200401165 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關輻射敏感性樹脂組成物，及應用它形成 透明膜與其製造方法。 【先前技術】 輻射敏感性樹脂組成物，舉例而言，作爲製成TFT 型液晶顯示裝置所使用之TFT絕緣膜以及透明膜之材料 頗爲有用。此TFT絕緣膜等，爲提高其生產性，對製成 絕緣膜之輻射敏感性樹脂組成物，要求具高感度，俾能縮 短曝光時間，及爲提高合格率所需之高顯像殘膜率與高耐 溶劑性。但是爲獲得高感度而提高對顯像液之溶解度，有 降低殘膜率及耐溶劑性之傾向。 【發明內容】 本輻射敏感性樹脂組成物含有之（A )鹼可溶性樹脂 ，可舉例如含有苯酚性羥基高分子化合物：酚醛淸漆樹脂 與聚羥基苯乙烯樹脂等，以及含有羥基高分子化合物之甲 基丙烯酸聚合體與丙烯酸聚合體等等，含有苯鼢性羥基或 羥基之樹脂。又鹼可溶性樹脂具有硬化性者較佳。如此具 有硬化性之高分子化合物，可舉例如含有乙烯基、環氧基 、氧雜環丁烷基、四氫呋喃基、丁內酯骨架等之化合物。 鹼可溶性樹脂而言，特別理想的高分子化合物是具有 羧基及氧雜環丁烷骨架之高分子化合物。氧雜環丁烷骨架 -4 _ (2) (2)200401165 意指氧雜環丁烷環（三伸甲基氧化物）。具有氧雜環丁烷 骨架之高分子化合物即意指含有前述氧雜環丁烷環（三伸 甲基氧化物）之高分子化合物。前記高分子化合物，可舉 例如由含有羧基單體導成的結構單元，以及由含有氧雜環 丁烷骨架導成的結構單元形成之共聚合體等，應需要也可 與由其他單體導成的結構單元形成共聚合體。 於此’含有羧基之單體，可舉例如不飽和單羧酸、不 飽和雙羧酸等’分子中含有一個或兩個以上羧基之不飽和 羧酸等，具體而言諸如丙烯酸、甲基丙烯酸、丁烯酸衣康 酸、馬來酸、富馬酸、檸康酸、中康酸等。 含有氧雜環丁烷骨架單體，可舉例如3-甲基-3( 間）丙烯醯西門甲基氧雜環丁烷、3-乙基- 3(間）丙烯 醯亞門氧雜環丁烷、3—甲基一3(間）丙烯醯西門乙基氧 雜環丁烷及3 —甲基- 3(間）丙烯醯西門乙基氧雜環丁 烷等。 其他單體則可舉例如含有聚合性碳素-碳素不飽和結 合之單體，具體而言諸如苯乙烯' α -甲基苯乙烯、乙烯 基甲苯等之芳香族乙烯化合物、丙烯酸甲酯、甲基丙烯酸 甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基 丙烯酸丁酯、2-羥基丙烯酸乙酯、2—羥基甲基丙烯酸乙 酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基 丙烯酸環己酯、異丙烯酸冰片酯、異甲基丙烯酸冰電酯等 不飽和羧酸酯；丙烯酸氨乙酯等之不飽和羧酸氨烷酯；醋 酸乙烯、丙酸乙烯等之羧酸乙烯酯；丙烯腈、甲基丙烯腈 (3) (3)200401165 、《 -氯腈等之氰化乙烯化合物等。這些其他單體可以各 自單獨或兩種以上組合使用。 從含有羧基之單體及含有氧雜環丁烷骨架之單體獲得 (A )鹼可溶性樹脂時，含有羧基之單體對全部單體之質 量百分比，通常使用5 — 50%，而較理想的是15〜4〇%範 圍內。含氧雜環丁烷骨架之單體時，對全部單體而言，通 常使用是95〜50%，理想是85〜60%。 含羧基之單體對全部單體之質量百分比爲5〜50%， 則對有機溶劑之溶解性有提高傾向，令人滿意；又，含有 氧雜環丁烷骨架之單體是95〜50%時，硬化速度有加速 傾向，很理想。更進而含有其他單體導成之構成亦佳。 (A )鹼可溶性樹脂具體而言，可舉例如3 -乙基- 3 -丙烯醯丙門甲基氧雜環丁烷/甲基丙烯酸苄酯/甲基丙 烯酸共聚合體、3 -乙基- 3 -甲基丙烯醯西門甲基氧雜環 丁烷/甲基丙烯酸苄酯/甲基丙烯酸/苯乙烯共聚合體、 3 -乙基- 3 -甲基丙醯西門甲基氧雜環丁烷/甲基丙烯酸 /苯乙烯共聚合體、3 -乙基- 3 -甲基丙烯醯西門甲基氧 雜環丁烷/甲基丙烯酸/甲基丙烯酸環己酯共聚合體，3 一乙基- 3 -甲基丙烯醯西門甲基氧雜環丁烷/甲基丙烯 酸/甲基丙烯酸甲基/苯乙烯共聚合體等。 前記（A )鹼可溶性樹脂之重量平均分子量（以聚乙 烯爲標準，使用凝膠滲透色譜法測定），通常在2，〇 〇 〇 〜4〇〇,〇〇〇範圍內’理想値是2,000〜1〇〇,〇〇〇之範圍，最 理想是3,000〜50,000。前記的重量平均分子量在2,〇〇〇〜 (4) (4)200401165 4 0 0，0 0 0之範圍’可得充分顯像速度，頗理想。 (A )鹼可溶液樹脂可混合2種以上使用。 本輻射敏感性組成物內（A )鹼可溶性樹脂的含量， 以除去溶劑後本輻射敏感性樹脂組成物的重量而言，質量 百分率通常是 5〜90%，理想値是30〜90%。（A)鹼可 溶性樹脂之含量5〜9 0 %時，具有充分顯像速度之傾向， 令人滿意。 本輻射敏感性組成物所含（B )輻射線敏感性化合物 ，在照射輻射線前，是延遲本組成物對鹼溶解速度之化合 物；但於接受輻射線時，前記化合物自身構造的變化，有 加速促成自身對鹼水溶液溶解速度之作用，結果是具有促 進本輻射敏感性樹脂組成物溶解速度作用之化合物，例如 含有苯醌二嗪基之化合物等。 前記苯酮二疊氮基化合物，可舉例如1，2 -苯并醌 二疊氮基磺酸酯、1，2-萘并醌二疊氮基磺酸基、1’ 2一 苯并醌二疊氮基磺酸胺、1，2 -萘并醌二疊氮基磺酸胺類 等。理想的是1，2 -萘并醌二疊氮基磺酸酯。 具體而言，2 ’ 3，4 _三羥基苯并醌一 1 ’ 2 -萘并酿 二疊氮基一 4一磺酸酯、2，3, 4一三羥基苯并醌一 1，2一 萘并醌二疊氮基一 5 —磺酸酯、2，4，ό —三羥基苯并醌一 1，2-萘并醌二疊氮基一 4一磺酸酯、2，4，6-三經基本 并醌—1，2 -蔡并醌二疊氮基—5 —磺酸酯等之二控基本 并醌類之1，2 -萘并醌二疊氮基磺酸酯、2 ’ 2 / ’ 4 ’ 4，一四羥基苯并醌一 1，2 -萘并醌二疊氮基一 4 一磺酸酯 (5) (5)200401165 、2，2 z ，4，4 — 一四羥基苯并醌一 1，2 —苯并醌二疊氮 基一 5 —磺酸酯、2，2 — ，4，3 / —四羥基苯并醌—1，2 一萘并醌二疊氮基—4 —磺酸酯、2，2 >，4，3 / —四羥 基苯并醒一 1，2-蔡并醒_疊氮基一 5 —礦酸醋、2，3，4 ，4 / —四羥基苯并醌一 1，2 —萘并醌二疊氮基一 4 一磺酸 酯、2，3，4，4 — 一四經基苯并醌一 1，2 —苯并醌二疊氮 基一 5 --磺酸酯、2，3，4，2 ——四羥基苯井醌—1，2 — 萘并醌二疊氮基一 4一磺酸酯、2，3，4，2 — -四羥基苯 醌一 1，2 —萘苯并醌二疊氮基一 5 -磺酸酯、2，3，4，4 —一四羥基一 3 〃 一甲基苯并醌—1，2 —萘并醌二疊氧基 —4一磺酸酯及 2，3，4，—四羥基——甲氧基苯 并醌- 1，2 -萘并醌二疊氧基- 5 -磺酸酯等之四羥基苯 并醌類之1，2 -萘并醌三疊氧基磺酸酯、2，3，4，2 / ，厂一五羥基苯并醌一 1，2 -萘并醌二疊氧基一 4 一磺酸 酯、2，3，4，2 /，6 / —五羥基苯并醌—1，2 —萘并醌 二疊氧基- 5 -磺酸酯等之五羥基苯并醌之1，2 -萘并醌 二疊氧基磺酸酯、2，4，6 ’ 3 / ’ 4 / ，5 > -六羥基苯并 苯酮—1，2 -萘并醌二疊氧基—4 —磺酸酯、2，4，6，/ ，4 - ，5 > -六羥基苯并醌一 1，2 —萘并醌二疊氧基一 4 —磺酸酯、3，4，5，3 — ，4 — ，5 > -六羥基苯并醌—1 ，2 —萘并醌二疊氧基—4 —磺酸酯、3，4，5，3 >，4 一 ，5 — -六羥基苯并醌類之1，2 -萘并醌二疊氧基一 5 -磺酸酯等之六羥基苯并醌類之1，2 -萘并醌二疊氧基磺 酸酯、雙（2，4 一二羥基苯基）甲烷一 1，2 -萘并醌二疊 -8- (6) (6)200401165 氧基一 5 -磺酸酯、雙（p-羥基苯基）甲烷一 1，2 —萘并 醌二疊氧基一 4 一磺酸酯、雙（p -羥基苯基）甲烷一 1，2 一萘并醌二疊氧基—5 -磺酸酯、1，1，1 一三（p —羥基 苯基）甲烷—1，2 -萘并醌二疊氧基一 4 —磺酸酯、1，1 ，1 一三（p-羥基苯基）甲烷一 1，2 —萘并醌二疊氧基一 5 -磺酸酯、雙（2，3，4一三羥基苯基）甲烷一 1，2 —萘 并醌二疊氧基一 4一磺酸酯、雙（2，3，4一三經基苯基） 甲烷—1，2-萘并醌二疊氧基一 5 —磺酸酯、2，2，一雙 (2，3，4一三羥基苯基）丙烷—1，2-萘并醌二疊氧基 一 4一磺酸酯、2，—雙（2，3，4一三羥基苯基）丙烷 一 1，2 -萘并醌二疊氧基—5 -磺酸酯、1，1，3 —三（2 ，5 — _•甲基—4 一 基苯基）—3 —苯丙— 1，2 -奈并 醌二疊氧基—4一磺酸酯、1，1，3 —三（2，5 -二甲基一 4一羥基苯基苯基）一 3 -苯丙烷一 1，2-萘并醌二疊氧基 —5—磺酸酯、4，4^ —〔1一 〔4—〔1—4〔羥基苯基〕 一 1 一甲基乙基〕苯基〕乙炔〕二酚一 1，2—萘并醌二疊 氧基一 5 -磺酸酯、雙（2，5 -二甲基一 4一羥基苯基）一 2 -羥基苯甲烷一 1，2 -苯并醌二疊氧基一 4 一磺酸酯、雙 (2，5-二甲基一 4一羥基苯基）—2—羥基苯甲烷一 1， 2 一 一萘并醌二疊氧基—5 —磺酸酯、3，3，3 ―，3 > —四 甲基一 1，1 ——螺旋雙茚滿酮—5，6，7，5 — ，6，，7 一 一己醇一 1，2 —萘并醌二疊氧基—4 —磺酸酯、3，3，3， ，3，—四甲基—1—1' 一螺旋雙茚滿酮—5，6，7，5^ ，，7 / —己醇—1，2 —萘并醌二疊氧基一 5—磺酸酯 Z i i 0 -9 - (7) (7)200401165 、2，2’4 —三甲基—7，2一 ，4 一 一三羥基黃烷—1，2 — 萘并醌二疊氧基一 4 一蟥酸酯、2，2, 4 —三甲基一 7，2 一 ，4 — 一三羥基黃烷一 1, 2 一萘并醌二疊氧基一 5 —磺酸酯 等之（聚羥基苯基）鏈烷類之1,2 -萘并醌二疊氧基磺 酸酯等。 前記醌二疊氧基化合物以各種單獨或組合兩種以上使 用。本輻射敏感性組成物中之（B )輻射線敏感化合物含 量’對本組成物之固體部分重量而言，質量百分比通常爲 2 - 5 0 %，理想値是5〜40 %。前記輻射線敏感化合物之 含量2 - 5〇%時’曝光部分與未曝光部分之溶解速度差有 加大傾向，令人滿意。 本輻射敏感性組成物所含（C )溶劑α -羥基異丁酸 酯類之含量，對全溶劑量之質量百分比而言，通常是16 %以上’理想値是35%以上。少於16%，則因降低對顯 像液之溶解度，感度化隨之下降。 α 一羥基異丁酸酯類，可舉例如α 一羥基異丁酸甲基 、α _羥基異丁酸乙基等，α -羥基異丁酸甲基較理想。 又，與α -羥基異丁酸酯類混合可能溶劑，可使用眾 所皆知輻射敏感性樹脂組成物之有機溶劑化合物。 上述混合可能溶劑，舉例如乙二醇一甲醚、乙二醇一 乙醚、乙二醇一丙醚、乙二醇一丁醚等之乙二醇一烷基醚 類；二甘醇二甲醚、二甘醇二乙醚、二甘醇二丙醚 '二甘 醇二丁醚等之二甘醇二烷基醚類；乙二醇一甲醚甲醚醌酸 酯、乙二醇一乙醚醋酸酯等之乙二醇烷基醚醋酸酯；丙二 -10- (8) (8)200401165 醇一甲基醚醋酸酯、丙二醇一乙基醚醋酸酯、丙二醇一丙 基醚醋酸酯等之丙二醇烷基醚醋酸酯類，苯、甲苯 '二甲 苯等之芳香族碳氫類；甲基乙基甲酮、丙酮、甲基戊基甲 酮、甲基異丁基甲酮、環己酮等三甲酮類；乙醇、丙醇、 丁醇、己醇、環己醇、乙二醇、丙三醇（甘油）等之醇類 ;3 -乙氧基丙酸乙基、3 —甲氧基丙酸甲基、乳酸乙基' 醋酸己基、醋酸戊基等之酯類，r -丁內酯等之環狀酯類 等。 α -羥基異丁酸酯類與其他溶劑之組合，令人滿意者 可舉例如α -羥基異丁酸甲基/丙基乙二醇一甲基醚醋酸 酯、α -羥基異丁酸甲基/ 3-乙氧基丙酸乙基、〇： -羥 基異丁酸甲基/乳酸乙基、α —羥基異丁酸甲基/ r 一丁 內酯等。 前記（C )溶劑之使用量，對未輻射敏感性組成物全 量而言’其質量百分率通常爲50— 95%，理想値是70-9 0 %。溶劑使用量5 0 - 9 5 %時’具有形成良好平坦性之 傾向，令人滿意。 本輻射敏感性組成物的其他成分，可含有（D )低分 子鹼可溶性化合物、（E )架橋劑及（F )聚合性單體等。 (D )低分子鹼可溶性化合物，是指分子中持有竣基 、苯酚性羥基等之鹼溶解性之能基，分子量〗，000以下之 化合物。 前記低分子量鹼可溶性化合物可列舉多價化合物、 羧酸化合物等。 (9) (9)200401165 多價酚化合物，舉例如三羥基苯幷醌、四羥基苯并酉昆 五羥基苯并醌、六羥基苯并醌、雙（2，4 —二羥基醌）甲 烷、雙（r 一羥基酚）甲烷、1，1，1一三（p —羥基苯基 )甲烷、1，1，3 -三（2，5 —二甲基一 4--羥基苯基）— 3 -苯基丙院、4’ 4 一〔1—〔4—〔1—〔4一經基苯基 〕一1 一甲基乙基〕苯基〕乙叉〕二酚、3,3，3，，3 一 —四甲基—1，1'一螺二茚一5’6，7’5，，6一，7一 — 己烷等。 羧酸化合物可舉例如環己烷羧酸、環己烷二羧酸 '丙 二酸、丁二酸' 苯酸、α -苯乙醇酸、十八酸、亞油酸等 〇 本輻射敏感性組成物中（D )低分子量鹼可溶性化合 物的含量，對本組成物固體部分之重量而言，質量百分比 通常是3 0 %以下，理想値是20 %以下。低分子量鹼可溶 性化合物之含量是固體部份重量之3 0 %以下時，所得膜 之殘膜率不會下降過多’能維持透明膜之性能。 (Ε )架橋劑可列舉環氧化合物、羥甲基化合物等。 環氧化合物則可列舉芳香族環氧化合物、脂環族環氧化合 物及脂肪族環氧化合物。 芳香族環氧化合物爲例’可列舉有苯基環氧丙基醚等 之單功能環氧化合物’至少具有一個芳香放核的多價酚、 或其烯烴氧化物附加體之聚環氧丙基醚，又可列舉如雙酚 A、四溴基雙酚A、雙酚F、雙酚S等之雙酚化合物，或 雙酚化合物之烯烴氧化物（例如乙烯氧化物、丙烯氧化物 -12- (10) (10)200401165 、丁烯氧化物等）附加體’與環氧氯丙烷反應製成之環氧 丙基醚類、漆用酚醛型環氧樹脂（如酚漆用酚醛型環氧樹 脂、甲鼢•漆用酚醛型環氧樹脂、溴化紛漆用酔醒型環氧 樹脂等）、三酚甲烷三環氧丙基醚等。 