200413848 玫、發明說明： 【發明所屬之技術領域】 本發明是關於感放射線性組成物以及使用前述感放射線 性樹脂組成物的透明硬化樹脂圖案的製造方法。 【先前技術】 感放射線性組成物，有利於作爲形成透明硬化樹脂圖案 的材料，而例如是用在薄膜電晶體(以下用TFT表示）型液晶顯 示器以及有機EL顯示器上的TFT的絕緣膜，反射型TFT所 使用的擴散反射板以及固體攝像元件(以下表示爲CCD)的保護 膜等。爲了得到更淸晰的成像，所以要求TFT的絕緣膜等材 料對於可視光有更高的透過率。另外，從TFT基板的生產性 這一方面看，還要求很高的耐溶劑性。再有感放射線性樹脂 組成物在TFT基板的生產性這一方面，對用於絕緣膜形成的 放射線，也要求有很高的靈敏度。 感光性樹脂組成物裏含有粘合樹脂、感光劑、光聚合引 發劑(請參照日本早期公開發明2001-281853號等公報）。現在 丙烯酸酯系列的聚合物以及氧雜環丁烷類共聚物作爲粘合樹 脂正在被開發，發現了氧雜環丁烷類物質會發生陽離子聚合 反應（請參照日本早期公開發明2000-239648號等公報）。 另外，有六氟磷酸陰離子形成的鑰鹽作爲陽離子聚合引 發劑而被普遍使用（例子參照9-304931號等公報）。但是，當 把用感放射線性樹脂組成物形成的圖案進行硬化的時候，存 在著圖案的熱變形速度比硬化的速度快的多，以及熱硬化後 透明硬化樹脂圖案的解析度及形狀不能維持的問題。 【發明內容】 本發明的目的是提供一種感放射線性樹脂組成物，對於 12448pif.doc/008 5 200413848 沒有著色的可視光的透過率高，形成具有充分耐溶劑性的透 明硬化樹脂圖案，而且形成形狀較好的透明硬化樹脂圖案。 所以本發明者們在致力於硏究上述應該解決的課題之 後，硏究出了本發明。 即：包含從(A)(al)不飽和羧酸中引導出來的構成單位以 及從含有(a2)氧雜環丁基的不飽和化合物，（不飽和羧酸除外） 中引導出來的構成單位的共聚物。 以及(B)醌二疊氮基化合物 由（C)六氟氧銻陰離子和鑰陽離子的鹽組成的含有陽離子 聚合引發劑的感放射線性樹脂組合物(以下寫作本樹脂組成物) 由本樹脂組成物而形成的透明硬化樹脂圖案及塗佈本樹脂組 成物隔著罩幕進行放射線照射之後，顯影並形成固定的圖案， 接下來提供包含照射放射線的透明硬化樹脂圖案的製造方 法。 【實施方式】 在本發明中，（A)包含(al)從不飽和羧酸引導出來的構成 單位以及從含有(a2)氧雜環丁基的不飽和化合物(但是，不飽 和羧酸除外）引導出來的共聚物(以下寫爲(A)共聚物），係爲不 飽和羧酸及含有氧雜環丁基的高分子化合物。 所謂的氧雜環丁基就是含有氧雜環丁院環(trimethylene oxide)的基。 作爲前述的（al)在不飽和羧酸引導出來的構成單位(以下 寫爲（al)單位）之不飽和羧酸，例如：不飽和單羧酸、不飽和 二羧酸等的分子中含有一個或二個以上的羧基的不飽和竣 酸。具體說來就是：丙烯酸、甲基丙烯酸、丁烯酸、衣康酸、 順丁烯二酸、反式丁烯二酸、甲基馬來酸、甲基反式丁烯二 12448pif.doc/008 6 200413848 酸、衣康酸等。作爲（al)單位，因爲其保存安定性不佳的傾向 較高，所以較佳爲不包含環氧基的構成單位。 從含有前述的（a2)氧雜環丁烷的不飽和物(但是，不飽和 羧酸除外）引導出來的構成單位(以下寫爲（a2)單位）中’作爲含 有氧雜環丁烷的不飽和化合物。例如：3-(甲基)丙烯氧基甲基 氧雜環丁烷、3-甲基-3-(甲基)丙烯氧基甲基氧雜環丁烷、3-乙 基-3-(甲基)丙烯氧基甲基氧雜環丁烷、2-苯基-3-(甲基)丙烯氧 基甲基氧雜環丁烷、2-三氟甲基-3-(甲基)丙烯氧基甲基氧雜環 丁烷、2-五氟-乙基-3-(甲基)丙烯氧基甲基氧雜環丁烷、3-甲 基-3-(甲基)丙烯氧基乙烷氧雜環丁烷、3-乙基-3-(甲基)丙烯氧 基乙基氧雜環丁烷、2-苯基-3-(甲基)丙烯氧乙基氧雑環丁烷、 2-三氟甲基-3-(甲基)丙烯氧基乙基氧雜環丁烷、2-五氟乙基-3-(甲基)丙烯氧基甲基氧雜環丁烷、3-甲基-3-(甲基)丙烯氧基乙 基氧雜環丁烷、3-乙基-3-(甲基)丙烯氧基乙基氧雜環丁烷、2-苯基-3-(甲基)丙烯氧基乙基氧雜環丁烷、2_三氟甲基-3-(甲基） 丙嫌氧基乙基氧雑垣丁《兀、2 -五氣乙基- 3- (甲基)丙稀氧基乙基 氧雜環丁烷等。 構成單位（a2)，較佳是從3-乙基-3-甲基丙烯甲基氧雜環 丁烷中引導出來的構成單位。 (A)共聚物還可以包括··從含有（a3)烯烴性雙鍵的羧酸酯 中引導出來的構成單位，從芳香族乙烯化合物中引導出來的 構成單位，從氰化乙烯化合物中引導出來的構成單位以及從N-取代馬來酸酐縮亞胺化合物中引導出來的構成單位中形成的 群體中選擇至少1種的構成單位(以下寫爲（a3)單位）。 前述的構成單位(a3)，例如··從聚合性的碳-碳不飽和結 合中引導出來的構成單位，具體地說，比如··苯乙烯、α-甲 12448pif.doc/008 7 200413848 基苯乙烯、乙烯基甲苯等芳香族乙烯化合物； 甲基丙烯酸酯、甲基甲基丙烯酸酯、乙基丙烯酸酯、乙 基甲基丙烯酸酯、丁基丙烯酸酯、丁基甲基丙烯酸酯、2-羥基 乙基丙烯酸酯、2-羥基乙基甲基丙烯酸酯、苄基丙烯酸酯、苄 基甲基丙烯酸酯、環己基丙烯酸酯、環己基甲基丙烯酸酯、 異冰片基丙烯酸酯、異冰片基甲基丙烯酸酯、丙基丙烯酸酯、 丙基甲基丙烯酸酯、戊基丙烯酸酯、戊基甲基丙烯酸酯、2-羥 基丁基丙烯酸酯、2-羥基丁基甲基丙烯酸酯、二環戊基丙烯酸 酯、二環戊基甲基丙烯酸酯、苯基丙烯酸酯、苯基甲基丙烯 酸酯、馬來酸二乙基、延胡索酸二乙基、衣康酸二乙基等的 不飽和羧酸脂； 氨基乙基丙烯酸酯等的不飽和羧酸氨基烷基脂； 乙酸乙烯基、3-戊酮酸乙烯基等的羧酸乙烯酯； 丙烯腈、甲基丙烯腈、氯丙烯腈等的腈素乙烯基化合 物； Ν-甲基馬來酸酐縮亞胺、Ν-乙基馬來酸酐縮亞胺、Ν-丁 基馬來酸酐縮亞胺、Ν-環乙基馬來酸酐縮亞胺、N-苄基馬來 酸酐縮亞胺、Ν-苯基馬來酸酐縮亞胺、Ν-(4-乙醯苯基)馬來酸 酐縮亞胺、Ν-(2,6-二乙基苯基)馬來酸酐縮亞胺、Ν-(4-二甲基 氨基-3,5-二硝基苯基)馬來酸酐縮亞胺、N-sucdnimidyl-3-馬來 酸酐縮亞胺苯甲酸酯、N-sucdnimidyl-3-馬來酸酐縮亞胺丙 酯、N-succinimidyl-4-馬來酸酐縮亞胺丁酯、N-琥班醯亞氨-6-馬來酸酐縮亞胺戊酯、N-(l-苯胺基萘基-4)-馬來酸酐縮亞胺、 N-[4-(2-苯噁唑基)苯基]馬來酸酐縮亞胺、（N-(9-吖啶基)馬來 酸酐縮亞胺等的N-取代馬來酸酐縮亞胺化合物等。 作爲(a3)單位，較佳是從雙環戊基甲基丙烯酸酯、雙環 12448pif.doc/008 8 200413848 戊基丙烯酸酯、環己基甲基丙烯酸酯、環己基丙烯酸酯、N_ 環乙馬來酸酐縮亞胺及N_苯馬來酸酐縮亞胺中引導出的構成 單位。 諸如此類的構成單位，可以是單獨或是2種以上的組合 來使用。 關於(A)共聚物的〇1)單位的含有量爲，對於(A)共聚物的 構成單位全體來說，通常量爲5至50莫耳％，較佳爲15至40 莫耳％。（a2)單位的含有量對於(A)共聚物的構成單位全體來， 通常量爲5至95莫耳％，較佳爲15至85莫耳％。 (A)共聚物在實質上只由（al)單位以及(a2)單位構成的情 況下（al)單位/(a2)單位(莫耳比），通常爲5/95至50/50， 較佳爲15/85至40/60。在上述範圍中，運用本樹脂組合物 而得到的透明硬化樹脂層，對顯影液的具有適當的溶解速度， 同時呈現出高硬化性的傾向而較佳。 (A共聚物在包含(a3)單位等其他構成單位的時候，（al)單 位的含有量爲：對於共聚物的全部構成單位來說，通常爲5 至50莫耳％，較佳爲15至40莫耳％。（a2)單位的含有量爲： 對於(A)共聚物的全體構成單位來說，通常爲94至5莫耳％， 較佳爲80至15莫耳％。（a3)單位等其他共聚物的構成單位’ 通常爲1至90莫耳％，較佳爲5至80莫耳％。 本發明中的（A)共聚物的具體例子如下：3-乙基-3-甲基丙 烯氧基甲基氧雜環丁烷/T基甲基丙烯酸酯/甲基丙稀酸共聚 物、3-乙基-3-甲基丙烯氧基甲基氧雜環丁烷/苄基甲基丙烯酸 酯/甲基丙烯酸/苯乙烯共聚物、3_乙基_3-甲基丙烯氧基甲基氧 雜環丁烷/甲基丙烯酸/苯乙烯共聚物、3-乙基-3 —甲基丙烯氧基 甲基氧雜環丁烷/甲基丙烯酸/環乙基甲基丙烯酸基共聚物、3- 12448pif.doc/008 9 200413848 乙基-3-甲基丙烯氧基甲基氧雜環丁烷/甲基丙烯酸/甲基丙嫌酸 甲基/苯乙烯共聚物、3-乙基-3-甲基丙烯氧基甲基氧雜環丁烷/ 甲基丙烯酸/t-丁基甲基丙烯酸酯共聚物、3-乙基-3-甲基丙嫌 氧基甲基氧雜環丁烷/甲基丙烯酸/異冰片甲基丙烯酸酯共聚 物、3-乙基-3-甲基丙烯氧基甲基氧雜環丁烷/甲基丙烯酸/节基 丙烯酸酯共聚物、3-乙基-甲基丙烯氧基甲基氧雜環丁烷/甲基 丙烯酸/環己基丙烯酸酯、3-乙基-3-甲基丙烯氧基甲基氧雜環 丁烷/甲基丙烯酸/異冰片丙烯酸酯共聚物、3-乙基-3-甲基丙煉 氧基甲基氧雜環丁烷/甲基丙烯酸/t-丁基丙烯酸酯共聚物、3-乙基-3-甲基丙烯氧基甲基氧雜環丁烷/甲基丙烯酸/苯基馬來酸 酐縮亞胺共聚物、3-乙基-3-甲基丙烯氧基甲基氧雜環丁烷/甲 基丙烯酸/環己基馬來酸酐縮亞胺共聚物等。 (A)共聚物是，以聚苯乙烯爲基礎的所要求的重量平均分 子量通常爲2,000至100,000，較佳爲2,000至5〇,〇〇0，更佳 爲3,000至30,000的範圍。前述的重量平均分子量是2,〇〇〇至 100,000的話，使用本樹脂組成物得到的透明硬化樹脂層的圖 案形成時，不但能保持顯影時的殘膜率，還能得到高效的顯 影速度而較佳。 在本樹脂的組成物中，（A)的共聚物含有量對於本樹脂組 成物的固體含量來說，在重量分率中通常爲50至94·99% ’較 佳爲60至90%。 並且，本說明書中本樹脂組成物的固體含纛就是在本樹 脂組成物中除去溶劑的所有成分的合計。 在本發明中的醌二疊氮基化合物(Β)如下·· ι，2-苯醌一® 氮基磺酸酯、I，2-萘醌二疊氮基磺酸酯、1，2-苯醌二疊氮基磺 酸氨基化合物、1，2-萘醌二疊氮基磺酸氨基化合物等。 12448pif.doc/008 10 200413848 具體地說有：2,3,4-三羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、2,3,4-三羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯、 2,4,6-三羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、2,4,6-三 羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯等的三羥基二苯甲 酮類的1,2-萘醌二疊氮基磺酸酯；2,2’，4,4’-四羥基二苯甲酮-1,2-萘醌二疊氮基-4-磺酸酯、2,2’，4,4’-四羥基二苯甲酮-1，2-萘 醌二疊氮基-5-磺酸酯、2,2’，4,3’-四羥基二苯甲酮-1，2-萘醌二 疊氮基-4-磺酸酯-2,2’，4,3-四羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯、2,3,4,45-四羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸 酯、2,3,4,4’四羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯、 2,3,4,2’-四羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、2,3,4,2’-四羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯、2,3,4,4’-四羥基 二苯甲酮-3’-甲氧基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、 2,3,4,4’-四羥基-3’-甲氧基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸 酯等的四羥基二苯甲酮類的1,2-萘醌二疊氮基磺酸酯； 2,3,4,2’，6’-五羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、 2,3,4,2’，6’-五羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯二疊氮 基等的五羥基二苯甲酮類的1，2-萘醌二疊氮基磺酸酯； 2,4,6,3’，4’，5’-六羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、 2,4,6,3’，4’，5’-六羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、 3,4,5,3’，4’，5’-六羥基二苯甲酮-1，2-萘醌二疊氮基-4-磺酸酯、 3,4,5,3’，4’，5’-六羥基二苯甲酮-1，2-萘醌二疊氮基-5-磺酸酯等 的六羥基二苯甲酮類的1，2-萘醌二疊氮基磺酸酯；雙（2,4-二羥 基苯基）甲烷-1，2-萘醌二疊氮基-4-磺酸酯、雙（2,4-二羥基苯基) 甲烷-1，2-萘醌二疊氮基-5-磺酸酯、雙(p-羥基苯基）甲烷-1，2-萘 醌二疊氮基-4-磺酸酯、雙(p-羥基苯基）甲烷-1，2-萘醌二疊氮基 12448pif.doc/008 11 200413848 -5-磺酸酯、l，l，l-H(p-羥基苯基）乙烷-I，2-萘醌二疊氮基-心石頁 酸酯、1，1，1-三(p-羥基苯基）乙烷-1，2-萘醌二疊氮基-5-摘酸酉曰、 雙（2,3,4-三羥基苯基）甲烷-1，2-萘醌二疊氮基冰磺酸酯、雙 (2,3,4-三羥基苯基）甲烷-1，2-萘醌二疊氮基-5-擴酸酯、2,2’-雙 (2、3、4_三羥基苯基)丙烷-1，2-萘醌二疊氮基_4-磺酸酿、2,2-雙（2,3,4-三羥基苯基)丙烷-l，2-萘醌二疊氮基-5-磺酸_、l5l’3_ 三（2,5-二甲基_4_羥基苯基)-3-苯基丙烷-I，2-萘醌二稾第基-4-磺酸酯、1，1，3_三（2,5-二甲基-4-羥基苯基)-3-苯基丙化 醌二疊氮基-5-磺酸酯、4,4，-〔 1-〔 4-〔卜〔4-羥基苯襄〕小甲 基乙基〕苯基〕亞乙基〕雙酚-1，2萘醌二疊氮基-5-g苯基、 雙（2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷-1，2-萘酿二疊氮基 -5-磺酸酯、3,3,3，，3、四甲基-1，1-螺二-5,6,7,5，，6，，7、己醇-1，2’ 萘醌二疊氮基-4-磺酸酯、3,3,3’，3’-四甲基-1，1’-螺二 ^ 5,6,7,5，，6，，7，-己醇],2-萘醌二疊氮基-5-磺酸酯、2,2，心^甲基· 7,2，，4，-三羥基黃烷-1，2_萘醌二疊氮基-4-磺酸酯、2,2,心三甲基 -7,2，,4，-三羥基黃烷-1，2-萘醌二疊氮基-5-磺酸酯等（多疼基苯 基)烷烴類的1，2-萘醌二疊氮基磺酸酯等。 前述的醌二疊氮基化合物可以各別獨自使用，也$以由2 種以上組合在一起使用。醌二疊氮基化合物，在本發明中的 含有量通常爲感射線性樹脂組成物的固體成分之重*分率的 2%至50%，較佳爲5%至40%。當醌二疊氮基化合物的含有里 爲2%至50%時，因爲未曝光部分與曝光部分的溶解速度差變 大，就可以保持較高的顯影殘膜率，從而達到理想效果。 