇酯、二（甲基丙烯酸）季戊四醇酯、四丙烯酸季戊四醇酯、 四（曱基丙烯酸）季戊四醇酯、五丙稀酸季戊四醇酯、五（曱 319342 27 200809412 參 基丙烯酸）季戊四醇醋、六丙烯酸二季戊四醇酯、六（曱基 丙烯酸）二季戊四醇酯等。 上述之具有可聚合之碳-碳不飽和鍵之該等化合物 中’車父佳使用雙官能或多官能可聚合化合物。更明確地說， 較佳使用四丙烯酸季戊四醇酯、六丙烯酸二季戊四醇酯 等，且更佳使用六丙烯酸二季戊四醇酯。雙官能或多官能 之可聚合化合物可與單官能可聚合化合物合併使用。 至於可陽離子聚合之可聚合化合物，可述及者有，例 =二具有陽離子可聚合官能基如乙烯基醚基、丙烯基鱗基、 環氧基、氧雜環丁基等之化合物。 上述之含有乙烯基醚基之化合物的實例包含三乙二醇 二^烯基醚、M_環己垸二甲醇二乙烯基醚、扣羥基丁基 乙烯基醚、十二烷基乙烯基醚等。 ^上述之含有丙烯基醚基之化合物的實例包含‘ 稀基氧基甲基)]，3_二氧雜環戊烧_2__等。 上述之含有環氧基之化合物的實例包含雙酚A型環氧 :肪:了”型環氧樹脂、甲軸_氧樹脂、i 基胺型^二⑽日、縮水甘油基s旨型環氧樹脂、縮水甘油 衣虱树月日、雜環族環氧樹脂等。 較佳為2000或# ^ s 、二％虱树脂具有 量。 —、，更么為1500或更小之重量平均分子 亡之之含有氧雜環丁基之化 乙基氧雜環丁基）曱基又㈣-甲氧基}苯、M^i3 P { _(乙基氧雜環丁基） 又{ (3_乙基氧雜環丁基）甲氧基}甲基 319342 28 200809412 § 笨1,4-雙{3-(3_乙基氧雜環丁基）曱氧基}環己烷、 • L，4_{3-(3-乙基氧雜環丁基）曱氧基}曱基環己烷、3 ^其 ，氧雜％丁基）甲基化清漆樹脂等。這些含有氧雜環丁基之: •脂具有較佳為2000或更小，更佳為15〇〇或更小曹旦: 均分子量。 里里平 上述之可聚合化合物（H)可單獨使用或者 種合併使用。 裡飞更夕 ，含有可聚合化合物(H)時，以正型彩色輻射線感應樹 月曰、、且成物之重量分率計之，其含量較佳為〇112()重量％。 、本發明之正型彩色輻射線感應樹脂組成物需要時亦可 進:步含有其他成分，例如，各種添加劑如界面活性劑、 抗氧化劑、溶解抑制劑、敏化劑、紫外線吸收劑、光安定 劑、黏著性改善劑、電子供體等。 本每月之正型彩色輪射線感應樹脂組成物可藉由將上 迟之（A)i双溶性可固化樹脂，（b)重氮醌化合物及（〇著色 劑，溶解或分散在有機溶劑（1))中再予以混合而製備之。較 佳的方法係將上述之（A)鹼溶性可固化樹脂，（b)重氮醌化 口物及（C)著色劑，各預先溶解在有機溶劑⑺）中，再混合 所得的溶液。亦可將有機溶_)添加至製備後之液體中: 與之心合。欲使用於上述之鹼溶性可固化樹脂（入），重氮醌 化合物（B)及著色劑（C)之有機溶劑（D)可彼此相同或不 同。只要該等為彼此可相容之溶劑，則可使用複數種有機 溶劑（D)。 再者，混合溶液後較佳藉由過濾移除固體物質。上述 319342 29 200809412 之過濾較佳使用孔徑為3㈣或更小（較佳為約Η至 m)的過濾器進行之。 , I發明之正型彩色輕射線感應樹脂組成物為正型，因 •此，與負型相較下，期望具有高解析度。 纟使用本發明之正型彩色輻射線感應樹 硬化樹脂圖樣時，可有助於，例如，在基板形成由上述Ϊ ^型彩色幸畐射線感應樹脂組成物所組成之層再藉由經由遮 罩以輪射線予以照射而曝光’然後再顯影。 、、至於基板，可述及者有，例如，透明玻璃板等。在上 述基板，可形成TFT，CCD等的電路，或彩色滤光片等。 由正型彩色輻射線感應樹脂組成物所組成之層可藉 由，例如，在基板施用該正型彩色輕射線感應樹脂組成斗: 之方法，及其他方法形成之。施用係藉由，例如，旋轉塗 佈法、流動澆鑄施用法、滾筒施用法、狹縫式暨旋轉塗佈 狹縫式塗佈法等進行之。施用之後，進行熱乾燥（預烤） 或藉由加熱進行㈣下的乾燥以蒸發揮發性成分如溶劑 等’因此’形成正型彩色輻射線感應樹月旨組成物層。此處， =熱溫度通常為70至200t：，較佳為8〇至13〇。〇。此正型 才> 色輻射線感應樹脂組成物層含稀少的揮發性成分。上述 輻射線感應樹脂組成物層的厚度為約丨·5至$ 。 ^ 《後，經由遮罩以輻射線照射正型彩色^射線感應樹 脂組成物層。依據樹脂圖樣所要的形狀適當地選擇遮罩圖 樣。至於輻射線，例如，可使用光束如g線、i線等。利 用韓射線照射較佳使用’例如，光罩對準機、步進機等進 319342 30 200809412 行之’支使該等幸田射光束平行覆蓋在正型彩色輻射線感應 樹脂組成物層的整個表面或部份表面。藉由如以上述之輕 射線照射時’其可正確地進行遮罩與正型彩色韓射線感應 樹脂組成物層的對準。 上述的曝光之後，進行顯影。曝光之後可藉由對該正 型彩色輻射線感應樹脂組成物層施加，例如，旋槳法、浸 潰法、喷淋法等進行顯影。至於顯影劑，通常使用鹼性水 溶液。至於鹼性水溶液，可使用鹼性化合物的水溶液，且 該鹼性化合物可為無機鹼性化合物或有機鹼性化合物。 尸無機鹼性化合物的實例包含氫氧化鈉、氫氧化鉀、磷 酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸 二氫鉀、磷酸氫二鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、 碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、氨等。 有機鹼性化合物的實例包含氫氧化四曱銨、氫氧化2_ 羥基乙基三曱銨、單曱胺、二曱胺、三曱胺、單乙胺、二 乙胺、三乙胺、單異丙胺、二異丙胺'乙醇胺等。 上述之鹼性化合物可單獨使用或者兩種或更多種合併 使用。以顯影劑之重量分率計之，顯影劑中之鹼性化合物 的含量較佳為0.01至10重量％，更佳為〇1至5重量％。 顯影劑可含有界面活性劑。界面活性劑的實例包含非 離子性界面活性劑、陽離子性界面活性劑、陰離子性界面 活性劑等。 非離子性界面活性劑的實例包含聚氧乙烯衍生物類， 如聚氧乙稀烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基^'基 319342 31 200809412 蜒等’氧乙烯/氧丙烯嵌段共聚物類、山梨糖醇酐脂肪酸酯 1、聚氧乙烯山梨糖醇酐脂肪酸酯類、聚氧乙稀山梨糖醇 :曰肪酉夂酉曰類、甘油脂肪酸酯類、聚氧乙烯脂肪酸酯類、聚 氧乙稀院基胺等。 陽離子性界面活性劑的實例包含胺鹽類如硬脂醯基胺 鹽酸鹽等，四級銨鹽如氯化月桂基三曱銨等。 陰離子性界面活性劑的實例包含高級醇硫酸酯鹽類如 月桂醇硫酸鈉、油醇硫酸鈉等； 烧基石反酉欠鹽類如月桂基硫酸納、月桂基硫酸銨等； 烷基芳基磧酸鹽類如十二烷基苯磺酸鈉、十二烷基萘 磺酸鈉等。 這二’I面活f生劑可單獨使用或者兩種或更多種合併使 用。 藉由,、、、員心使在正型彩色輻射線感應樹脂組成物層之Polymer, silk benzene ethoxy styrene copolymer, and the like. This B may be mentioned as one or more of the above-mentioned group of acid or resin. For example, one or more compounds of the group, the group of fish, and the group of fish are selected from the group consisting of (4) and (4) The resin of the compound. % 田3 has the above-mentioned multivalent compound (F), and the content thereof is preferably from 0.01 to 40% by weight, more preferably 以, based on the weight fraction of the solid content of the positive color light ray-sensitive resin composition. .1 to 25% by weight. As the above crosslinking agent (6), a methyl compound or the like can be mentioned. As the above-mentioned methyl compound, there may be mentioned an alkoxymethylated amine-based resin such as a silk methylated melamine resin or a silk-based sulfhydryl resin. Examples