脂環族環氧化合物列舉有4 -乙烯環己烯單環氧化物 、原疲院單環氧化物、檸檬燏單環氧化物、3，4 -環氧環 己基甲基一 3’ 4一環氣環己院一甲竣酸醋、二（3，4 一環 氧環己基甲基）己二酸酯、2-（3，4 —環氧環己基一 5, 5 -螺旋一 3，4一環氧）環己酮—間一二氧雜環己院、二 (2’ 3 -環氧環己基戊基）酸、2— (3，4 一環氧環己基 一 5，5 —螺旋—3’ 4一環氧）環己烷—間一二氧雜環己烷 ' 2, 2 —二〔4— (2，3_環氧丙氧基）環己基〕六氟丙 烷、BHPE— 3150(大謝化工公司製造）等。 脂肪族環氧化合物’可舉例如1，4 - 丁燒二醇二環 氧丙基醚、1，6—己烷二醇二環氧丙基醚、乙烯乙二醇雙 環氧丙基醚、乙烯乙二醇單環氧丙基醚 '丙烯乙二醇雙環 氧丙基醚、丙稀乙二醇單環氧丙基酸、聚乙稀乙二醇雙環 氧丙基醚、丙烯乙二醇雙環氧丙基醚、新戊基乙二醇雙環 氧丙基醚、新戊基乙二醇單環氧丙基醚 '丙三醇雙環氧丙 基醚、丙三醇三環氧丙基醚、二羥甲基丙院雙環氧丙基醚 、三羥甲基丙烷單環氧丙基醚、三羥甲基丙烷三環氧丙基 醚、二丙三醇三環氧丙基醚、山梨糖醇四環氧丙基醚、烯 丙基環氧丙基醚、2-乙基己基環氧丙基醚等。 羥甲基化合物列舉有烷氧基甲基化三聚氰胺樹脂、烷 ·} λ ；-： -13- (11) (11)200401165 氧基甲基化尿素樹脂等之烷氧基甲基化氨基樹脂等。這裡 所謂烷氧基甲基化三聚氰胺樹脂有甲氧基甲基化三聚氧胺 樹脂、乙氧基甲基化三聚氰胺樹脂、丙氧基甲基化三聚氰 胺樹脂、丁氧基甲基化三聚氰胺樹脂等，而烷氧基甲基化 尿素樹脂則列有甲氧基甲基化尿素樹脂、乙氧基甲基化尿 素樹脂、丙氧基甲基化尿素樹脂、丁氧基甲基化尿素樹脂 等。前記架橋劑，可以按各種各類單獨或兩種以上組合使 用。 本輻射敏感性組成物內架橋劑之含量，對本組成物固 體部分之重量而言，其質量百分率小於 5 0 %時最理想。 5 0 %以下時，曝光部分與未曝光部分之溶解性差異變大， 具有容易形成圖形之傾向，令人滿意。 本輻射敏感性組成物含有（F )聚合性單體時亦佳。 含有聚合性單體，可形成硬度較高之絕緣膜等。所謂聚合 性單體例如可用經由加熱得有基聚合之聚合性單體，得有 陽離子聚合之聚合性單體等。 所謂獲得基聚合之聚合性單體，列舉例如含有聚合性 碳素-碳素不飽和結合之化合物，但是單功能基聚合性單 體亦可，二功能基聚合性單體、三功能基聚合性單體或多 功能基聚合性單體也好。 單功能基之聚合性單體可列舉如壬基苯基卡必醇丙烯 酸酯、壬基苯基甲基卡必醇丙烯酸酯、2 -羥基- 3 -苯氧 基丙基丙烯酸酯、2 -羥基- 3-苯氧基丙基甲基丙烯酸酯 、2 -乙基己基卡必醇丙烯酸酯、2 -乙基己基卡必醇甲基 -14- (12) 200401165 丙烯酸酯、2 -羥基乙基丙烯酸酯、2一羥基乙基甲 酸酯、N -乙烯基吡咯烷酮等。 雙功能基之聚合性單體可列舉如丨，6 -己院 丙烯酸酯、1 ’ 6 -己烷二醇二甲基丙烯酸酸酯、乙 醇丙烯酸酯、乙烯乙二醇雙甲基丙烯酸酯、新戊基 雙丙烯酸酯、新戊基乙二醇雙甲基丙烯酸酯、三乙 醇雙丙烯酸酯、三乙烯乙二醇雙甲基丙烯酯、雙g 雙（丙烯醯氧乙基）醚、3 —甲基戊烷乙二醇雙甲 酸酯等。 又’三功能基以上之聚合性單體，可例舉如三 丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、 醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四 烯酸酯、季戊四醇四甲基丙烯酸酯、季戊四醇五丙 、季戊四醇五甲基丙烯酸酯、雙季戊四醇六丙烯酸 季戊四醇六甲基丙烯酸酯等。 前記聚合性單體中’以二功能基或三功能基以 合性單體較令人喜歡使用。又，以二功能基或三功 上之聚合性單體，與單功能基聚合性單體組合使用 得有陽離子聚合之聚合性單體，可例舉含有乙 、丙烯基醚基等陽離子聚合性之功能基之聚合性單 體而言，有三乙烯乙二醇雙乙烯基醚、1，4-環己 醇雙乙烯醚、4-羥基丁基乙烯醚、十二基乙烯醚 一 CURE PEPC(1SP英培達公司製）。 使用前記聚合性單體時，可單獨或兩種以上組 基丙烯 二醇二 烯乙二 乙一酉争 基乙二 》A之 基丙烯 經甲基 季戊四 醇四丙 烯酸酯 酯、雙 上之聚 能基以 亦佳。 烯醚基 體 ' 具 烷二甲 、RAP1 合使用 (13) (13)200401165 。本輻射敏感性組成物中，前記聚合性單體含量，對本組 成物固體部份重量而言，質量百分率50%以下者較理想 。5 0 %以下時，有抑制曝光部份溶解速度下降之傾向，令 人滿意。 本輻射敏感性組成物，爲必要對應不阻礙本發明之效 果範圍，例可含有界面活性劑、氧化防止劑、溶解抑止劑 、增感劑、紫外線吸收劑、光安定劑、接著性改良劑、電 子供與體等各種添加物。 本輻射敏感性組成物，例如可將（A)鹼可溶性樹脂 溶於（C )溶劑後之溶液，與（B )輻射線感應化合物溶 於（C )溶劑後之溶液混合後製造。使用多價苯酚化合物 、架橋劑、聚合性單體及添加劑等場合時，亦可更進而添 加此等成分。又混合後，爲降低固體成分濃度，亦可追加 溶劑。混合後最好去除過濾固形物，如以孔徑3 /z m以 下，最好是〇 5 // m以上2 A m以下之過濾器進行過濾 較理想。 在使用本輻射性組成物製成透明膜時，例如可以在基 板（圖1(2))上形成來自本組成物之薄層，使揮發成 分揮發減少溶劑含量後’形成輻射性組成物層（圖1 ( a )):介有正圖罩對該物層照射輻射線（圖1(4)，曝 光後顯像。 對基板（圖1 ( 2 )而言，例如可舉出透明玻璃板等 。於前記基板上亦可形成TFT或CCD等迴路及彩色過濾 器等。 (14) (14)200401165 溶劑含量減少後，來自輻射敏感性樹脂組成物之層（ 圖1(1)) ’通常方法，例如可按在基板（圖1 ( 2 )上 塗布本組成物之方法。塗布照例可按旋轉塗布法，流延塗 布法、滾筒塗布法、切削旋轉塗布法等進行。塗布後，加 熱乾燥（前烘）或加熱後真空乾燥，使溶劑等揮發成分揮 發，溶劑含量減少’形成輻射敏感性樹脂組成物層（圖1 (1 ))。但此組成物層，對其質量而言，通常含有質量 百分比1〜10%之α -羥基異丁酸酯類。此α 一羥基異丁 酸議類含量是1〜1 〇質量％時，顯像速度增加，有高感度 化傾向，頗爲理想。 又，此溶劑含量減少後，輻射敏感性樹脂組成物層（ (圖1(1))之厚度，照例是1 5〜5 程度。 其次，溶劑含量減少後幅射敏感性樹脂組成物層（圖 1(1))，介有正圖罩（圖1 ( 3 ))照射輻射線（圖1 ( 4))。正圖罩（圖1(3))之圖形，應透明膜之目的圖 形’加以適當疊擇。輻射線按例可用g線及i線等光線。 輻射線溶劑含量減少後之輻射敏感性樹脂組成物層（圖1 (1 ))能全面繼續平行照射，例如使用圖罩調整器照射 也令人滿意。這種輻射線照射所得結果，可使正圖罩與溶 劑減少後輻射敏感性樹脂組成物之位置，正確吻合。 如此曝光後顯像。顯像是將溶劑含量減少後之輻射敏 感性樹脂組成物層（圖1(1))，曝光後所得之層（以 下稱爲曝光後輻射敏感性樹脂組成物層），使之接觸顯像 液之方法進行。顯像液可用鹼性化合物的水溶液，包括無 -17- (15) (15)200401165 機及有機兩種均可。無機鹼性化合物可舉例如氫氧化鈉、 氫氧化鉀、磷酸氫三鈉、磷酸二氫鈉、磷酸氫二銨、磷酸 二氫化銨、磷酸二氫化鉀、矽酸銨、矽酸鉀、硼酸鈉、硼 酸鉀及氨等。 有機鹼性化合物可舉例如四甲基羥酸銨、2 -氫氧乙 基三甲基羥酸銨、一甲基胺、二甲基胺、三甲基胺、一乙 基胺、二乙基胺、三乙基胺、一丙基胺、二異丙基胺、乙 醇胺等。 前記驗性化合物可以按各種類單獨或兩種以上組合吏 用。 顯像液以其質量爲1 〇 〇時，鹼性化合物通常含量爲 0 1〜1 0，理想値是0 2〜5。 顯像液含有表面活性劑亦佳。表面活性劑可舉例如非 離子系表面活性劑、陽離子表面活性劑、陰離子表面活性 劑等。 非離子系表面活性劑可舉例如聚羥基乙烯烷基醚、聚 羥基乙烯芳基醚、聚羥基乙烯烷基芳基醚等之聚羥基乙烯 誘導體、羥基乙烯/羥基丙烯嵌段聚合物、山梨糖醇軒脂 肪酸酯、聚羥基乙烯山梨糖醇酐酯肪酸酯、聚烴基乙烯脂 肪酸酯、聚羥基乙烯烷基胺等。 陽離子系表面活性劑可舉例如硬脂醯胺鹽酸鹽等之胺 鹽、氯化月桂基三甲基銨等之第四級銨鹽等。 陰離子系表面活性劑可舉例如月桂醇硫酸酯鈉、油醇 硫酸酯鈉等之高級醇硫酸酯鹽、月桂基硫酸鈉、月桂基硫 -18 - (16) (16)200401165 酸銨等之烷基硫酸鹽、月桂基苯磺酸鈉、月桂基萘磺酸鈉 等之烷基芳基磺酸鹽等。此等表面活性劑可以各種類單獨 或兩種以上組合使用。 又，顯像液含有有機溶劑亦佳。所含有機溶劑諸如甲 醇、乙醇等水溶性有機溶劑等。 使曝光後輻射敏感性樹脂組成物層接觸顯像液時，最 好是能使組成物層形成的基板（圖1 ( 2 ))浸漬於顯像 液。依據顯像處理，曝光後輻射敏感性樹脂組成物層中， 先前曝光被輻射線照射之輻射線照射部份（圖1(12)) 溶解於顯像液裡，未被輻射線照射之輻射線未照射部份（ 圖1 ( 11))不溶解於顯像液而殘留著，形成圖形（圖1 (5 ) ) 〇 本輻射敏感性組成物因含有具水溶性之α -羥基異丁 酸酯，曝光後組成物層與顯像液接觸，曝光部份迅速溶解 ，圖形形成時之感度高。又對輻射線敏感化合物（Β )， 使用苯酮二氮雜苯化合物時，曝光後輻射敏感性樹脂組成 物層，即使與顯像液接觸時間短，輻射線照射部分（圖1 (11 ))更容易溶解除去。又組成物層與顯像液長時間接 觸，輻射線未照射部份（圖1 ( 12 )也不溶解於顯像液而 消失。 顯像後通常水洗乾燥。乾燥後，更對所得圖形（圖1 (5 ))全面繼續照射輻射線，獲得更爲透明之透明膜最 理想。這裡照射輻射線單位面積的照射量，通常較先前曝 光時的照射量多。 -19 - (17) 200401165 如此形成的圖形（圖1(5))，更進行加熱 後烘），俾能提高透明膜的耐熱性及耐溶劑性。加 全面性照射後之基板，置於熱盤或烤爐等加熱設備 處理。加熱溫度通常是1 5 0 — 2 5 0 °C，理想是 1 8 0 -程度。加熱溫度150— 250 °C時，硬化充分，也有 溶劑性；又因加熱沒有塗層著色，透明性也有良好 加熱時間通常5 - 9 0分鐘，理想是15 — 9 0分鐘。 分鐘時硬化充分，耐溶劑性良好，生產性也不易降 爲理想。 以本輻射敏感性樹脂組成物，按上述要領製成 膜，例如有用於作爲構成TFT的透明膜，特別是 緣膜、塗覆、間隔物、半透氣型之厚膜重合部分。 舉例 以上所記，說明本發明之實施形態。但上述所 發明的實施形態，終完是例示，本發明的範圍並不 此等形態。本發明的範圍，如申請專利範圍項內所 包含與此範圍之記載同等意義及範圍內所有的變更 按實施例詳細說明本發明，但本發明並不僅限於此 例。 合成例 裝有攪拌機、冷卻管及溫度計、容量200 ml 燒杯內，裝入以下原料。於氮氣流下，將四口燒杯 處理（ 熱是將 視加熱 -24 0〇C 良好耐 傾向。 5-90 低，頗 的透明 層間絕 開示本 僅限於 表示， 。以下 等實施 之四口 浸於油 -20 - (18) 200401165 槽，杯內溫度保持8 5 - 9 5 °C，攪拌3小時，進行反應後 得樹脂A1。此樹脂A1之聚苯乙烯換算重量，平均分子量 爲 1 5,000。 原料 甲基丙烯酸 6 6g 環己基甲基丙烯酸酯 1 1 4g 8 3 3 g 〇.9g 3 一乙基一 3一甲基丙烯醯西門甲基氧雜環丁烷 l78g α -羥基異丁酸甲基 偶氮二異丁腈 【實施方式】 實施例1 樹脂A1 ( 70質量部份）、 式（1 )200401165 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive resin composition, and a transparent film formed by using the same and a method for manufacturing the same. [Prior Art] For example, the radiation-sensitive resin composition is useful as a material for a TFT insulating film and a transparent film used in a TFT-type liquid crystal display device. In order to improve the productivity of the TFT insulating film, the radiation-sensitive resin composition made of the insulating film is required to have high sensitivity, which can shorten the exposure time, and the high imaging residual film rate required to improve the pass rate. With high solvent resistance. However, in order to obtain a high sensitivity, the solubility in the developing solution is increased, and the residual film rate and the solvent resistance tend to be lowered. [Summary of the Invention] The (A) alkali-soluble resin contained in the radiation-sensitive resin composition