在本發明中（C)六氟氧銻陰離子與鑰陽離子的鹽所形成的 陽離子聚合引發劑(以下用（C)聚合引發劑來表示)這種引發劑 中的鑰陽離子的構造一般可用下面化學式（1)和（2)來表示。 12448pif.doc/008 12 200413848 R1-1-R2 ⑴ + R1-S-R3 (2) (從R1到R3，分別獨立地表示幾個基’它們是· 苯基，它的苯環上至少有一個氫原子可以從碳數1到18 的烷基，碳數1到18的烷氧基，鹵素原子’羧基’氫硫基’ 氰基以及硝基所組之族群任意選擇一個取代。 _ 萘基，它的萘環上的氫原子至少有一個可以被選自碳數1 到12的院氧基、鹵素原子、羧基、氫硫基、氰基以及硝基所 組之族群的基取代。 碳數1到18的直鏈狀烷基，此烷基的氫原子至少有一個 可以被選自鹵素原子、竣基、氮硫基、氛基以及硝基所組之 族群的基取代。 碳數3到18的支鍵狀院基’此院基的氣原子至少有一*個 可以被選自鹵素原子、竣基、氫硫基、氛基以及硝基所組之 鲁 族群的基取代。 還有，碳數3到18的環狀烷基’此烷基的氫原子至少有 一個可以被選自鹵素原子、羧基、氫硫基、氰基以及硝基所 組之族群的基取代。） 化學式（1)的鏺陽離子，具體說來有··二苯基碘鑰、雙(P-甲苯基)碘鑰、雙(p-t-丁基苯基)碘鑰、雙（P-辛基苯基)碘鑰、 雙(P-十八烷基苯基)碘鑰、雙(P-辛基羥基苯基)碘鑰、雙(P-十 八烷基羥基苯基)碘鐵、苯基(p-十八院基羥基苯)碑鑰、（p-甲 12448pif.doc/008 13 200413848 苯基)(p-異丙基苯基)碘鑰等。 化學式（2)的鑰陽離子，具體說來有：三苯基锍、三(P-甲 苯基）锍、三(P_異丙基苯基）锍、三（2,6_二甲基苯基)锍、三（p- 氰基苯基)锍、三（P-氯苯基)毓、二甲基（甲氧基)锍、二甲基（乙 氧基）鏡、二甲基(丙氧基）鏑、二甲基(丁氧基)鏑、二甲基(辛 基經基)毓、二甲基(十八烷基羥基)鏑、二甲基（異丙氧基)鏑、 二甲基(t-丁氧基）鏑、二甲基(環戊基羥基)鏑、二甲基(環己基 羥基）鏑、二甲基（氟甲氧基)鏑、二甲基(2-氟丁氧基)锍、二甲 基（3-漠丙氧基）鏡、二甲基(心氰基丁氧基）鏑、一甲基硝基 辛基羥基)鏑、二甲基（18，18，18-三氟十八烷基羥基)毓、二甲 基（2-經基異丙氧基）鏑、二甲基(三（三氯甲基）甲基）鏑等。較 佳的碘鐵鹽有：雙(P-甲苯基)碘:鑰、（P-甲苯基)(P-異丙氧基)碘 鐵、雙(P+丁基苯基)碘鐵等’而最佳的是(P-甲苯基)(P_異丙 氧基)碘:鑰。 在本發明中，（C)聚合引發劑的含有量爲對於本樹脂組成 物的固體含量來說，通常的重量分率爲〇·〇ι至1〇%，較佳爲 0.1至5%。當(c)聚合引發劑的含有量爲ο·οι至10%時，在利 用本樹脂組成物製成的透明硬化樹脂圖案的形成過程中，在 顯影後的促進硬化的時候，具有抑制熱硬 傾向而較佳。 化時解析度降低的 在樹脂組成物中含有，（Α)共聚物(Β)酿=缝^ 聚合引發劑之外，因應需要可以含有(D)萘酿，氮基以及(C) 合物，（F)交聯劑，（G)聚合性單體，（H)溶劑等。(E)多元苯酚化 (D)萘酚化合物如下：h萘酚、2_萘酣、丨，2 二經萘、1，4·二經萘、1，5-二經萘、ι，6-二趨萘、1 、丨’3- 1，8-二羥萘、2,3·二羥萘、2,6_二羥萘、2,7_二 j；7·:羥萘、 基、甲氧基· 12448pif.doc/008 14 200413848 1-萘酚等。特別是丨-萘酚、2-萘酚、4-甲氧基-1-萘酚更佳。 在含有(D)萘酚化合物的情況下，它的含有量相對於本樹 脂組成物的固體含有量來說，較佳重量分率爲0.1至10%，更 佳的重量分率爲0·1至5%。當萘酚化合物以前述的基準含有 量0.1至10%時，在利用本樹脂組成物製成透明硬化樹脂圖案 時之顯影後的曝光中，作爲(C)聚合引發劑的敏化劑使用以促 進曝光時的光硬化，這種情況下能夠理想地防止熱硬化時解 析度的降低而較佳。 (E)多元化苯酚化合物的理想狀況是含有在分子中存在2 個以上的苯酚性羥基的化合物。（E)多元化苯酚化合物包括： 三羥基二苯甲酮類、四羥基二苯甲酮類、五羥基二苯甲酮類、 六羥基二苯甲酮類、（聚羥基苯基)鏈烷烴類等的多元苯酚類， 具體的說，在(B)醌二疊氮基化合物中記載的具體例化合物的 1，2-萘醌二疊氮基-4或5-硫基部分可以被氫原子取代的化合 物。 另外，作爲上述的多元苯酚化合物，至少有以羥基苯乙 烯爲原料單體的聚合物。具體地例如是聚羥基苯乙烯、羥基 苯乙烯/甲基甲基丙烯酸酯共聚物、羥基苯乙烯/環己基甲基丙 烯酸酯共聚物、羥基苯乙烯/乙烯共聚物、羥基苯乙烯/烷氧基 苯乙烯共聚物等的羥基苯乙烯所聚合的樹脂。特別是諸如從 苯酚類、甲酚類以及鄰苯二酚類形成的群體中選擇出至少一 種化合物和乙醛類及甲酮類形成的群體中選擇的一種以上的 化合物凝縮聚合而得到的酚醛樹脂等。 在含有（E)多元苯酚化合物的情況下它的含有量是對於本 樹脂組成物的固體含量來說，較佳的重量分率爲0.1至40%， 更佳爲1至25%。當多元苯酚化合物的含有量爲0·1至40%時， 12448pif.doc/008 15 200413848 由於利用本樹脂組成物製成的透明硬化樹脂圖案的可視光透 過率會增大，性能也會提高而較佳。 作爲(F)交聯劑，例如是羥甲基化合物等。 作爲羥甲基化合物，包括烷氧基甲基化三聚氰胺樹脂、 烷氧基甲基化尿素樹脂等的烷氧甲基化氨基樹脂等。在這提 到的烷氧基甲基三聚氰氨樹脂例如是所舉的甲氧基甲基化三 聚氰氨樹脂、乙氧基甲基化三聚氰氨樹脂、丙氧基甲基化三 聚氰氨樹脂、丁氧基甲基化三聚氰氨樹脂等；烷氧基甲基化 尿素樹脂例如是所舉的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，丁基甲基化尿素樹脂 等。（F)交聯劑可以各自單獨或任意2種以上的組合使用。 在含有(F)交聯劑的情況下，它的含有量是，對於本樹脂 組成物的固體含量來說，較佳爲〇·1至15%。當(F)交聯劑的 含有量爲〇·1至15%時，由於利用本樹脂組成物製成的透明硬 化樹脂圖案的耐藥品性等的可靠度會提高，性能也會提高而 較佳。 作爲(G)聚合性單體’例如是藉由加熱，以使自由基聚合 從而得到聚合性單體，陽離子聚合從而得到聚合性單體等， 較佳爲陽離子聚合而得到聚合性單體。 在(G)聚合性單體中因自由基聚合而得到聚合性單體，例 如是所舉的有聚合性碳-碳不飽和結合的化合物，有單官能的 聚合性單體也可以’有2官能的聚合性以及3官能和3官能 以上的聚合性單體等多官能的聚合性單體也可以。 單官能的聚合性單體有如下：壬基苯基卡必醇丙烯酸醋、 壬基苯基卡必醇甲基丙烯酸酯、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 12448pif.doc/008 200413848 烯酸酯、2-乙基己基卡必醇甲基丙烯酸酯、2-羥基乙基丙烯酸 酯、2-羥基乙基甲基丙烯酸酯、乙烯基吡咯烷酮等。 2官能的聚合性單體有如下：l，6-己二醇丙烯酸酯、1，6- 己二醇甲基丙烯酸酯、乙二醇丙烯酸酯、乙二醇甲基丙烯酸 酯、新戊二醇丙烯酸酯、新戊二醇甲基丙烯酸酯、三乙二醇 二丙烯酸酯、三乙二醇二甲基丙烯酸酯、雙酚A的雙(丙烯醯 基氧基乙基）醚、3-甲基戊二醇二丙烯酸酯、3-甲基戊二醇二 甲基丙燦酸酯等。 3官能以上的聚合性單體有如下：三羥甲基丙烷三丙烯酸 酯、三羥甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、 季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇 四甲基丙烯酸酯、季戊四醇五丙烯酸酯、季戊四醇五甲基丙 烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸 酯等。前述的聚合性單體中也適用於2官能或是3官能以上 的聚合性單體。具體地說，如：季戊四醇四丙烯酸酯，二季 戊四醇六丙烯酸酯等也可以，而最佳爲二季戊四醇六丙烯酸 酯。並且，2官能或是3官能以上的聚合性單體也可以和單官 能聚合性單體組合。 在(G)聚合性單體中的陽離子聚合而得到的聚合性單體有 如下：乙烯基醚基，丙烯基醚基，氧雜環丁基等的陽離子聚 合性的官能基的聚合性單體。具體如下：作爲含有乙烯基醚 基的化合物有：三乙二醇二乙烯基醚、M-環己烷二甲醇乙烯 基醚、4-羥基丁基乙烯基醚、十二烷基乙烯基醚等。作爲含有 丙烯基醚基的化合物有：心（卜丙烯基氧基甲基）-1，3-二氧戊環-2-酮等。作爲含有氧雜環丁基的化合物有：雙{ 3-(3-乙基氧雜 環丁基）甲基}醚；1，4-雙{ 3-(3-乙基氧雜環丁基）甲氧基}苯、 12448pif.doc/008 17 200413848 I，4-雙{ 3-(3-乙基氧雜環丁基）甲氧基丨甲基苯、μ-雙{ 3-(3-乙基氧雜環丁基）甲氧基}環己烷、1，4-雙{ 3-(3-乙烷氧雜環 丁基）甲氧基}甲基環己烷等。 (G) 聚合性單體可以單獨或是2種以上組合起來用，在使 用（G)聚合性單體的情況下它的含量較佳爲對於本樹脂組成物 固體的重量分率爲0.1至20%。 本樹脂組成物一般存在於(H)溶劑中，在被稀釋的狀態下 使用。（H)溶劑爲如下：乙二醇單甲醚、乙二醇單乙基醚、乙 二醇單丙基醚、乙二醇單丁基醚等乙二醇單烷基醚類；二乙 二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基基醚、 二乙二醇二丁基醚等的二乙二醇二烷基醚類；甲基乙二醇乙 醚醋酸鹽、乙基乙二醇乙醚醋酸鹽等的乙二醇烷基醚醋酸鹽 類；丙二醇單甲基醚醋酸鹽、丙二醇單乙基醚醋酸鹽、丙二 醇單丙基醚醋酸鹽等的丙二醇烷基醚醋酸鹽類；苯基、甲苯、 二甲苯、三甲苯等的芳香族碳化氫類；甲基乙酮、丙酮、甲 基戊酮、甲基異丁酮、環己院等的酮類；乙醇、丙醇、丁醇、 己醇、環己烷醇、乙二醇、丙三醇等的醇類；2-羥基異丁烷酸 甲基、乳酸乙基、3-乙氧基二乙基甲酮酸乙基、3-甲氧基二乙 基甲酮酸甲基等的脂類；r -丁內脂等環狀脂等。較佳的溶劑 有·· 2-羥基異丁烷酸甲基、乳酸乙基、丙二醇單甲基醚醋酸鹽、 3-乙氧基二乙基甲酮酸乙基等。其中，2-羥基異丁烷酸甲基爲 最佳。 (H) 溶劑是，分別或是組合成2種以上來使用，其含量對 於本樹脂組成物的合計量來說，在重量分率中較佳爲50至 95%，更佳爲60至90%。 本樹脂組成物，因應其所需包含著其他成分，例如：界 12448pif.doc/008 18 200413848 面活性劑、抗氧化劑、溶解抑制劑、紫外線吸收劑、接著性 改良劑、電子施體等各種添加物。 本樹脂組成物是根據如：（A)共聚物在(η)溶劑中溶解成的 溶液，（B)醌二疊氮基化合物在(H)溶劑中溶解成的溶液，以及 (C)聚合引發劑在(H)溶劑中溶解成的溶液混合而成的方法製造 出來的。在使用萘酚化合物，多元苯酚化合物，交聯劑，聚 合性單體’添加劑等的情況下，再加上這些化學物也可以。 或是經過混合後才加（H)溶劑。混合後，最好是把過濾出來的 固體物質去掉。如··最好的過濾方法是利用內徑爲3 Atn以下， 較佳爲〇_l//m以上2//m以下的過濾器來進行過濾。對於以 上所述的各成分溶劑是一種溶劑也行，不同種類但能相溶的 溶劑也可以。 利用本樹脂組成物形成的透明硬化樹脂圖案如下：在基 板(2)上形成該樹脂組成物層（1)(第ία圖），隔著正型遮光罩幕 (3)以放射線照射該層（1)曝光後進行顯影即可。 基板(2)，包括：除透明的玻璃板、矽晶圓以外，舉出了 聚碳酸鹽基板、聚酯基板、芳香族聚醯胺基板、聚醯胺醯亞 胺基板、聚醯亞氨基板等。在前面所說的基板中，也可以事 先形成CCD或TFT的電路、彩色濾光片、透明電極等。 本樹脂組成物的層（1)用通常的方法，例如：把本樹脂組 成物塗在基板(2)上的方法可以形成。塗佈的方法一般有旋轉 塗佈法（spin coating法）、流延塗佈法、輥塗佈法、縫隙與旋 轉塗佈法、縫隙塗佈法等用節省塗料的塗料器塗佈的方法等 衆所周知的塗佈法在基板上塗佈，接下來對溶劑的揮發成分 進行加熱乾燥(也稱爲預供烤)或者減壓乾燥，使溶劑揮發，這 樣就形成了本樹脂組成物層（1)，揮發了溶劑的本樹脂組成物 12448pif.doc/008 19 200413848 層（1)，是來自本樹脂組成物的固體成分，所以幾乎不含有任 何揮發成分，而且本樹脂組成物層的厚度可達到例如是1.5至 5 " m 〇 接下來，用放射線(4)透過正型遮光罩幕（3)來照射本樹脂 組成物層（1)。正型遮光罩幕(3)的圖案，係因應能夠達成透明 硬化樹脂圖案的圖案而適當選擇。放射線例如是使用g線，i 線等光線，放射線較佳爲使用例如是遮光罩幕曝光對準器和 步進機來照射。 這樣曝光以後，顯影出來。顯影可以藉由本樹脂組成物 層曝光後接觸顯影液的方法來進行。顯影液可以用通常使用 的鹼性水溶液。例如通常的鹼性化合物水溶液。鹼性化合物 水溶液中，用有機鹼性化合物和無機鹼性化合物都可。 無機鹼性化合物，如··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， 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、銨等。 有機鹼性化合物，如：四甲基銨氫氧化物、2-羥基乙基三 甲基銨氫氧化物、單甲胺、二甲胺、三甲胺、單乙胺、二乙 胺、三乙胺、單異丙胺、二異丙胺、乙醇胺等。上述的鹼性 化合物，可單獨地或由兩種以上組合使用。對應於顯影液100 重量份，鹼性化合物通常爲0.01至10重量份。較佳爲含有0.1 至5個重量份。顯影液也可以含有界面活性劑。作爲界面活 性劑，例如有：非離子系界面活性劑，陽離子系界面活性劑、 陰離子系界面活性劑等等。 非離子系界面活性劑，如：聚氧基乙烯烷基醚、聚氧基 乙烯芳基醚、聚氧乙烯烷基芳基醚等的聚氧基乙烯衍生物、 12448pif.doc/008 20 200413848 氧基乙烯/氧基丙烯嵌段共聚物、山梨糖醇酐脂肪酸酯、聚氧 基乙烯山梨糖醇酐脂肪酸酯、聚氧基乙烯山梨糖醇脂肪酸酯、 丙三醇脂肪酸酯、聚氧基乙烯脂肪酸酯、聚氧基乙烯烷基銨 等。 陽離子界面活性劑，如：硬脂醯胺鹽酸鹽等的胺鹽、月 桂基三甲基銨氯化物等的第四級銨鹽等。 陰離子系界面活性劑，如：月桂基醇硫酸酯鈉、油醇硫 酸酯鈉等高級乙醇硫酸酯鹽；月桂基硫酸鈉、月桂基硫酸銨 等烷基硫酸鹽、月桂基苯磺酸鈉、月桂基萘磺酸鈉等的烷基 芳基磺酸鹽等。這些界面活性劑可以分別單獨使用或由兩種 以上組合起來使用。 顯影液也可以含有有機溶劑。作爲上述的有機溶劑，如： 甲醇、乙醇等水溶性的有機溶劑等。 本樹脂組成物層（1)曝光後，讓它接觸顯影液。例如，由 本樹脂組成物層（1)形成的基板(2)曝光後，浸在顯影液就可以 了。根據顯影，本樹脂組成物層（1)上，在之前的曝光中被放 射線照射到的領域（12)溶解在顯影液裏，沒有被照射到的領域 (11)卻沒有溶解，而是殘留下來形成圖案（5)。 本發明的感放射線性樹脂組成物，因爲含有(B)醌二疊氮 基化合物，使該樹脂組成物和顯影液相接觸的時間變短，放 射線照射領域（Π)也能容易地溶解並去除。另外，因爲含有(B) 醌二疊氮基化合物，即使本樹脂組成物和顯影液的接觸時間 變長，放射線未照射到的領域也不會在顯影液中溶解並消失。 顯影後，通常先用水洗，再把其乾燥。乾燥的時候，在 所得到的圖案（5)上用放射線照射。放射線的照射，通常對基 板上形成的圖案直接而不通過遮光罩幕的進行，最好是能使 12448pif.doc/008 21 200413848 圖案的全面都受到放射線的照射。另外，放射線從基板的背 面進行照射也可以。這裏所說的放射線最好是含有250至 330nm波長的放射線的紫外線或深紫外線。單位面積的照射量 通常比先前所放入的遮光罩幕曝光時候的照射量多。 像這樣形成的圖案（5)，再通過加熱處理（曝後烤），以提高 透明硬化樹脂圖案的耐熱性，耐溶劑性等，因而最好進行該 處理。