of the alkoxymethylated melamine resin include methoxylated melamine mercapine 6 oxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated honey Amine tree month and so on. Examples of the alkoxymethylated urea resin include a decyloxymethylated urea resin, an ethoxymethylated urea resin, a propoxymethylated urea resin, a butoxylated urea resin, and the like. The above crosslinking agents (g) may be used singly or in combination of two or more. When the crosslinking agent (G) is contained, it is preferably from 1 to 15% by weight based on the weight fraction of the solid content of the positive type color radiation sensing resin composition. The content of the crosslinking agent is preferably within the above range, so that the properties such as the hardened resin pattern can be improved. As the above polymerizable compound, for example, there may be mentioned a polymerizable compound which can be radically polymerized by 319342 26 200809412 or a cationically polymerizable hydrazine: a chelating compound or the like. As the preferred polymerizable compound (8), a polymerizable compound which can be cationically polymerized can be mentioned. Further, as for the above-mentioned radically polymerizable polymerizable compound, for example, a compound having a polymerizable carbon-carbon unsaturated bond may be used. The compound having a polymerizable carbon-carbon unsaturated bond may be a monofunctional polymerizable compound and a g-b-b compound, or a polyfunctional tri- or more-functional polymerizable compound. Examples of the soap-functional polymerizable compound include nonylphenyl carbene acrylate, decyl phenyl carbitol methyl propyl acrylate, 2 _ _ 3 phenoxypropyl acrylate, methacrylic acid 2 _hydroxy_3_phenoxypropyl ester, 2 ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol decyl acrylate, propylene fluorene 2-per yl ketone, methacrylic acid 2 _ Base ethyl ester, fluorene vinyl pyrrolidone, and the like. Examples of the difunctional polymerizable compound include bismuth diacrylate, hexanediol ester, hexamethylene methacrylate, ethylene glycol diacrylate, and bis(mercaptopropionic acid) ethylene. Alcohol ester, neopentyl glycol dipropanoate, neopentyl glycol di(methacrylate), triethylene glycol diacrylate, diethylene glycol di(methacrylate), double bisphenol A (Allyloxyethyl)ether, 3-methylpentanediol diacrylate, 2-methylpentanediol di(methacrylic acid), and the like. Examples of the polymerizable compound of the B-month b include trimethyl methacrylate, tris(methacrylic acid) trimethylolpropane ester, pentaerythritol triacrylate, pentaerythritol di(methacrylate), pentaerythritol tetraacrylate. , tetrakis(methacrylic acid) pentaerythritol ester, pentaerythritol pentaerythritol ester, pentaerythritol vinegar of pentaerythritol vinegar, dipentaerythritol hexaacrylate, dipentaerythritol hexa(methacrylate), and the like. Among the above-mentioned compounds having a polymerizable carbon-carbon unsaturated bond, the carmaker uses a difunctional or polyfunctional polymerizable compound. More specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or the like is preferably used, and dipentaerythritol hexaacrylate is more preferably used. A difunctional or polyfunctional polymerizable compound can be used in combination with a monofunctional polymerizable compound. As the cationically polymerizable polymerizable compound, there may be mentioned, for example, a compound having a cationic polymerizable functional group such as a vinyl ether group, a propenyl squaring group, an epoxy group, an oxetanyl group or the like. Examples of the above-mentioned vinyl ether group-containing compound include triethylene glycol dienyl ether, M_cyclohexane dimethanol divinyl ether, hydroxybutyl