may include, for example, a phenolic hydroxyl polymer compound: a phenolic lacquer resin and a polyhydroxystyrene resin, and a polymer containing a hydroxyl polymer compound. Methacrylic polymer, acrylic polymer, and the like, resins containing phenylhydrazone or hydroxyl. It is also preferred that the alkali-soluble resin has curability. Examples of the polymer compound having such a hardening property include compounds containing a vinyl group, an epoxy group, an oxetanyl group, a tetrahydrofuranyl group, and a butyrolactone skeleton. As the alkali-soluble resin, a particularly preferable polymer compound is a polymer compound having a carboxyl group and an oxetane skeleton. The oxetane skeleton -4 _ (2) (2) 200401165 means an oxetane ring (trisex methyl oxide). The polymer compound having an oxetane skeleton means a polymer compound containing the aforementioned oxetane ring (trimethyl oxide). The above-mentioned polymer compounds may include, for example, a structural unit derived from a carboxyl group-containing monomer, and a copolymer formed from a structural unit derived from an oxetane skeleton, and may be derived from other monomers if necessary. The structural units form a copolymer. Here, the carboxyl-containing monomer may include, for example, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and the like, an unsaturated carboxylic acid having one or two or more carboxyl groups in a molecule, and specifically, such as acrylic acid and methacrylic acid. , Butenoic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and the like. The oxetane skeleton-containing monomer may be, for example, 3-methyl-3 (m-acryl) simene methyloxetane, 3-ethyl-3 (m-acryl) imidooxetane Alkanes, 3-methyl-3 (m-acryl) siemenethyloxetane, and 3-methyl-3 (m-acryl) siemenethyloxetane. Other monomers include, for example, monomers containing a polymerizable carbon-carbon unsaturated bond, specifically aromatic vinyl compounds such as styrene 'α-methylstyrene, vinyltoluene, and the like, methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylic acid esters such as esters, cyclohexyl acrylate, cyclohexyl methacrylate, norbornyl isoacrylate, and isoelectric methacrylate; unsaturated carboxylic acid urethanes such as aminoethyl acrylate; vinyl acetate, Vinyl carboxylic acid esters such as ethylene propionate; acrylonitrile, methacrylonitrile (3) (3) 200401165, and cyanide vinyl compounds such as chloronitrile. These other monomers can be used individually or in combination of two or more. When the (A) alkali-soluble resin is obtained from a carboxyl group-containing monomer and an oxetane skeleton-containing monomer, the mass percentage of the carboxyl group-containing monomer to the total monomers is usually 5-50%, and it is more desirable. It is in the range of 15 to 40%. In the case of an oxetane skeleton-containing monomer, it is usually 95 to 50%, and preferably 85 to 60% of the total monomers. The mass percentage of the carboxyl group-containing monomer to the total monomer is 5 to 50%, and the solubility of the organic solvent tends to be improved, which is satisfactory; and the monomer containing the oxetane skeleton is 95 to 50% At this time, the hardening speed tends to accelerate, which is ideal. Furthermore, it is also preferable to include a structure derived from other monomers. (A) Specifically, the alkali-soluble resin includes, for example, 3-ethyl-3 -propene-propanemethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3 -Methacrylic acid simon methyloxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3 -methacrylic simon methyloxetane / methyl Acrylic acid / styrene copolymer, 3 -ethyl-3 -methacrylic acid simon methyloxetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3 monoethyl-3 -methyl Acrylic-Simon methyloxetane / methacrylic acid / methacrylic acid methyl / styrene copolymer and the like. Foreword (A) The weight-average molecular weight of alkali-soluble resin (determined by gel permeation chromatography with polyethylene as the standard), usually in the range of 2,000 to 400,000. 'Ideal' is 2,000 to The range of 100,000, most preferably 3,000 to 50,000. The weight average molecular weight in the foregoing range is in the range of 2,000 to (4) (4) 200 401 165 4 0, 0 0 ', and a sufficient development speed is obtained, which is ideal. (A) The alkali-soluble resin can be used in combination of two or more. The content of the (A) alkali-soluble resin in the radiation-sensitive composition is usually 5 to 90% by mass, and ideally 30 to 90% by weight of the radiation-sensitive resin composition after removing the solvent. (A) When the content of the alkali-soluble resin is 5 to 90%, there is a tendency that the development speed is sufficient, which is satisfactory. (B) Radiation-sensitive compounds contained in the radiation-sensitive composition are compounds that delay the dissolution rate of the composition to alkali before irradiation with the radiation. However, when receiving radiation, the changes in the structure of the compound described above may include: The compound that accelerates the dissolution rate of the alkaline aqueous solution is accelerated, and as a result, the compound having the effect of promoting the dissolution rate of the radiation-sensitive resin composition, such as a compound containing a benzoquinone diazine group, is obtained. The benzophenone diazide compound described above may be, for example, 1,2-benzoquinonediazide sulfonate, 1,2-naphthoquinonediazide sulfonate, 1 '2-benzobenzoquinone di Azidosulfonic acid amines, 1,2-naphthoquinonediazidesulfonic acid amines and the like. Desirably, 1,2-naphthoquinonediazidesulfonate. Specifically, 2'3,4-trihydroxybenzoquinone-1'2-naphthobenzodiazide-4monosulfonate, 2,3,4-trihydroxybenzoquinone-1,2-one Naphthoquinonediazide-5-sulfonate, 2,4, ό-trihydroxybenzoquinone-1,2-naphthoquinonediazide-4-monosulfonate, 2,4,6- Three basic basic