加熱是根據顯影後用電熱板、無塵烘箱等加熱裝置加 熱放射線照射過的基板的方法進行的。加熱溫度通常爲攝氏 150度至攝氏250度，較佳爲攝氏180度至攝氏240度；加熱 時間通常爲5至12分，較佳爲15至90分。根據加熱程度， 圖案越來越硬，於是形成了更堅固的透明硬化樹脂圖案。 像這樣形成的透明硬化樹脂圖案，使本發明的感放射線 性樹脂組成物硬化，例如，作爲TFT基板的絕緣膜，有機EL 元件的絕緣膜，CCD的保護膜等透明硬化樹脂圖案而發揮作 用。 上述的內容中，雖對於本發明的實施形式作了說明，而 在上述被明示了的本發明的實施形式始終只是舉例說明。本 發明的範圍不被限定在這些實施形式當中。本發明的範圍可 通過申請專利範圍來顯示，而且和關於申請專利的記載有均 等意義’並包含了此範圍內的所有變更。以下，用實施例更 詳細地對本發明進行說明，但本發明並不限定於此些實施例。 合成例1 在攪拌器、冷卻管以及裝有溫度計，容量爲200ml的四 口燒瓶中’加入下面的原料，讓氮氣流入，把四口燒瓶浸入 油浴中，燒瓶內部溫度保持在攝氏85度至攝氏95度之間， 攪拌3小時使其反應，得到樹脂A1，這個樹脂A1的聚苯乙 12448pif.doc/008 22 200413848 烯換算重量時的平均分子量爲15,000。 甲基丙烯酸 6.4g 環己基甲基丙烯酸鹽酯 11.7g 3-乙基-3-甲基丙烯氧基甲基氧雜環丁基 17.7g 2-羥基異丁烷酸甲基 83.3g 偶氮雙異丁腈 〇.9g 合成例2 在攪拌器、冷卻管以及裝有溫度計， 容量爲200ml的四 口燒瓶中，加入下面的原料，讓氮氣流入 ，把四口燒瓶浸入 油浴中，燒瓶內部溫度保持在攝氏85度至攝氏95度之間， 攪拌3小時使其反應，得到樹脂A2。樹脂A2的聚苯乙烯換 算重量時的平均分子量爲15,000。 甲基丙烯酸 6.8g N-苯基馬來酸酐縮亞銨 13.7g 3-乙基-3-甲基丙烯氧基甲基氧雜環丁基 17.8g 2-羥基異丁烷酸甲基 89.5g 偶氮雙異丁腈 〇.9g 合成例3 在攪拌器、冷卻管以及裝有溫度計， 容量爲200ml的四 口燒瓶中，加入下面的原料，讓氮氣流入 ，把四口燒瓶浸入 油浴中，燒瓶內部溫度保持在攝氏85度至攝氏95度之間， 攪拌3小時使其反應，得到樹脂A3。這個樹脂A3的聚苯乙 烯換算重量時的平均分子量15,000。 甲基丙烯酸 6.8g N-環己基馬來酸酐縮亞胺 14.2g 3-乙基-3-甲基丙烯氧基甲基氧雜環丁基 17.8g 12448pif.doc/008 23 200413848 90.5g 〇.9g 2-羥基異丁烷酸甲基 偶氮雙異丁腈 尙且，上述聚苯乙烯換算重量的平均分子量的測定條件， 係如同以下所述。 裝置·· HLC-8120GPC(TORAY(股）製）200413848 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive composition and a method for producing a transparent hardened resin pattern using the radiation-sensitive resin composition. [Prior art] The radiation-sensitive composition is useful as a material for forming a transparent hardened resin pattern, and is, for example, a thin film transistor (hereinafter referred to as TFT) type liquid crystal display and an organic EL display. The diffuse reflection plate used in the TFT and the protective film of a solid-state imaging element (hereinafter referred to as a CCD). In order to obtain a clearer image, materials such as an insulating film of a TFT are required to have a higher transmittance for visible light. In addition, in terms of productivity of the TFT substrate, high solvent resistance is also required. The radiation-sensitive resin composition is also required to have high sensitivity in terms of productivity of a TFT substrate, and also to radiation used for forming an insulating film. The photosensitive resin composition contains a binder resin, a photosensitizer, and a photopolymerization initiator (for example, refer to Japanese Early Laid-Open Publication No. 2001-281853 and the like). Acrylate polymers and oxetane copolymers are currently being developed as binder resins, and it has been found that oxetane-type substances undergo cationic polymerization (see Japanese Early Publication No. 2000-239648, etc.) Bulletin). In addition, a key salt formed by a hexafluorophosphate anion is widely used as a cationic polymerization initiator (for example, refer to Publication No. 9-304931). However, when the pattern formed by the radiation-sensitive resin composition is hardened, the thermal deformation rate of the pattern is faster than the hardening rate, and the resolution and shape of the transparent hardened resin pattern cannot be maintained after heat curing. problem. [Summary of the invention] The object of the present invention is to provide a radiation-sensitive resin composition, for 12448pif. doc / 008 5 200413848 The untransmitted visible light has high transmittance, forms a transparent hardened resin pattern with sufficient solvent resistance, and forms a transparent hardened resin pattern with a good shape. Therefore, the present inventors have invented the present invention after devoting themselves to studying the above-mentioned problems to be solved. That is, the constituent units derived from (A) (al) unsaturated carboxylic acids and the constituent units derived from unsaturated compounds containing (a2) oxetanyl groups (except unsaturated carboxylic acids) Copolymer. And (B) a quinonediazide-based compound comprising (C) an antimony hexafluorooxide anion and a salt of a key cation, a radiation-sensitive resin composition containing a cationic polymerization initiator (hereinafter referred to as the present resin composition) The formed transparent hardened resin pattern and the coated resin composition are irradiated with radiation through a mask, and then developed and formed into a fixed pattern. Next, a method for manufacturing a transparent hardened resin pattern including radiation is provided. [Embodiment] In the present invention, (A) includes (al) a constitutional unit derived from an unsaturated carboxylic acid and an unsaturated compound containing (a2) an oxetanyl group (except for an unsaturated carboxylic acid) The introduced copolymer (hereinafter referred to as (A) copolymer) is an unsaturated carboxylic acid and an oxetanyl-containing polymer compound. The so-called oxetanyl group is a group containing a trimethylene oxide ring. As the aforementioned (al) unsaturated carboxylic acid constituting a unit (hereinafter referred to as (al) unit) derived from an unsaturated carboxylic acid, for example, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or the like contains one molecule Or two or more carboxylic acid unsaturated unsaturated acids. Specifically: acrylic acid, methacrylic acid, butenoic acid, itaconic acid, maleic acid, trans-butenedioic acid, methyl maleic acid, methyl trans-butenedi 12448pif. doc / 008 6 200413848 acid, itaconic acid, etc. The (al) unit has a high tendency for poor storage stability, and is therefore preferably a constituent unit not containing an epoxy group. Among the constituent units (hereinafter referred to as (a2) units) derived from the unsaturated substance containing the aforementioned (a2) oxetane (except for unsaturated carboxylic acid), as the Saturated compounds. For example: 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (methyl Propyl) propenyloxymethyloxetane, 2-phenyl-3- (meth) propenyloxymethyloxetane, 2-trifluoromethyl-3- (meth) propenyloxy Methylmethyloxetane, 2-pentafluoro-ethyl-3- (meth) propenyloxymethyloxetane, 3-methyl-3- (meth) propenyloxyethane Oxetane, 3-ethyl-3- (meth) propenyloxyethyloxetane, 2-phenyl-3- (meth) propenyloxyethyloxocyclobutane, 2 -Trifluoromethyl-3- (meth) propenyloxyethyloxetane, 2-pentafluoroethyl-3- (meth) propenyloxymethyloxetane, 3-methyl Methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) acryloxyethyloxetane, 2-phenyl-3- (methyl Propyl) propenyloxyethyloxetane, 2-trifluoromethyl-3- (methyl) propanyloxyethyloxobutanidine, 2-pentafluoroethyl-3- (methyl Propyl) ethoxyethyloxetane and the like. The constituent unit (a2) is preferably a constituent unit derived from 3-ethyl-3-methacrylmethyloxetane. (A) The copolymer may further include a constituent