butyl vinyl ether, dodecyl vinyl ether, and the like. . ^ Examples of the above-mentioned compound containing a propenyl ether group include 'sweet oxymethyl)], 3-dioxolane-2__ and the like. Examples of the above epoxy group-containing compound include bisphenol A type epoxy: fat: "type epoxy resin, armature _ oxy resin, i amide type ^ two (10) days, glycidyl s type epoxy Resin, glycidyl eucalyptus, heterocyclic epoxy resin, etc. Preferably, 2000 or #^s, bis% bismuth resin has an amount. -,, more preferably 1500 or less, the weight average molecular weight Oxetane-containing ethyl oxetanyl) fluorenyl (tetra)-methoxy}benzene, M^i3 P { _(ethyloxetanyl) and { (3_ethyl Oxecyclobutyl)methoxy}methyl 319342 28 200809412 § Stupid 1,4-double {3-(3_ethyloxetanyl)nonyloxy}cyclohexane, • L, 4_{3 -(3-Ethyloxetanyl)nonyloxy}nonylcyclohexane, 3^, oxaxyl butyl) methylated varnish resin, etc. These contain oxetanyl: It has a 2,000 or less, more preferably 15 Å or less Cao Dan: average molecular weight. The above polymerizable compound (H) can be used singly or in combination. Positive color radiation when polymerizing compound (H) The content of the sensing tree, and the weight fraction of the product, is preferably 〇112 ()% by weight. The positive color radiation sensing resin composition of the present invention can also be used if necessary: the step contains other Ingredients, for example, various additives such as surfactants, antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, adhesion improvers, electron donors, etc. This monthly positive color wheel ray induction The resin composition can be prepared by mixing the (A)i double-soluble curable resin, (b) a diazonium compound, and (a hydrazine coloring agent, dissolved or dispersed in the organic solvent (1)). Preferably, the above-mentioned (A) alkali-soluble curable resin, (b) diazonium halide and (C) coloring agent are each dissolved in an organic solvent (7), and the resulting solution is mixed. The organic solvent may also be added to the liquid after preparation: in combination with the organic solvent of the above-mentioned alkali-soluble curable resin (in), diazonium compound (B) and coloring agent (C). (D) may be the same or different from each other as long as they are each other For compatible solvents, a plurality of organic solvents (D) may be used. Further, it is preferred to remove the solid matter by filtration after mixing the solution. The filtration of the above 319342 29 200809412 preferably uses a pore diameter of 3 (four) or less (preferably For the filter of about Ηm to m), the positive color light ray-sensitive resin composition of the invention I is positive, and therefore, it is desirable to have high resolution compared with the negative type. The positive type color radiation sensing tree hardening resin pattern can help, for example, to form a layer composed of the above-mentioned color-sensitive radiation-sensitive resin composition on the substrate and then to pass the radiation through the mask. Exposure to illumination and then development. As for the substrate, there may be mentioned, for example, a transparent glass plate or the like. In the above substrate, a circuit such as a TFT or a CCD, or a color filter or the like can be formed. The layer composed of the positive type color radiation sensing resin composition can be formed by, for example, a method of applying the positive color light ray-sensitive resin to the substrate, and other methods. The application is carried out by, for example, a spin coating method, a flow casting application method, a roll application method, a slit type and a spin coating slit coating method, or the like. After the application, heat drying (pre-baking) or drying