benzoquinones-1,2-Ceidoquinonediazide-5-sulfonate, etc. Two basic basic quinones, 1,2-naphthoquinonediazide sulfonate, 2 '2 / '4' 4, monotetrahydroxybenzoquinone-1,2-naphthoquinonediazide-4 monosulfonic acid ester (5) (5) 200401165 、 2,2 z 、 4,4-tetrahydroxy Benzoquinone-1,2-benzoquinonediazide-5-sulfonate, 2,2-, 4,3 / -tetrahydroxybenzoquinone-1,2-naphthoquinonediazide- 4 —sulfonic acid ester, 2, 2 >, 4, 3 / —tetrahydroxybenzo-1,2-Cai and benzo-azido-5 —mineral vinegar, 2,3,4,4 / —tetrahydroxy Benzoquinone-1,2-naphthoquinonediazide-4 monosulfonate, 2,3,4,4—tetramene benzoquinone-1,2-benzobenzodiazide-1 5 --sulfonic acid Ester, 2,3,4,2 ——tetrahydroxybenzoquinone 1,2, naphthoquinonediazide-4 monosulfonate, 2,3,4,2 — -tetrahydroxybenzoquinone 1 , 2-naphthobenzoquinonediazide-5-sulfonate, 2,3,4,4-tetrahydroxy-1,3,1-methylbenzoquinone-1,2-naphthoquinonediazoxy —4-monosulfonate and 2,3,4, —tetrahydroxy——methoxybenzobenzoquinone-1,2-naphthoquinonediazoxy-5—sulfonate and other tetrahydroxybenzoquinones Of 1,2-naphthoquinonetriacetoxy sulfonate, 2,3,4,2 //, factory one pentahydroxybenzobenzoquinone-1,2-naphthoquinone diazido-4 monosulfonate , 2,3,4,2,, 6 / -pentahydroxybenzoquinone-1,2-naphthoquinonediazoxy-5-sulfonate and other 1,2-naphthobenzopentaquinones Quinone diacetoxy sulfonate, 2,4,6 '3 /' 4 /, 5 > -hexahydroxybenzophenone-1,2-naphthoquinone diacetoxy-4 -sulfonate, 2,4,6, /, 4-, 5 > -Hexahydroxybenzoquinone-1,2-naphthoquinonediazoxy-4-sulfonate, 3,4,5,3-, 4- , 5 > -Hexahydroxybenzoquinone-1, 2 —Naphthoquinonediazoxy-4-sulfonate, 3,4,5,3 >, 4,1,5 —-hexahydroxybenzoquinones 1,2-naphthoquinonediazoxy-1 Hexahydroxybenzoquinones such as 5-sulfonates, 1,2-naphthoquinone diazidosulfonates, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone di Zid-8- (6) (6) 200401165 Oxy-5-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazoxy-1, 4-monosulfonate, bis ( p-hydroxyphenyl) methane-1,2-naphthoquinonediazoxy-5-sulfonate, 1,1,1, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonedione Epoxy-4-sulfonic acid ester, 1,1,1, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazido-5-sulfonic acid ester, bis (2,3, 4-trihydroxyphenyl) methane-1,2-naphthoquinonediazyloxy-4 monosulfonate, bis (2,3,4-trimerylphenyl) methane-1,2-naphthoquinone Diacetoxy-5-sulfonate, 2,2,1-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediacetoxy-4-sulfonate, 2 ,-double 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazoxy-5-sulfonate, 1,1,3-tri (2,5 — _ • methyl-4 1 Phenyl) —3 —phenylpropane —1,2-naphthoquinonediazoxy-4 monosulfonate, 1,1,3-tris (2,5-dimethyl-1,4-hydroxyphenylbenzene Phenyl)-3-phenylpropane-1,2-naphthoquinonediazido-5-sulfonate, 4,4 ^ — [1— [4-—1-4—hydroxyphenyl] — 1—1 Ethyl] phenyl] acetylene] diphenol-1,2-naphthoquinonediazoxy- 5-sulfonate, bis (2,5-dimethyl-4 4-hydroxyphenyl) -2 -hydroxyl Benzyl methane-1,2-benzoquinonediazyloxy-4 monosulfonate, bis (2,5-dimethyl-4 4-hydroxyphenyl) -2-hydroxybenzenemethane-1,2-naphthalene Benzoquinonediazoxy-5-sulfonate, 3,3,3 ―, 3 > —tetramethyl-1,1 —spirobisindanone—5,6,7,5 —, 6, , 7-hexanol-1,2-naphthoquinonediazoxy-4-sulfonate, 3,3,3,, 3, -tetramethyl-1-1-1'-spiral bisindanone— 5,6,7,5 ^ ,, 7 / —hexanol —1,2 —naphthoquinonediazoxy — 5-sulfonate Z ii 0 -9-(7) 200401165, 2, 2'4 —trimethyl-7, 2 1,4-trihydroxyflavan-1,2-naphthoquinonediazoxy-4 monophosphonate, 2,2,4-trimethyl-7,2 1,4-trihydroxyflavan 1,2-naphthoquinonediazyloxy-5-sulfonate and other (polyhydroxyphenyl) alkanes 1,2-naphthoquinonediazyloxysulfonate and the like. The foregoing quinonediazoxy compounds are used singly or in combination of two or more kinds. The content of the (B) radiation-sensitive compound in the radiation-sensitive composition is usually 2 to 50% by mass, and ideally 5 to 40% by weight of the solid portion of the composition. When the content of the radiation-sensitive compound is 2 to 50%, the dissolution rate difference between the exposed portion and the unexposed portion tends to increase, which is satisfactory. The content of the (C) solvent α-hydroxyisobutyric acid esters contained in the radiation-sensitive composition is usually 16% or more of the total solvent amount, and ideally 35% or more. If it is less than 16%, the sensitivity will decrease due to the decrease in the solubility of the developer. Examples of the α-hydroxyisobutyric acid esters include α-hydroxyisobutyric acid methyl ester and α-hydroxyisobutyric acid ethyl, and the like, and α-hydroxyisobutyric acid methyl is preferable. Further, as a possible solvent to be mixed with α-hydroxyisobutyrate, an organic solvent compound of a known radiation-sensitive resin composition can be used. The above-mentioned mixed possible solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like; ethylene glycol monoalkyl ethers; and diethylene glycol dimethyl ether. , Diethylene glycol diethyl ether, diethylene glycol dipropyl ether 'diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ethers; ethylene glycol monomethyl ether methyl ether quinone ester, ethylene glycol monoethyl ether acetate Ethylene glycol alkyl ether acetate; propylene glycol (10) (8) (8) 200401165 Alcohol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Ether ether acetates, aromatic hydrocarbons such as benzene, toluene 'xylene, etc .; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other trimethyl ketones; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol (glycerol), etc .; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, Ethyl lactate esters such as hexyl acetate, amyl acetate, and cyclic esters such as r-butyrolactone. A combination of α-hydroxyisobutyrate and other solvents, for example, α-hydroxyisobutyric acid methyl / propyl ethylene glycol monomethyl ether acetate, α-hydroxyisobutyric acid methyl / Ethyl 3-ethoxypropionate, 0: -hydroxyisobutyric acid methyl / lactic acid ethyl, α-hydroxyisobutyric acid methyl / r monobutyrolactone, and the