unit derived from a carboxylic acid ester containing (a3) an olefinic double bond, a constituent unit derived from an aromatic vinyl compound, and a vinyl cyanide compound. At least one kind of constitutional unit (hereinafter referred to as (a3) unit) is selected from the group consisting of the constitutional unit derived from the N-substituted maleic anhydride imine compound and the constitutional unit derived from the N-substituted maleic anhydride imine compound. The aforementioned constitutional unit (a3) is, for example, a constitutional unit derived from a polymerizable carbon-carbon unsaturated bond, specifically, for example, styrene, α-formaldehyde 12448pif. doc / 008 7 200413848 Aromatic vinyl compounds such as styrene, vinyltoluene; methacrylate, methmethacrylate, ethylacrylate, ethylmethacrylate, butylacrylate, butylmethacrylate Ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, Isobornyl methacrylate, propyl acrylate, propyl methacrylate, pentyl acrylate, pentyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, bicyclic Unsaturated carboxylic acids such as amyl acrylate, dicyclopentyl methacrylate, phenyl acrylate, phenyl methacrylate, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. Fatty acid; Unsaturated carboxylic acid amino alkyl esters such as amino ethyl acrylate; vinyl carboxylates such as vinyl acetate and 3-pentanone acid vinyl; nitriles such as acrylonitrile, methacrylonitrile, and chloroacrylonitrile Vegetarian Vinyl compounds; N-methyl maleic anhydride imine, N-ethyl maleic anhydride imine, N-butyl maleic anhydride imine, N-cycloethyl maleic anhydride imine, N -Benzylmaleic anhydride imine, N-phenylmaleic anhydride imine, N- (4-acetamidine) maleic anhydride imine, N- (2,6-diethylphenyl) ) Maleic anhydride imine, N- (4-dimethylamino-3,5-dinitrophenyl) maleic anhydride imine, N-sucdnimidyl-3-maleic anhydride imine benzoic acid Ester, N-sucdnimidyl-3-maleic anhydride imidate, N-succinimidyl-4-maleic anhydride imidate, N-succinimidyl-6-maleic anhydride amidopentyl ester N- (l-anilinonaphthyl-4) -maleic anhydride imine, N- [4- (2-phenyloxazolyl) phenyl] maleic anhydride imine, (N- (9- Acridineyl) N-substituted maleic anhydride imine compounds such as maleic anhydride imine, etc. As the (a3) unit, preferred are dicyclopentyl methacrylate, bicyclic 12448 pif. doc / 008 8 200413848 The constituent units derived from amyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, N_cycloethylmaleic anhydride imine and N_benzenemaleic anhydride imine. Such constituent units may be used alone or in combination of two or more. The content of 〇1) units of the (A) copolymer is usually 5 to 50 mol%, preferably 15 to 40 mol% for the entire constituent units of the (A) copolymer. The content of the (a2) unit is usually 5 to 95 mole%, and preferably 15 to 85 mole% with respect to the entire constitutional unit of the (A) copolymer. (A) In the case where the copolymer is substantially composed only of (al) units and (a2) units, (al) units / (a2) units (molar ratio), usually 5/95 to 50/50, preferably 15/85 to 40/60. Within the above range, the transparent hardened resin layer obtained by using the present resin composition preferably has a suitable dissolution rate for the developer and exhibits a tendency to have high hardenability. (When the A copolymer contains other constituent units such as (a3) units, the content of the (al) unit is: for all the constituent units of the copolymer, usually 5 to 50 mole%, preferably 15 to 40 mol%. The content of the (a2) unit is: For the entire constituent unit of the (A) copolymer, it is usually 94 to 5 mol%, preferably 80 to 15 mol%. (A3) Unit The constituent units of other copolymers are usually 1 to 90 mole%, preferably 5 to 80 mole%. Specific examples of the (A) copolymer in the present invention are as follows: 3-ethyl-3-methyl Allyloxymethyloxetane / T-based methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzylmethyl Acrylate / methacrylic acid / styrene copolymer, 3_ethyl_3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methyl Acryloxymethyloxetane / methacrylic acid / cycloethylmethacrylic copolymer, 3-12448pif. doc / 008 9 200413848 Ethyl-3-methacryloxymethyloxetane / methacrylic acid / methacrylic acid methyl / styrene copolymer, 3-ethyl-3-methylpropene Oxymethyloxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methylpropoxymethyloxetane / methacrylic acid / isobornyl Methacrylic acid ester copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / benzyl acrylate copolymer, 3-ethyl-methacryloxymethyl Oxetane / methacrylic acid / cyclohexyl acrylate, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / isobornyl acrylate copolymer, 3-ethyl 3-Methylpropaneoxymethyloxetane / methacrylic acid / t-butyl acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / Methacrylic acid / phenylmaleic anhydride imine copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexylmaleic anhydride imine copolymer, etc. . (A) The copolymer has a required weight average molecular weight based on polystyrene, usually in the range of 2,000 to 100,000, preferably 2,000 to 50,000, more preferably 3,000 to 30,000. When the aforementioned weight average molecular weight is 2,000 to 100,000, the pattern formation of the transparent hardened resin layer obtained using the resin composition can not only maintain the residual film rate during development but also obtain an efficient development speed. good. In the composition of the present resin, the copolymer content of (A) is usually 50 to 94.99% by weight ratio, and more preferably 60 to 90%, based on the solid content of the resin composition. In addition, in the present specification, the solid content of the resin composition is the total of all the components except the solvent in the resin composition. The quinonediazide compound (B) in the present invention is as follows: ι, 2-benzoquinone azide, 1,2-naphthoquinonediazide sulfonate, 1,2-benzene Quinonediazidesulfonic acid amino compounds, 1,2-naphthoquinonediazidesulfonic acid amino compounds, and the like. 12448pif. doc / 008 10 200413848 Specifically: 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4-trihydroxydibenzene Ketone-1,2-naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, Trihydroxybenzophenones such as 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc. Acid esters; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2', 4,4'-tetrahydroxydione Benzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,2 ', 4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4 -Sulfonate-2,2 ', 4,3-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,45-tetrahydroxydiphenyl