under (4) by heating to evaporate volatile components such as a solvent or the like ' thus forming a positive color ray-ray sensing tree composition layer. Here, the =heat temperature is usually 70 to 200 t: preferably 8 to 13 Torr. Hey. This positive type > color radiation sensing resin composition layer contains rare volatile components. The radiation-sensitive resin composition layer has a thickness of about 丨·5 to $. ^ "Afterwards, the positive color ray-sensing resin composition layer is irradiated with radiation through a mask. The mask pattern is appropriately selected depending on the desired shape of the resin pattern. As for the radiation, for example, a light beam such as a g line, an i line, or the like can be used. It is preferable to use the Korean ray irradiation, for example, a reticle aligner, a stepper, etc., into the 319342 30 200809412 line, so that the singular beam is covered in parallel on the entire surface of the positive color ray-ray sensing resin composition layer or Part of the surface. The alignment of the mask with the positive-type color Korean ray-sensing resin composition layer can be correctly performed by irradiation with the above-mentioned light ray. After the above exposure, development is carried out. After the exposure, development can be performed by applying the positive color ray-irradiation-inducing resin composition layer, for example, a paddle method, a dipping method, a shower method, or the like. As for the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of a basic compound may be used, and the basic compound may be an inorganic basic compound or an organic basic compound. Examples of cadaveric inorganic basic compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium citrate, Potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Examples of the organic basic compound include tetraammonium hydroxide, 2-hydroxyethylammonium hydroxide, monodecylamine, diamine, tridecylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine. , diisopropylamine 'ethanolamine and the like. The above basic compounds may be used singly or in combination of two or more. The content of the basic compound in the developer is preferably from 0.01 to 10% by weight, more preferably from 1 to 5% by weight, based on the weight fraction of the developer. The developer may contain a surfactant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and the like. Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl group, 319342 31 200809412, etc. 'oxyethylene/oxygen Propylene block copolymers, sorbitan fatty acid esters 1, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol: fatty steroids, glycerol fatty acid esters, polyoxygen Ethylene fatty acid esters, polyoxyethylene-based amines, and the like. Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and the like, and quaternary ammonium salts such as lauryl triammonium chloride and the like. Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate, sodium oleyl sulfate, and the like; base stones such as sodium lauryl sulfate, ammonium lauryl sulfate, etc.; alkyl aryl hydrazine; The acid salts are, for example, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate and the like. These two surfactants may be used singly or in combination of two or more. By means of , , , and the members of the positive color radiation sensing resin composition layer

頒影劑可含有有機溶劑。至於上述之有機溶劑，可述 有例如水可;谷之有機溶劑如甲醇、乙醇等。 顯影劑中，而且未 而予以保留，沒有 由於本發明之正划赵A ^ 4丄Μ β Ah .The toner can contain an organic solvent. As the above organic solvent, for example, water may be mentioned; an organic solvent such as methanol, ethanol or the like may be mentioned. In the developer, it is not retained, and it is not due to the positive delineation of the invention.