like. The amount of the solvent (C) mentioned above is generally 50 to 95% of the mass of the non-radiation-sensitive composition, and ideally 70 to 90%. When the solvent is used in an amount of 50 to 95%, '' tends to form a good flatness, which is satisfactory. Other components of the radiation-sensitive composition may contain (D) a low-molecular alkali-soluble compound, (E) a bridging agent, and (F) a polymerizable monomer. (D) A low-molecular alkali-soluble compound refers to a compound having an alkali-soluble energy group, such as a phenyl group, a phenolic hydroxyl group, and the like, having a molecular weight of 10,000 or less. Examples of the aforementioned low-molecular-weight alkali-soluble compound include polyvalent compounds and carboxylic acid compounds. (9) (9) 200401165 Polyvalent phenol compounds, such as trihydroxybenzoquinone, tetrahydroxybenzopyrene pentahydroxybenzoquinone, hexahydroxybenzoquinone, bis (2,4-dihydroxyquinone) methane, Bis (r-hydroxyphenol) methane, 1,1,1tris (p-hydroxyphenyl) methane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) — 3 -Phenylpropanone, 4 '4- [1- [4-[1- [4-Cyridylphenyl]-1-methylethyl] phenyl] ethylidene] diphenol, 3,3,3 ,, 3 1-tetramethyl-1,1'-spirobiindene-1 5'6, 7'5 ,, 6-1, 7-1-hexane and the like. Examples of the carboxylic acid compound include cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid 'malonic acid, succinic acid' benzoic acid, α-phenylglycolic acid, octadecanoic acid, and linoleic acid. The content of the (D) low-molecular-weight alkali-soluble compound in the solid content of the composition is usually 30% or less by mass, and ideally 20% or less. When the content of the low-molecular-weight alkali-soluble compound is 30% or less by weight of the solid portion, the residual film rate of the obtained film will not decrease too much, and the performance of the transparent film can be maintained. (E) Examples of the bridging agent include epoxy compounds and methylol compounds. Examples of the epoxy compound include an aromatic epoxy compound, an alicyclic epoxy compound, and an aliphatic epoxy compound. Aromatic epoxy compounds are exemplified as 'monofunctional epoxy compounds including phenylglycidyl ether and the like', polyvalent phenols having at least one aromatic nucleating polyvalent phenol, or polyepoxypropyl groups of olefin oxide additions thereof Ethers include bisphenol compounds such as bisphenol A, tetrabromobisphenol A, bisphenol F, and bisphenol S, or olefin oxides of bisphenol compounds (eg, ethylene oxide, propylene oxide-12- (10) (10) 200401165, butene oxide, etc.) Additives are epoxy-propyl ethers made of epoxy resin and epichlorohydrin, and phenolic epoxy resins for paints (such as phenolic epoxy resins for phenol paints) , Phenolic epoxy resin for formazan • lacquer, awakening epoxy resin for brominated varnish, etc.), triphenol methane triglycidyl ether, etc. Cycloaliphatic epoxy compounds are listed as 4-vinylcyclohexene monoepoxide, proton monoepoxide, lemon hydrazone monoepoxide, 3,4-epoxycyclohexylmethyl-1,3'4-one ring gas Cyclohexanone monomethyl succinate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5, 5 -helix-3,4 (Oxy) cyclohexanone-m-dioxane, bis (2 '3 -epoxycyclohexylpentyl) acid, 2- (3,4-epoxycyclohexyl-5,5-helix-3' 4-epoxy) cyclohexane-m-dioxane '2, 2-bis [4- (2,3_glycidoxy) cyclohexyl] hexafluoropropane, BHPE-3150 (Da Xie Chemical company)). Examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, Ethylene glycol monoglycidyl ether 'propylene glycol diglycidyl ether, propylene glycol monoglycidyl acid, polyethylene glycol diglycidyl ether, propylene glycol Alcohol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether 'glycerol diglycidyl ether, glycerol triepoxy Propyl ether, dimethylolpropane diglycidyl ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether Ether, sorbitol tetraglycidyl ether, allylglycidyl ether, 2-ethylhexylglycidyl ether and the like. Examples of methylol compounds include alkoxymethylated melamine resins and alkane} λ;-: -13- (11) (11) 200401165 alkoxymethylated amino resins such as oxymethylated urea resin . The alkoxymethylated melamine resin here includes methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc. The alkoxymethylated urea resin includes methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like. Foreword bridging agent can be used alone or in combination of two or more types. The content of the bridging agent in the radiation-sensitive composition is most ideal when the mass percentage of the solid portion of the composition is less than 50%. When it is 50% or less, the difference in solubility between the exposed portion and the unexposed portion becomes large, and it tends to be easy to form a pattern, which is satisfactory. This radiation-sensitive composition is also preferable when it contains (F) a polymerizable monomer. Containing a polymerizable monomer, it can form an insulating film with high hardness. As the polymerizable monomer, for example, a polymerizable monomer having a radical polymerization obtained by heating, a polymerizable monomer having a cationic polymerization can be used. Examples of the polymerizable monomer to be group-polymerized include compounds containing a polymerizable carbon-carbon unsaturated bond, but monofunctional polymerizable monomers are also possible, difunctional polymerizable monomers, and trifunctional polymerizable polymers. A monomer or a multifunctional polymerizable monomer is also preferable. Examples of the monofunctional polymerizable monomer include nonylphenylcarbitol acrylate, nonylphenylmethylcarbitol acrylate, 2-hydroxy-3 -phenoxypropyl acrylate, 2-hydroxy -3-phenoxypropyl methacrylate, 2-ethylhexylcarbitol acrylate, 2-ethylhexylcarbitol methyl-14- (12) 200401165 acrylate, 2-hydroxyethyl acrylic acid Esters, 2-hydroxyethyl formate, N-vinylpyrrolidone and the like. Examples of bifunctional