Methanone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-3 -Methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1 1,2-naphthoquinonediazide-5-sulfonate, such as 1,2-naphthoquinonediazide sulfonate; 2,3,4,2 ', 6' -Pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone 1,2-naphthoquinonediazidesulfonic esters of pentahydroxybenzophenones such as diazide-5-sulfonate; 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1 2,2-naphthoquinonediazide-4-sulfonate, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4 -Sulphonate, 3,4,5,3 ', 4', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc. Ketones 1,2-naphthoquinonediazidesulfonate; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2 , 4-dihydroxyphenyl) methane-1,2-naphthoquinone -5-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthalene Quinonediazide 12448 pif. doc / 008 11 200413848 -5-sulfonate, l, l, lH (p-hydroxyphenyl) ethane-I, 2-naphthoquinonediazide-cardiolite, 1,1,1- Tris (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-pic acid, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone Diazide glacial sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-propanoate, 2,2'-bis (2, 3, 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2 -Naphthoquinonediazide-5-sulfonic acid_, 15l'3_tris (2,5-dimethyl-4_hydroxyphenyl) -3-phenylpropane-I, 2-naphthoquinone difluorenyl 4-sulfonate, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropionated quinonediazide-5-sulfonate, 4, 4,-[1- [4- [BU [4-hydroxyphenoxane] small methylethyl] phenyl] ethylene] bisphenol-1,2naphthoquinonediazide-5-gphenyl, Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthalene diazide-5-sulfonate, 3,3,3,, 3, Tetramethyl-1,1-spirobi-5,6,7,5,, 6,7, Hexanol-1,2 Naphthoquinonediazide-4-sulfonate, 3,3,3 ', 3'-tetramethyl-1,1'-spirobi ^ 5,6,7,5,6,7,- Hexanol], 2-naphthoquinonediazide-5-sulfonate, 2,2,2-methyl, 7,2,, 4, -trihydroxyflavan-1,2-naphthoquinonediazide 4-sulfonate, 2,2, carditrimethyl-7,2,4, -trihydroxyflavane-1,2-naphthoquinonediazide-5-sulfonate, etc. 1,2-naphthoquinonediazide sulfonate and the like. The aforementioned quinonediazide compounds can be used individually or in combination of two or more kinds. The content of the quinonediazide-based compound in the present invention is usually 2% to 50%, preferably 5% to 40%, based on the weight * fraction of the solid content of the radiation-sensitive resin composition. When the content of the quinonediazide-based compound is 2% to 50%, since the difference in dissolution rate between the unexposed portion and the exposed portion becomes larger, a high residual film development rate can be maintained, thereby achieving an ideal effect. In the present invention, (C) a cationic polymerization initiator formed by an antimony hexafluorooxide anion and a salt of a key cation (hereinafter referred to as (C) a polymerization initiator). The structure of the key cation in this initiator can generally use the following chemical formula (1) and (2). 12448pif. doc / 008 12 200413848 R1-1-R2 ⑴ + R1-S-R3 (2) (from R1 to R3, each independently represents several groups' they are · phenyl groups, which have at least one hydrogen atom on the benzene ring One substitution can be arbitrarily selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom 'carboxy', a hydrogenthio group, a cyano group, and a nitro group. At least one of the hydrogen atoms on the naphthalene ring may be substituted with a group selected from the group consisting of an oxo group, a halogen atom, a carboxyl group, a hydrogen thio group, a cyano group, and a nitro group. A linear alkyl group of which at least one of the hydrogen atoms of the alkyl group may be substituted with a group selected from the group consisting of a halogen atom, a condensing group, a nitrogen sulfur group, an aryl group, and a nitro group. Bonded courtyard group 'At least one of the gas atoms of this courtyard group can be substituted with a group selected from the group consisting of a halogen atom, a condensing group, a hydrogen sulfide group, an aryl group, and a nitro group. Also, the carbon number is 3 to 18 cyclic alkyl 'at least one hydrogen atom of this alkyl group may be selected from the group consisting of halogen atom, carboxyl group, hydrogen thio group, cyano group and nitro group The group of the group is substituted.) The phosphonium cation of the chemical formula (1) specifically includes: diphenyliodo key, bis (P-tolyl) iodo key, bis (pt-butylphenyl) iodo key, and bis ( P-octylphenyl) iodine, bis (P-octadecylphenyl) iodine, bis (P-octylhydroxyphenyl) iodine, bis (P-octylhydroxyphenyl) iodine Iron, phenyl (p-octadecylhydroxybenzene) stele, (p-methyl 12448pif. doc / 008 13 200413848 phenyl) (p-isopropylphenyl) iodo key and the like. Key cations of the chemical formula (2) include, specifically, triphenylphosphonium, tri (P-tolyl) fluorene, tri (P_isopropylphenyl) fluorene, and tri (2,6_dimethylphenyl) ) 锍, tris (p-cyanophenyl) 锍, tris (P-chlorophenyl) 毓, dimethyl (methoxy) 锍, dimethyl (ethoxy), dimethyl (propoxy) Yl) hydrazone, dimethyl (butoxy) fluorene, dimethyl (octyl), dimethyl (octadecylhydroxy) fluorene, dimethyl (isopropyloxy) fluorene, dimethyl (T-butoxy) 镝, dimethyl (cyclopentylhydroxy) 镝, dimethyl (cyclohexylhydroxy) 镝, dimethyl (fluoromethoxy) 镝, dimethyl (2-fluorobutane) Oxy) pyrene, dimethyl (3-propoxyl) mirror, dimethyl (cardiocyanobutoxy), monomethylnitrooctylhydroxy) pyrene, dimethyl (18,18, 18-trifluorooctadecylhydroxy) fluorene, dimethyl (2-acylisopropoxy) fluorene, dimethyl (tri (trichloromethyl) methyl) fluorene and the like. The preferred iron iodide salts are: bis (P-tolyl) iodine: molybdenum, (P-tolyl) (P-isopropoxy) iron iodide, bis (P + butylphenyl) iron iodide, etc. Preferred is (P-tolyl) (P_isopropoxy) iodine: key. In the present invention, the content of the (C) polymerization initiator is usually from 0.1 to 10% by weight with respect to the solid content of the present resin composition, and preferably from 0.1 to 0.1%. 1 to 5%. When the content of the (c) polymerization initiator is ο · οι to 10%, in the process of forming a transparent hardening resin pattern made of the present resin composition, the hardening is suppressed when the hardening is promoted after development. Tend to be better. When the resolution is lowered during the conversion, it is contained in the resin composition. In addition to the (A) copolymer (B), it is possible to contain (D) naphthalene, nitrogen, and (C) compounds in addition to the polymerization initiator. (F) a crosslinking agent, (G) a polymerizable monomer, (H) a solvent, and the like. (E) Polyphenolation (D) Naphthol compounds are as follows: h-naphthol, 2-naphthyl, naphthalene, 2, 2-naphthalene, 1,4- · naphthalene, 1,5-naphthalene, i Dinaphthalene, 1, 3'- 1,8-dihydroxynaphthalene, 2,3 · dihydroxynaphthalene, 2,6_dihydroxynaphthalene, 2,7_dij; 7 ·: hydroxynaphthalene, radical, Oxygen12448pif. doc / 008 14 200413848 1-naphthol and the like. In particular, 丨 -naphthol, 2-naphthol, and 4-methoxy-1-naphthol are more preferred. In the case of containing (D) a naphthol compound, its content is preferably 0% by weight relative to the solid content of the resin composition. 