319342 32 200809412 $ 解在頭影劑中不消失。 在鹼性顯影之；^^ , f ，古夕#丨 之後通索以水沖洗及乾燥之。卷兩|齡 回之耐光性時， 田而要較 _ _ 仏在乾、J：呆後進一步以輻射線昭 較佳為紫外線或深此處，照射用的輕射線 於先别曝光的照射量。 仪1夂间 由改善取終所得到彩色硬化樹脂圖樣之 !L的觀點來看，由此所形成之樹脂圖樣較佳二= 執ϋΓϋ共烤）·加熱係藉由如加熱板、乾淨洪箱等加 :，、、衣置加熱基板之方法進行之。加熱溫度通常為15〇至25〇319342 32 200809412 $ Solution does not disappear in the cephalopod. After alkaline development; ^^, f, 古夕#丨, the cable is rinsed and dried with water. When the volume is light-resistant, the field is better than _ _ 仏 干 、 、 、 、 、 、 、 、 、 、 、 、 J J J J J J J J J J J J J J J J 辐射 辐射. From the viewpoint of L, the color hardened resin pattern obtained by the improvement is taken from the point of view of L, the resin pattern thus formed is preferably two = ϋΓϋ ϋΓϋ ϋΓϋ ) · · · · · 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热 加热And the addition:,,, and the method of heating the substrate by clothes. Heating temperature is usually 15〇 to 25〇

Hi為約180至240°c，且加熱時間通常為5分鐘至 I里’較佳為約15分鐘至90分鐘。藉由加熱，使圖 才水硬化以形成彩色硬化樹脂圖樣。 由此所形成之樹脂圖樣係藉由使本發明之正型彩色輻 射線感應樹脂組成物硬化所得到之圖樣，且可使 成，例如，液晶面板用之光感應間隙材、液晶方位控制用 之投影、黑色矩陣等之彩色硬化樹脂圖樣。 ，藉由使用本發明之正型彩色輻射線感應樹脂組成物， 使形成精細的彩色硬化樹脂圖樣成為可能。 實施例 本發明將基於以下的實施例予以更詳細的說明，但不 用5兄本發明亚不偈限於這些實施例。 合成例1 在備有攪拌器，冷卻管及溫度計之200mL四頸燒瓶中 319342 33 200809412 置入下述原料’在氮氣流下將四頸燒瓶浸潰在油浴中，將 3小時同時使燒瓶中的溫度保持在85至95 C 乂付到树月曰A1。以聚苯乙稀校正計之，此樹脂A1的 重蓋平均分子量為8000。 7.9g 14.5g 21.4g 90.7g l.lg 甲基丙烯酸 N-環己基馬來醯亞胺 3-乙基-3-曱基丙烯醯氧基曱基氧雜環丁烷 二乙二醇甲基乙基醚 偶氮雙異丁腈 此樹脂A1之以聚苯乙烯校正計之重量平均分子量係 在下述條件下測量。 裝置·· HLC_8120GPC(Tosoh 公司出品） 管柱·· TSK-GELG2000HXL，TSK-GELG4000HXL 系 列Hi is about 180 to 240 ° C, and the heating time is usually from 5 minutes to 1 mile, preferably from about 15 minutes to 90 minutes. The water is hardened by heating to form a colored hardened resin pattern. The resin pattern thus formed is obtained by curing the positive-type color radiation-sensitive resin composition of the present invention, and can be used, for example, for a light-sensing gap material for a liquid crystal panel or for liquid crystal orientation control. Color hardened resin pattern for projection, black matrix, etc. By using the positive type color radiation sensing resin composition of the present invention, it is possible to form a fine color hardened resin pattern. EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not limited to these examples. Synthesis Example 1 In a 200 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 319342 33 200809412 The following raw materials were placed. The four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask was allowed to stand for 3 hours. The temperature is maintained at 85 to 95 C and is paid to the tree moon A1. Based on the polystyrene calibration, the average molecular weight of the resin A1 was 8,000. 7.9g 14.5g 21.4g 90.7g l.lg N-cyclohexylmaleimide methacrylate 3-ethyl-3-mercaptopropenyloxydecyloxybutane diethylene glycol methyl b The base weight azobisisobutyronitrile The weight average molecular weight of this resin A1 measured by polystyrene was measured under the following conditions. Device ···············

管柱溫度·· 40°C 移動相溶劑··四氳吱鳴 流動速率：l.OmL/min 注射量：50//L 偵測器：RI 測量試樣濃度：0.6重量％(溶劑··四氫呋喃）Column temperature · · 40 ° C mobile phase solvent · · four humming flow rate: l.OmL / min injection volume: 50 / / L detector: RI measurement sample concentration: 0.6% by weight (solvent · tetrahydrofuran )