polymerizable monomers include hexamethylene acrylate, 1'6-hexanediol dimethacrylate, ethanol acrylate, ethylene glycol dimethacrylate, and Amyl diacrylate, neopentyl glycol dimethacrylate, triethanol diacrylate, triethylene glycol dimethacrylate, bisg bis (acryloxyethyl) ether, 3-methyl Pentaneethylene glycol diformate and the like. Also, the polymerizable monomer having more than three functional groups may be exemplified by tripropane triacrylate, trimethylolpropane trimethacrylate, alcohol triacrylate, pentaerythritol trimethacrylate, pentaerythritol Esters, pentaerythritol tetramethacrylate, pentaerythritol pentapropene, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate pentaerythritol hexamethacrylate and the like. Among the aforementioned polymerizable monomers, a bifunctional group or a trifunctional group is preferably used as a polymerizable monomer. In addition, a polymerizable monomer having a difunctional group or a trifunctional polymer can be used in combination with a monofunctional polymerizable monomer to obtain a cationic polymerizable polymerizable monomer. Examples of the polymerizable monomer include a cationic polymerizable group such as an ethyl and acryl ether group. As the polymerizable monomer of the functional group, there are triethylene glycol divinyl ether, 1,4-cyclohexanol divinyl ether, 4-hydroxybutyl vinyl ether, and dodecyl vinyl ether-CURE PEPC (1SP (Impeda). When using the aforementioned polymerizable monomers, the propylene glycol alone, or two or more kinds of propylene glycol diene ethylene diethylene glycol ethylene di "A" propylene can be passed through methyl pentaerythritol tetraacrylate ester, and the polymerizable group on both sides. Also good. Allyl ether matrix '' with alkane dimethyl and RAP1 (13) (13) 200401165. In the radiation-sensitive composition, the content of the polymerizable monomer described above is ideal for a solid portion of the composition with a mass percentage of 50% or less. Below 50%, there is a tendency to suppress the decrease in the dissolution rate of the exposed portion, which is satisfactory. The radiation-sensitive composition needs to correspond to a range that does not hinder the effect of the present invention. For example, it may contain a surfactant, an oxidation inhibitor, a dissolution inhibitor, a sensitizer, an ultraviolet absorber, a light stabilizer, an adhesion improver, Various additives such as electron donors. The radiation-sensitive composition can be produced, for example, by dissolving a solution of (A) an alkali-soluble resin in a (C) solvent and mixing a solution of a (B) radiation-sensitive compound in a (C) solvent. When polyvalent phenol compounds, bridging agents, polymerizable monomers, and additives are used, these components can be further added. After the mixing, a solvent may be added to reduce the solid content concentration. After mixing, it is best to remove the filtering solids. For example, filtering with a filter with a pore diameter of 3 / z m or less, preferably from 0 5 // m to 2 A m is preferable. When a transparent film is formed by using the radiation composition, for example, a thin layer derived from the composition can be formed on a substrate (FIG. 1 (2)), and the volatile component is reduced to reduce the solvent content to form a radiation composition layer ( Fig. 1 (a)): The front layer is irradiated with radiation from the object layer (Fig. 1 (4), and developed after exposure. For the substrate (Fig. 1 (2), for example, a transparent glass plate, etc.) .Circuits such as TFT or CCD and color filters can also be formed on the substrate mentioned above. (14) (14) 200401165 After the solvent content is reduced, the layer from the radiation-sensitive resin composition (Figure 1 (1)) 'General method For example, the method of coating the composition on a substrate (Fig. 1 (2) can be used. As usual, coating can be performed by a spin coating method, a cast coating method, a roll coating method, a cutting spin coating method, etc. After coating, heat drying ( Pre-baking) or vacuum drying after heating to volatilize volatile components such as solvents and reduce the solvent content to form a radiation-sensitive resin composition layer (Figure 1 (1)). However, in terms of quality, this composition layer usually contains Α-hydroxyisobutyric acid esters in a mass percentage of 1 to 10%. When the content of the α-hydroxyisobutyric acid is 1 to 10% by mass, the development speed is increased, and the sensitivity tends to be high, which is ideal. Furthermore, after the content of the solvent is reduced, the radiation-sensitive resin composition layer ( (Figure 1 (1)), as usual, is about 15 to 5. Secondly, after the solvent content is reduced, the radiation-sensitive resin composition layer (Figure 1 (1)) has a front cover (Figure 1 (3 )) Irradiate the radiation (Figure 1 (4)). The pattern of the front cover (Figure 1 (3)) should be appropriately stacked with the target pattern of the transparent film. The radiation can be used according to the example of g-line and i-line. The radiation-sensitive resin composition layer (Fig. 1 (1)) with reduced radiation solvent content can continue to be irradiated in parallel, for example, using a mask adjuster is also satisfactory. The results obtained by such radiation irradiation can make the The front view mask and the position of the radiation-sensitive resin composition after the solvent are reduced are correctly matched. The image is developed after exposure as such. The imaging is the radiation-sensitive resin composition layer after the solvent content is reduced (Figure 1 (1)). Layer (hereinafter referred to as the radiation-sensitive resin composition layer after exposure) The developing solution is touched. The developing solution can be an aqueous solution of an alkaline compound, including -17- (15) (15) 200401165 and organic. The inorganic basic