1 to 10%, more preferably a weight fraction of 0.1 to 5%. When the naphthol compound contains the content of 0. At 1 to 10%, in the exposure after development when a transparent hardening resin pattern is made using the resin composition, the sensitizer is used as a (C) polymerization initiator to promote light hardening during exposure. In this case, It is preferable to be able to prevent a decrease in resolution during thermal curing. (E) The polyphenol compound is preferably a compound containing two or more phenolic hydroxyl groups in the molecule. (E) Diversified phenol compounds include: trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, (polyhydroxyphenyl) paraffins Polyhydric phenols such as, specifically, the specific examples of compounds described in (B) quinonediazide compounds may be substituted by a hydrogen atom in the 1,2-naphthoquinonediazide-4 or 5-thio group. compound of. In addition, as the polyvalent phenol compound, there is at least a polymer using hydroxystyrene as a raw material monomer. Specific examples are polyhydroxystyrene, hydroxystyrene / methmethacrylate copolymer, hydroxystyrene / cyclohexylmethacrylate copolymer, hydroxystyrene / ethylene copolymer, hydroxystyrene / alkoxy Resin polymerized by hydroxystyrene such as styrene copolymer. In particular, a phenolic resin obtained by condensation polymerization of at least one compound selected from the group consisting of phenols, cresols, and catechols and one or more compounds selected from the group consisting of acetaldehydes and ketones. Wait. In the case where the (E) polyhydric phenol compound is contained, the content thereof is for the solid content of the resin composition, and the preferred weight fraction is 0. 1 to 40%, more preferably 1 to 25%. When the polyphenol compound content is from 0.1 to 40%, 12448 pif. doc / 008 15 200413848 Since the visible light transmittance of the transparent hardened resin pattern made of the resin composition is increased, the performance is also improved and it is better. Examples of the (F) crosslinking agent include methylol compounds. Examples of the methylol compound include alkoxymethylated melamine resins, alkoxymethylated amino resins such as alkoxymethylated urea resins, and the like. The alkoxymethyl melamine resins mentioned here are, for example, the methoxymethylated melamine resins, ethoxymethylated melamine resins, and propoxymethylated resins. Melamine resin, butoxymethylated melamine resin, etc .; alkoxymethylated urea resin is, for example, the methoxymethylated urea resin, ethoxymethylated urea resin, Propoxy methylated urea resin, butyl methylated urea resin, etc. (F) Crosslinking agents can be used individually or in combination of any two or more. When the (F) crosslinking agent is contained, its content is preferably from 0.1 to 15% with respect to the solid content of the present resin composition. When the content of the (F) cross-linking agent is from 0.1 to 15%, the reliability of the chemical resistance and the like of the transparent hardened resin pattern made of the resin composition will be improved, and the performance will be improved. . The (G) polymerizable monomer 'is, for example, a polymerizable monomer obtained by radical polymerization by heating and a polymerizable monomer obtained by cationic polymerization, and a polymerizable monomer is preferably obtained by cationic polymerization. (G) The polymerizable monomer is obtained by radical polymerization in the polymerizable monomer, for example, the compound having a polymerizable carbon-carbon unsaturated bond is mentioned, and a polymerizable monomer having a monofunctional property may also be included. Polyfunctional polymerizable monomers, such as a functional polymerizable polymer and a trifunctional polymer or more, may be used. Monofunctional polymerizable monomers are as follows: nonylphenylcarbitol acrylate, nonylphenylcarbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy- 3-phenoxypropyl methacrylate, 2-ethylhexylcarbitol propylene 12448 pif. doc / 008 200413848 enoate, 2-ethylhexylcarbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, vinylpyrrolidone and the like. The bifunctional polymerizable monomers are as follows: 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, ethylene glycol acrylate, ethylene glycol methacrylate, neopentyl glycol Acrylate, neopentyl glycol methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (propenyloxyethyl) ether of bisphenol A, 3-methyl Pentylene glycol diacrylate, 3-methylpentanediol dimethyl propionate, and the like. The trifunctional or more polymerizable monomers are as follows: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate Methacrylate, pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Among the aforementioned polymerizable monomers, bifunctional or trifunctional or higher polymerizable monomers are also suitable. Specifically, for example, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. may be used, and dipentaerythritol hexaacrylate is most preferable. Moreover, a bifunctional or trifunctional or more polymerizable monomer may be combined with a monofunctional polymerizable monomer. (G) The polymerizable monomer obtained by cation polymerization among the polymerizable monomers is as follows: a polymerizable monomer having a cationic polymerizable functional group such as a vinyl ether group, a propenyl ether group, and an oxetanyl group. . The details are as follows: As the compound containing a vinyl ether group, there are triethylene glycol divinyl ether, M-cyclohexane dimethanol vinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, etc. . Examples of the compound containing a propenyl ether group include cardiac (bupropenyloxymethyl) -1,3-dioxolane-2-one and the like. As oxetanyl-containing compounds: bis {3- (3-ethyloxetanyl) methyl} ether; 1,4-bis {3- (3-ethyloxetanyl) Methoxy) benzene, 12448 pif. doc / 008 17 200413848 I, 4-bis {3- (3-ethyloxetanyl) methoxy-1-methylbenzene, μ-bis {3- (3-ethyloxetanyl) methyl Oxy} cyclohexane, 1,4-bis {3- (3-ethaneoxetanyl) methoxy} methylcyclohexane, and the like. (G) The polymerizable monomer may be used alone or in combination of two or more. In the case of using (G) the polymerizable monomer, its content is preferably 0% by weight with respect to the solid weight of the resin composition. 