校正用之標準物質：TSK STANDARD POLYSTYRENE F-40，t? β w ，pq，a-2500，A-500(Tosoh 公司出品） 實施例1 混合樹脂Al(l〇〇重量份），下式（1)之化合物（30重量 34 319342 200809412 ) 伤）’ KBM-303(Shin-Etsu Silicones 出品，3 重量份），二乙 二醇曱基乙基醚（3重量份），乳酸丁酯（i 6重量份）， SH8400(Dow Corning Toray出品，〇·〇3重量份）與黑色著色 、劑（藉由混合黑色顏料19重量❹/。，分散劑5重量。/。，丙二醇 單曱基醚乙酸酯76重量〇/❻所得到者；1〇重量份）以得到正 型彩色輻射線感應樹脂組成物1。 OQ4Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, t? β w , pq, a-2500, A-500 (produced by Tosoh Corporation) Example 1 Mixed resin Al (100 parts by weight), the following formula (1) ) compound (30 weight 34 319342 200809412 ) wound) ' KBM-303 (Shin-Etsu Silicones, 3 parts by weight), diethylene glycol decyl ethyl ether (3 parts by weight), butyl lactate (i 6 weight份), SH8400 (Dow Corning Toray, 〇·〇 3 parts by weight) and black coloring agent (by mixing black pigment 19 weight ❹ /, dispersing agent 5 weight / propylene glycol monodecyl ether acetate 76% by weight/❻ obtained; 1 part by weight) to obtain a positive type color radiation sensing resin composition 1. OQ4

在透明玻璃基板（#1737，Corning公司出品）旋轉塗佈 上述所得到之正型彩色輻射線感應樹脂組成物i，再使用 乾淨烘箱於100°C加熱（預烤）3分鐘，以形成厚度為3//m 之輻射線感應樹脂組成物層。此膜厚度係藉由膜厚度計 (DEKTAK3 ; ULVAC Κ·Κ·出品）測量之。 之後’藉由使用接觸式對準機（M-2Li ; MIKASA Κ.Κ. 出品）經由遮罩以輻射線（在波長365nm標準的強度； 15〇mJ/cm2)照射而使所得之正型彩色輻射線感應樹脂^成 物層曝光。此操作中所使用之遮罩含有線/間隔=3〇#m/3() V m ’ 20 # m/20 /zm’ 10//m/10//m，9/z m/9 // m，8 // m/8 # m，7 // m/7 // m，6 /z m/6 // m，5 // m/5 // m。 曝光後，使該層在23°C之顯影劑（含有濃度為〇1%重 量分率之氫氧化鉀且含有非離子性界面活性劑之水溶液） 319342 35 200809412 中浸潰150秒以造成顯影，然後以超純水予以沖洗，乾燥， 然後於220 C進行後烘烤30分鐘以得到樹脂圖樣。使用掃 描式電子顯微鏡觀察所得之樹脂圖樣，結果確認形成於6 // m/6 // m或更大之線/間隔圖樣的樹脂圖樣。 比較例1 混合樹脂B1[式（2)之共聚物，結構單元的比率： a/b/c/d=10/54/21/15，以聚苯乙烯校正計之重量平均分子 里· 15000，此處，以聚苯乙烯校正計之重量平均分子量係 在與樹脂A1相同的條件下測量]，可光聚合化合物 KAYARAD DPHA(Nipp〇n Kayaku 公司出品）（5〇 重量份）， 光起始劑 Irgacure 369(Ciba Specialty Chemicals 出品）(3 重 量份），光起始助劑 EAB-F(H〇dogaya Chemicals 出品）（1 重量份），丙二醇單甲基醚乙酸酯（1丨3重量份），丙酸3_乙 氧基乙酯（24重量份）與黑色著色劑（藉由混合黑色顏料19 重量°/◦’分散劑5重量％及丙二醇單甲基醚乙酸酯76重量 %所得到者；10重量份）以得到正型彩色輻射線感應樹脂組 成物2 〇The positive-type color radiation sensing resin composition i obtained above was spin-coated on a transparent glass substrate (#1737, manufactured by Corning Co., Ltd.), and then heated (pre-baked) at 100 ° C for 3 minutes in a clean oven to form a thickness of A radiation sensing resin composition layer of 3//m. This film thickness was measured by a film thickness meter (DEKTAK3; ULVAC Κ·Κ·). After that, the resulting positive color was obtained by irradiating with a radiation (intensity at a wavelength of 365 nm; 15 〇 mJ/cm 2 ) through a mask using a contact aligner (M-2Li; MIKASA Κ.Κ.). The radiation sensing resin is exposed to the layer. The mask used in this operation contains line/space=3〇#m/3() V m ' 20 # m/20 /zm' 10//m/10//m,9/zm/9 // m ,8 // m/8 # m,7 // m/7 // m,6 /zm/6 // m,5 // m/5 // m. After exposure, the layer was immersed in a developer (containing an aqueous solution containing potassium hydroxide having a concentration of 〇1% by weight and containing a nonionic surfactant) at 319342 35 200809412 for 150 seconds to cause development. It was then rinsed with ultrapure water, dried, and then post-baked at 220 C for 30 minutes to obtain a resin