compound can be sodium hydroxide, hydrogen, etc. Potassium oxide, trisodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium silicate, potassium silicate, sodium borate, potassium borate and ammonia, etc. Organic alkaline compounds can be Examples include tetramethylammonium hydroxyammonium, 2-hydroxyethyltrimethylammonium hydroxyammonium, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethyl Amine, monopropylamine, diisopropylamine, ethanolamine, etc. The prescriptive compounds can be used individually or in combination of two or more kinds. When the mass of the developing solution is 100, the content of the basic compound is usually 0 1 to 10, and ideally, 0 2 to 5. It is also preferable that the developing solution contains a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants. Non-ionic surfactants include, for example, polyhydroxyethylene alkyl ethers, polyhydroxyethylene aryl ethers, polyhydroxyethylene alkyl aryl ethers, polyhydroxyethylene inducers, hydroxyethylene / hydroxypropylene block polymers, and Yamanashi. Sugar alcohol fatty acid esters, polyhydroxyethylene sorbitan fatty acid esters, polyalkylene glycol fatty acid esters, polyhydroxyethylene alkylamines, and the like. Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride, and fourth-order ammonium salts such as lauryltrimethylammonium chloride. Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, and lauryl sulphur-18-(16) (16) 200401165 ammonium acid, etc. Alkylaryl sulfonates, sodium laurylbenzenesulfonate, sodium laurylnaphthalenesulfonate, etc. These surfactants can be used alone or in combination of two or more kinds. It is also preferable that the developing solution contains an organic solvent. It contains organic solvents such as water-soluble organic solvents such as methanol and ethanol. When the radiation-sensitive resin composition layer is brought into contact with the developing solution after the exposure, it is preferable that the substrate (Fig. 1 (2)) on which the composition layer is formed is immersed in the developing solution. According to the imaging process, after the exposure, in the radiation-sensitive resin composition layer, the previously exposed portion irradiated with radiation (Figure 1 (12)) was dissolved in the imaging solution, and the radiation that was not irradiated by radiation was exposed The unirradiated part (Figure 1 (11)) does not dissolve in the developing solution and remains, forming a pattern (Figure 1 (5)). The radiation-sensitive composition contains water-soluble α-hydroxyisobutyrate After exposure, the composition layer is in contact with the developing solution, and the exposed part is quickly dissolved, and the sensitivity is high when the pattern is formed. For radiation-sensitive compounds (B), when using benzophenone diazabenzene compounds, the radiation-sensitive resin composition layer after exposure, even if the contact time with the imaging solution is short, the radiation-irradiated part (Figure 1 (11)) Easier to dissolve and remove. In addition, the composition layer is in contact with the developing solution for a long time, and the unirradiated part of the radiation (Figure 1 (12) does not dissolve in the developing solution and disappears. It is usually washed and dried after development. After drying, the obtained pattern is more accurate (Figure 1 (5)) Continue to irradiate radiation in all directions to obtain a more transparent transparent film. The amount of radiation per unit area of radiation here is usually more than that during previous exposure. -19-(17) 200401165 Pattern (Fig. 1 (5)), and then baking after heating), it can improve the heat resistance and solvent resistance of the transparent film. The substrate after comprehensive irradiation is placed in a heating device such as a hot plate or an oven for processing. The heating temperature is usually 1 50-2 50 ° C, ideally 1 8 0 -degree. When the heating temperature is 150-250 ° C, the hardening is sufficient, and it is also solvent; and because the coating is not colored due to heating, the transparency is also good. The heating time is usually 5-90 minutes, ideally 15-90 minutes. It hardens sufficiently in minutes, has good solvent resistance, and is not easy to reduce productivity. A film made of the radiation-sensitive resin composition according to the above-mentioned method is used, for example, as a transparent film constituting a TFT, particularly a thick film overlapping portion of an edge film, a coating, a spacer, and a semi-breathable type. Examples The foregoing describes the embodiments of the present invention. However, the embodiments of the present invention described above are exemplifications, and the scope of the present invention is not the same. As for the scope of the present invention, the scope of the present invention includes all changes within the meaning and scope equivalent to those described in the scope of the patent application. The present invention will be described in detail with reference to the examples, but the present invention is not limited to this example. Synthesis Example A 200 ml beaker equipped with a stirrer, a cooling tube, a thermometer, and the following materials were charged. Under a stream of nitrogen, treat a four-neck beaker (the heat is dependent on the temperature of -24 0 ° C. Good resistance. 5-90 Low, quite transparent interlayer insulation is limited to display only.) The following four implementations are immersed in oil -20-(18) 200401165 tank, keep the temperature in the cup at 8 5-9 5 ° C, stir for 3 hours, and react to obtain resin A1. The polystyrene equivalent weight of this resin A1 is 15,000. Acrylic acid 6 6 g Cyclohexyl methacrylate 1 1 4 g 8 3 3 g 0.9 g 3 Monoethyl-3 methyl methacryl simon methyloxetane 178 g α-hydroxyisobutyric acid methyl azo Diisobutyronitrile [Embodiment] Example 1 Resin A1 (70 mass parts), Formula (1)