pattern. The obtained resin pattern was observed using a scanning electron microscope, and as a result, a resin pattern formed on a line/space pattern of 6 // m/6 // m or more was confirmed. Comparative Example 1 Mixed resin B1 [copolymer of formula (2), ratio of structural units: a/b/c/d = 10/54/21/15, weight average molecular weight in terms of polystyrene correction, 15,000, Here, the weight average molecular weight measured by polystyrene is measured under the same conditions as the resin A1], photopolymerizable compound KAYARAD DPHA (produced by Nipp〇n Kayaku Co., Ltd.) (5 parts by weight), photoinitiator Irgacure 369 (produced by Ciba Specialty Chemicals) (3 parts by weight), photoinitiator EAB-F (produced by H〇dogaya Chemicals) (1 part by weight), propylene glycol monomethyl ether acetate (1丨3 parts by weight) , 3 - ethoxyethyl propionate (24 parts by weight) and a black colorant (by mixing black pigment 19 wt / ◦ 'dispersant 5 wt% and propylene glycol monomethyl ether acetate 76 wt% 10 parts by weight) to obtain a positive color radiation sensing resin composition 2 〇

以與實施例1相同之方式由上述得到之正型彩色輻射 36 319342 200809412 、，泉感應树知組成物形成 VI ih ^ ^ 1 田、、、、襄感應樹脂組成物層。再者， 以與貫施例丨相同 H匕知A、‘ S E | 万式使所侍之正型彩色輻射線感應樹 脂組成物層曝光。 q 旦冰光後斤使ϋ亥層在23。〇之顯影劑（含有濃度為〇·05% 重量分率之氫氧化钾且含有非離子性界面活性劑之水溶 中π /貝120 &以造成顯影’然後以超純水予以沖洗，乾燥， 然後於22(TC進行後烘烤3G分鐘以得到樹脂圖樣。使用婦 描式電子顯微鏡觀察所得之樹脂圖樣，結果確認形成於 // m/20/z m或更大之線/間隔圖樣的樹脂圖樣。然而，w // m/10 // m或更小之圖樣顯示部份的殘留。 319342 37In the same manner as in Example 1, the positive-type color radiation 36 319342 200809412 obtained in the above manner was used to form a VI ih ^ ^ field, resin composition layer. Furthermore, it is the same as the conventional example. H匕 know A, ‘S E | 10,000-type exposes the positive color radiation-sensing resin composition layer. q After the ice is light, the jin layer is at 23. a developer of bismuth (containing potassium hydroxide at a concentration of 〇·05% by weight and containing a nonionic surfactant in water-soluble π/bei 120 & to cause development' and then rinsing with ultrapure water, drying, Then, it was post-baked at 22 °C for 3 G minutes to obtain a resin pattern. The obtained resin pattern was observed using a woman-like electron microscope, and as a result, a resin pattern formed in a line/space pattern of // m/20/zm or more was confirmed. However, a pattern of w // m/10 // m or smaller shows a portion of the residue. 319342 37

Claims (1)

200809412 » 十、申請專利範圍： 1. -種正型彩色輕射線感應樹脂組成物，包括⑷驗溶性 可固化樹脂，（B)重氮醌化合物及（c)著色劑，其中該 .驗溶性可固化樹脂係含有下述結構單元之共聚物：⑻ 衍生自不飽和羧酸之結構單元及（a2)衍生自具有不飽和 羧駄以外之氧雜環丁基之不飽和化合物之結構單元。 2. 如申切專利範圍第J項之樹脂組成物，其中該（八)鹼溶 性可固化樹脂進一步含有（a3)選自下述所成群組之至少 一種結構單元：（a31)衍生自4有碳-破不飽和鍵之羧酸 酉曰之結構單元’（a32)衍生自具有碳·碳不飽和鍵之芳香 =化合物之結構單元，（a33)衍生自丙烯腈化合物之結構 單元，（a34)衍生自在N位置上視需要具有取代基之馬 來醯亞胺化合物之結構單元及（a35)衍生自具有碳-碳不 飽和鍵之環氧化合物之結構單元。 3. 如申請專利範圍第丨或2項之樹脂組成物，其中該著色 制（C)係選自有機顏料及黑色無機顏料所成群組之至少 種顏料。 4. 如申請專利範圍第u 3項中任一項之樹脂組成物，其 中進一步包括（D)有機溶劑。 5 ·種彩色硬化樹脂圖樣，係使用如申請專利範圍第1至 4項中任一項之樹脂組成物所形成者。 6· —種彩色硬化樹脂圖樣之製造方法，包括在基板施用如 申請專利範圍第1至4項任一項中之樹脂組成物，移除 ;谷劑’經由遮罩以輻射線照射該樹脂組成物，然後以驗 319342 38 200809412 性水溶液進行顯影以形成圖樣。 7·如申请專利範圍第6項之彩色硬化樹脂圖樣之製造方 法’其_在圖樣形成之後’進一步加熱該圖樣。 8·種彩色硬化樹脂圖樣之製造方法，包括在基板施用如 申請專利範圍第〗至4項中任一項之正型彩色輻射線感 應樹脂組成物，移除溶劑，經由遮罩以輻射線照射該樹 脂組成物，以鹼性水溶液進行顯影以形成既定圖樣，然 後以輻射線照射基板之圖樣的整個表面或部份表面。 9.如申請專利範圍第8項之彩色硬化樹脂圖樣之製造方 法，其中在以輻射線照射基板之圖樣的整個表面或部份 表面之後，進一步加熱該圖樣。 319342 39 200809412 七、指定代表圖：本案無圖式 (一） 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無代表化學式 319342200809412 » X. Patent application scope: 1. - A positive color light-ray-sensitive resin composition, including (4) a testable curable resin, (B) a diazonium compound and (c) a colorant, wherein the test solubility can be The cured resin is a copolymer containing the structural unit of (8) a structural unit derived from an unsaturated carboxylic acid and (a2) a structural unit derived from an unsaturated compound having an oxetanyl group other than the unsaturated carboxylic acid. 2. The resin composition of claim J, wherein the (eight) alkali-soluble curable resin further comprises (a3) at least one structural unit selected from the group consisting of: (a31) derived from 4 The structural unit '(a32) having a carboxylic acid ruthenium having a carbon-unsaturated bond is derived from a structural unit having a carbon=carbon unsaturated bond aromatic=compound, (a33) is derived from a structural unit of an acrylonitrile compound, (a34) And a structural unit derived from a maleimide compound having a substituent at the N position and (a35) a structural unit derived from an epoxy compound having a carbon-carbon unsaturated bond. 3. The resin composition of claim 2 or 2, wherein the coloring (C) is at least one selected from the group consisting of organic pigments and black inorganic pigments. 4. The resin composition according to any one of claims 5 to 3, further comprising (D) an organic solvent. (5) A color hardening resin pattern formed by using the resin composition according to any one of claims 1 to 4. 6. A method for producing a color hardened resin pattern, comprising: applying a resin composition as in any one of claims 1 to 4 on a substrate, removing; the paste agent illuminating the resin by radiation through a mask The material was then developed with a 319342 38 200809412 aqueous solution to form a pattern. 7. A method of producing a colored hardened resin pattern as claimed in claim 6 of the patent application, wherein the pattern is further heated after the pattern is formed. 8. A method for producing a color hardened resin pattern, comprising: applying a positive color radiation sensing resin composition according to any one of claims 1-4 to 4 on a substrate, removing the solvent, and irradiating the radiation through the mask The resin composition is developed with an aqueous alkaline solution to form a predetermined pattern, and then the entire surface or part of the surface of the pattern of the substrate is irradiated with radiation. 9. The method of producing a color hardened resin pattern according to claim 8 wherein the pattern is further heated after irradiating the entire surface or a portion of the surface of the pattern of the substrate with radiation. 319342 39 200809412 VII. Designated representative map: There is no schema in this case (1) The representative representative figure in this case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No representative chemical formula 319342
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