-21 - (19) (19)200401165 式中所示化合物（2 5質量部份）、p -羥基苯乙烯/ 苯乙烯（95/5)共聚合體（聚苯乙烯換算重量平均分子 量16,000) ( 30質量份）a —羥基異丁酸甲基（474質量 部份）（全溶劑中α -羥基異丁酸甲基100% )，約23°C 下混合後，以孔徑15 // m之微孔過濾器加壓過濾，其 濾液即爲輻射敏感性樹脂組成物。 大小5 08 crax 5 08 cm之透明玻璃基板（康寧公司產 品#705 9 )〔圖1(2)〕，以中性洗劑洗淨後，水洗，再 以異丙醇洗淨乾燥，將上述輻射敏感性樹脂組成物旋轉塗 布於其表面。於淨化爐中1 0 0 °C加熱2分鐘（前烘），減 少溶劑含量後形成組成物層〔圖1(1)〕，其膜厚度爲 3 5 # m (圖 1 ( a )，以 UL VAC 公司 DEKT AK 3 測定〕。 其後’使用圖罩調整儀〔米開撒公司產品Μ - 2Li型 )〕在此輻射敏感性樹脂組成物層上，可有正圖罩照射輻 射線（圖1(4))，曝光。正圖罩（圖1 ( 3 )是爲在透 明膜上形成間隔1 0 // m之線格圖形（線路空間圖形）所 使用者。輻射線波長3 6 5 n m基準以強度1 0 0 m J / c m 2照 射之。 曝光後，於23 t之四甲基氫氧化銨水溶液（100質量 部份中含有0 7質量部份之四甲基氫氧化銨）內，顯像處 理7 0秒鐘後’以超純水洗淨，乾燥。乾燥後，以超高壓 水銀燈全面繼續照射輻射線（波長3 6 5 nm基準，強度 300 mJ/cm2) ’於淨化爐中220°C 30分鐘加熱，形成 透明膜（圖1 ( 5 )及1 ( c ))。 -22- (20) 200401165 所得透明膜（圖1 C 5 ))，是間隔1 0 # m平行 之圖形（寬1 0 // m )，厚度以膜厚計測定結果是3 〇 使用顯微分光光度計（奧林包林公司產品0 s p — )，於波長4 6 Ο n m測定所得透明膜1 A m之光線透 ，結果顯示9 8 6 %之高度透明性。又將透明膜形成之 浸漬於23 °C甲基乙基甲酮或N—甲基吡咯烷酮30分 進行耐溶劑性試驗結果，全未發現浸漬前後變化。 實施例2 使用α -羥基異丁酸甲基（19〇質量部份）及丙 二醇單甲基醚醋酸酯（284質量部份）（全溶劑中α 基異丁酸甲基4 0 % )爲溶劑外，與實施例1同樣操 獲得輻射敏感性樹脂組成物。 進行與實施例1同樣操作，與實施例1同樣操作 光線透過率’結果爲9 8 7 %，浸漬前後耐溶劑性試驗 變化，殘膜率良好。 比較例1 使用0： -羥基異丁酸甲基（71質量部份）及丙 二醇單甲基醚醋酸酯（403質量部份）（全溶劑中α 基異丁酸甲基1 5 % )外’與實施例1同樣操作，獲 射敏感性樹脂組成物。 進行與實施例1同樣操作結果，因低感度之故 線狀 μ m -200 過率 基板 鐘， 烯乙 一羥 作， 測定 未見 烯乙 一羥 得輻 100 -23- (21) (21)200401165 mJ / cm 2的曝光量，未能分離ι〇 μιη線格圖形。 本發明之輻射敏感性樹脂組成物，圖形形成時之感度 較高，殘膜率及耐溶劑性良好。因此曝光時間能夠減短’ 能形成良好生產性良好，合格率高之透明膜。 【圖式簡單說明】 (圖Ο使用本輻射敏感性樹脂組成物形成透明膜之 步驟的模式圖。 (符號之說明） 1 :使’用本輻射敏感性樹脂組成物塗佈，除去揮發成分 後之溶劑含量減少之輻射敏感性樹脂組成物所構成之層。 2 :基板 3 :正圖罩 4 :輻射線 5 :透明膜 1 1 :未照射輻射線區域 1 2 :照射輻射線區域 -24--21-(19) (19) 200401165 Compound represented by formula (25 parts by mass), p-hydroxystyrene / styrene (95/5) copolymer (polystyrene equivalent weight average molecular weight 16,000) (30 Parts by mass) a —Methyl hydroxyisobutyrate (474 parts by mass) (100% of α-hydroxyisobutyric acid methyl in all solvents), after mixing at about 23 ° C, micropores with a pore diameter of 15 // m The filter is filtered under pressure, and the filtrate is a radiation-sensitive resin composition. 5 08 crax 5 08 cm transparent glass substrate (product of Corning Corporation # 705 9) [Figure 1 (2)], washed with neutral detergent, washed with water, then washed with isopropyl alcohol and dried to irradiate The sensitive resin composition is spin-coated on its surface. Heat in a purification furnace at 100 ° C for 2 minutes (pre-baking) to reduce the solvent content to form a composition layer [Fig. 1 (1)]. Its film thickness is 3 5 # m (Fig. 1 (a), UL Measured by DEKT AK 3 of VAC company.] Then 'using a mask adjustment device [Mikasa product M-2Li type]] On this radiation-sensitive resin composition layer, a front mask may be irradiated with radiation (Figure 1) (4)), exposure. The front cover (Figure 1 (3) is for the user to form a grid pattern (line space pattern) with a distance of 1 0 // m on the transparent film. The wavelength of the radiation is 3 6 5 nm with an intensity of 100 m J / cm 2 irradiation. After exposure, in a 23 t tetramethylammonium hydroxide aqueous solution (100 parts by mass containing 0 7 parts by mass of tetramethylammonium hydroxide), after 70 seconds of imaging treatment 'Wash with ultrapure water and dry. After drying, continue to irradiate the radiation with the ultra-high pressure mercury lamp (wavelength 3 6 5 nm, intensity 300 mJ / cm2)' Heating in a purification furnace at 220 ° C for 30 minutes, forming a transparent Film (Figures 1 (5) and 1 (c)). -22- (20) 200401165 The obtained transparent film (Figure 1C5)) is a parallel pattern with a distance of 0 # m (width 1 0 // m), The thickness was measured by a film thickness meter, and the light transmittance of the transparent film 1 A m measured at a wavelength of 4 6 〇 nm was measured using a micro-spectrophotometer (Olympium product 0 sp —), and the result showed 9 8 6 % High transparency. The transparent film formed was immersed in methyl ethyl ketone or N-methylpyrrolidone at 23 ° C for 30 minutes. As a result of a solvent resistance test, no change was observed before and after the immersion. Example 2 Using α-hydroxyisobutyric acid methyl ester (190 mass parts) and propylene glycol monomethyl ether acetate (284 mass parts) (40% of α-isobutyric acid methyl ester in all solvents) as solvents A radiation-sensitive resin composition was obtained in the same manner as in Example 1. The same operation as in Example 1 was performed, and the same operation as in Example 1 was performed. The light transmittance was 987%, the solvent resistance test before and after the immersion was changed, and the residual film ratio was good. Comparative Example 1 0: -Except methyl hydroxyisobutyrate (71 parts by mass) and propylene glycol monomethyl ether acetate (403 parts by mass) (15% of methyl α-isobutyrate in total solvent) The same procedure as in Example 1 was performed to obtain a radiation-sensitive resin composition. As a result of the same operation as in Example 1, due to low sensitivity, the linear μ m -200 substrate substrate clock was used, and ethylene glycol was used as the measurement. No ethylene glycol was measured when measured. 100 -23- (21) (21) 200401165 mJ / cm 2 exposure, failed to separate the ιμμη grid pattern. The radiation-sensitive resin composition of the present invention has high sensitivity during pattern formation, good residual film rate and good solvent resistance. Therefore, the exposure time can be shortened, and a transparent film with good productivity and high yield can be formed. [Brief description of the figure] (Figure Schematic diagram of the steps of forming a transparent film using the radiation-sensitive resin composition. (Description of symbols) 1: After coating with the radiation-sensitive resin composition and removing volatile components A layer made of a radiation-sensitive resin composition having a reduced solvent content. 2: Substrate 3: Front cover 4: Radiation 5: Transparent film 1 1: Unirradiated area 1 2: Irradiated area-24-