1 to 20%. The resin composition is generally present in a (H) solvent and used in a diluted state. (H) The solvents are as follows: ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol Diethylene glycol dialkyl ethers such as alcohol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; methyl glycol Glycol alkyl ether acetates such as diethyl ether acetate, ethyl glycol diethyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Alkyl ether acetates; aromatic hydrocarbons such as phenyl, toluene, xylene, xylene; methyl ethyl ketone, acetone, methylpentanone, methyl isobutyl ketone, cyclohexanone, etc. ; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexane alcohol, ethylene glycol, glycerol; 2-hydroxyisobutanoic acid methyl, ethyl lactate, 3-ethoxydiethyl Lipids such as ethyl methyl ketoate and methyl 3-methoxydiethyl keto ketone; cyclic lipids such as r-butyrolactone and the like. Preferable solvents are: methyl 2-hydroxyisobutanoate, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxydiethylketonate, and the like. Of these, methyl 2-hydroxyisobutanoate is most preferred. (H) The solvent is used singly or in combination of two or more kinds. The content of the solvent is preferably 50 to 95%, more preferably 60 to 90% of the total weight of the resin composition. . The resin composition contains other components according to its needs, for example: circles 12448pif. doc / 008 18 200413848 Various additives such as surfactants, antioxidants, dissolution inhibitors, ultraviolet absorbers, adhesion improvers, and electron donors. The resin composition is based on, for example: (A) a solution in which the copolymer is dissolved in (η) a solvent, (B) a solution in which the quinonediazide compound is dissolved in (H) a solvent, and (C) polymerization initiation It is produced by mixing the solution in which the agent is dissolved in the (H) solvent. When a naphthol compound, a polyhydric phenol compound, a crosslinking agent, a polymerizable monomer 'additive, etc. are used, these chemicals may be added. Or add (H) solvent after mixing. After mixing, it is best to remove the filtered solids. For example, the best filtering method is filtering with a filter having an inner diameter of 3 Atn or less, preferably 0-1 // m or more and 2 // m or less. The solvent for each of the components described above may be a single solvent, and different types of solvents that are compatible with each other may be used. The transparent hardened resin pattern formed by using this resin composition is as follows: the resin composition layer (1) is formed on the substrate (2) (FIG. Αα), and the layer is irradiated with radiation through a positive light-shield screen (3) ( 1) Development can be performed after exposure. The substrate (2) includes a polycarbonate substrate, a polyester substrate, an aromatic polyimide substrate, a polyimide substrate, and a polyimide plate in addition to a transparent glass plate and a silicon wafer. Wait. In the aforementioned substrate, a circuit of a CCD or a TFT, a color filter, and a transparent electrode may be formed in advance. The layer (1) of the resin composition can be formed by a conventional method, for example, a method of applying the resin composition to the substrate (2). The coating method generally includes a spin coating method, a cast coating method, a roll coating method, a slit and spin coating method, a slit coating method, and the like using a coater-saving coating method, etc. A well-known coating method is applied on the substrate, and then the volatile components of the solvent are heated and dried (also called pre-baking) or dried under reduced pressure to volatilize the solvent, thus forming the resin composition layer ( 1), the resin composition 12448 pif volatile. doc / 008 19 200413848 The layer (1) is a solid component derived from the resin composition, so it hardly contains any volatile components, and the thickness of the resin composition layer can be, for example, 1. 5 to 5 " m 〇 Next, the resin composition layer (1) is irradiated with radiation (4) through the positive-type light-shielding screen (3). The pattern of the positive hood curtain (3) is appropriately selected in accordance with a pattern capable of achieving a transparent hardened resin pattern. The radiation is, for example, light using a g-line or an i-ray, and the radiation is preferably irradiated using, for example, a hood curtain exposure aligner and a stepper. After exposure in this way, it develops. The development can be performed by a method in which the resin composition layer is exposed to a developer after exposure. As the developing solution, a commonly used alkaline aqueous solution can be used. For example, a general aqueous solution of an alkaline compound. As the basic compound, both an organic basic compound and an inorganic basic compound can be used in the aqueous solution. Inorganic basic compounds, such as sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, carbonate Sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonium, etc. Organic basic compounds, such as: tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine, etc. These basic compounds may be used alone or in combination of two or more. Corresponding to 100 parts by weight of the developer, the basic compound is usually 0. 01 to 10 parts by weight. Preferably it contains 0. 1 to 5 parts by weight. The developer may contain a surfactant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Non-ionic surfactants, such as: polyoxyethylene alkyl ether, polyoxy ethylene aryl ether, polyoxyethylene alkyl aryl ether and other polyoxyethylene derivatives, 12448pif. doc / 008 20 200413848 Oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin Alcohol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylammonium, and the like. Cationic surfactants, such as amine salts such as stearylamine hydrochloride, quaternary ammonium salts such as lauryltrimethylammonium chloride, and the like. Anionic surfactants, such as: higher alcohol sulfates such as sodium lauryl sulfate, sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl benzene sulfonate, lauryl Alkyl aryl sulfonates and the like such as sodium naphthalene sulfonate. These surfactants can be used individually or in combination of two or more kinds. The developing solution may contain an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol and ethanol. After exposing this resin composition layer (1), it is brought into contact with a developer. For example, the substrate (2) formed of the resin composition layer (1) may be immersed in a developing solution after exposure. According to the development, the area (12) that was irradiated with radiation during the previous exposure was dissolved in the developing solution on the resin composition layer (1), but the area (11) that was not irradiated was not dissolved but remained. Forming a pattern (5). Since the radiation-sensitive resin composition of the present invention contains (B) a quinonediazide-based compound, the contact time between the resin composition and the developing liquid phase is shortened, and the radiation irradiation area (Π) can be easily dissolved and removed. . In addition, since the quinonediazide-based compound is contained, even if the contact time between the resin composition and the developing solution becomes longer, the area not exposed to the radiation will not dissolve and disappear in the developing solution. After development, it is usually washed with water and then dried. When drying, the obtained pattern (5) is irradiated with radiation. Radiation, usually the pattern formed on the substrate directly without going through the hood curtain, it is best to make 12448pif. doc / 008 21 200413848 The whole pattern is exposed to radiation. The radiation may be radiated from the back surface of the substrate. The radiation here is preferably ultraviolet or deep ultraviolet rays containing radiation having a wavelength of 250 to 330 nm. The exposure per unit area is usually more than the exposure when the previously placed mask is exposed. The pattern (5) formed in this way is further subjected to a heat treatment (post-exposure baking) to improve the heat resistance and solvent resistance of the transparent hardened resin pattern. Therefore, this treatment is preferably performed. The heating is performed according to a method of heating the irradiated substrate with a heating device such as a hot plate or a dust-free oven after development. The heating temperature is usually 150 ° C to 250 ° C, preferably 180 ° C to 240 ° C; the heating time is usually 5 to 12 minutes, preferably 15 to 90 minutes. Depending on the degree of heating, the pattern becomes harder and harder, and a stronger transparent hardened resin pattern is formed. The transparent hardened resin pattern formed in this manner hardens the radiation-sensitive resin composition of the present invention. For example, the transparent hardened resin pattern functions as a transparent hardened resin pattern such as an insulating film for a TFT substrate, an insulating film for an organic EL element, or a protective film for a CCD. In the foregoing, the embodiments of the present invention have been described, but the embodiments of the present invention that have been explicitly described above are merely examples. The scope of the present invention is not limited to these embodiments. The scope of the present invention can be displayed by the scope of the patent application, and has the same meaning as the description of the patent application ', and includes all changes within the scope. Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. Synthesis Example 1 In a stirrer, a cooling tube, and a four-necked flask equipped with a thermometer and a capacity of 200 ml, the following materials were added, nitrogen was allowed to flow in, and the four-necked flask was immersed in an oil bath. Between 95 degrees Celsius, stir for 3 hours to make it react to obtain resin A1, this resin A1's polystyrene 12448pif. doc / 008 22 200413848 The weight average molecular weight in terms of olefin is 15,000. Methacrylic acid 6. 4 g of cyclohexyl methacrylate 11. 7g 3-ethyl-3-methacryloxymethyloxetan 17. 7g methyl 2-hydroxyisobutanoate 83. 3g azobisisobutyronitrile 〇. 9g Synthesis Example 2 In a stirrer, a cooling tube, and a four-necked flask with a capacity of 200 ml equipped with a thermometer, add the following materials, let nitrogen flow in, and immerse the four-necked flask in an oil bath. The temperature inside the flask is maintained at 85 ° C To 95 ° C, it was stirred for 3 hours to react to obtain resin A2. The average molecular weight of polystyrene of resin A2 in terms of weight was 15,000. Methacrylic acid 6. 8g N-phenylmaleic anhydride 7g 3-ethyl-3-methacryloxymethyloxetan 17. 8g methyl 2-hydroxyisobutanoate 89. 5g azobisisobutyronitrile 〇. 9g Synthesis Example 3 In a stirrer, a cooling tube, and a four-necked flask with a capacity of 200ml equipped with a thermometer, the following materials were added, nitrogen was allowed to flow in, and the four-necked flask was immersed in an oil bath. The internal temperature of the flask was maintained at 85 ° C To 95 ° C, it was stirred for 3 hours for reaction to obtain resin A3. This resin A3 has a weight average molecular weight of 15,000 in terms of polystyrene. Methacrylic acid 6. 8g N-cyclohexylmaleic anhydride imine 14. 2g 3-ethyl-3-methacryloxymethyloxetan 17. 8g 12448pif. doc / 008 23 200413848 90. 5g 〇. 9 g of 2-hydroxyisobutanoic acid methyl azobisisobutyronitrile 尙 The conditions for measuring the average molecular weight of the polystyrene-equivalent weight are as follows. Device ·· HLC-8120GPC (TORAY)
管柱：TSK-GELG2000HXL 以及 TSK-GELG4000HXL 管柱溫度：攝氏40度 溶劑：四氫喃 流速： 注入量：50/Z 1 檢測器：RI 測定試樣濃度：0.6% 校正用標準物質：TSK STANDARD POLYSTYRENE F-40、F-4、 F-l、A-2500、A-500(TORAY(股)製） 實施例1 將（A)樹脂Al(100重量份） (B)式(4)所示的化合物(22重量份）Column: TSK-GELG2000HXL and TSK-GELG4000HXL Column temperature: 40 ° C Solvent: Tetrahydrogen Flow rate: Injection volume: 50 / Z 1 Detector: RI Measurement sample concentration: 0.6% Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, Fl, A-2500, A-500 (manufactured by TORAY) Example 1 (A) Resin Al (100 parts by weight) (B) A compound represented by formula (4) ( 22 parts by weight)
(式中，Q4表示在式4-1中的取代基) 12448pif.doc/008 24 200413848(Wherein Q4 represents a substituent in formula 4-1) 12448pif.doc / 008 24 200413848
(4-1) (C)下面所記的鹽(4-1) (C) The salt noted below
[商品名：SAN-AID SI-100、三新化學工業股份有限公司 制](2重量份)以及2-經基異丁院酸脂(429重量份），以攝氏23 度的溫度混合以後，通過內徑爲m的聚四氟乙烯製的濾筒 來加壓過濾，得到的濾液就是感放射線性樹脂組成物。 在4英寸的矽晶圓（2)上旋轉塗佈上面所得到的感放射線 性組成物，用熱板以攝氏200度的溫度加熱2分鐘(預烘烤)以 形成感放射線性樹脂組成物層（1)，用測膜厚計[LAMBDA ACE(大日本SCREEN製造(股）製）]對這個膜的厚度進行測定， 係爲2.6 // m(第1A圖）。 之後，i射線步進機[NSR-1755i7A(NA=0.5)nikon股份有 限公司製造]透過正型遮光罩幕(3)來照射得到的感放射線性樹 脂組成物層（1)以進行曝光(第1B圖）。正型遮光罩幕（3)要用爲 了在透明硬化樹脂圖案間隔m時可以形成線幅爲3 “历的 接觸孔圖案的那種正型遮光罩幕(3)。 12448pif.doc/008 25 200413848 曝光後’把它浸漬在攝氏23度的（100重量份中有0.2重 量份四甲基銨氫氧化物)水溶液中70秒，顯影後用超純水洗 淨、乾燥。在顯影後的圖案中，以接觸孔的直徑成爲3//m之 以遮光罩幕的曝光量作爲實效靈敏度，此實效靈敏度爲 79mJ/cm2的’測得圖案斷面和基板所夾的角度θ爲90度。乾 燥後，用DUV電子管〔VXM-501MD(USHIO(股)製）〕的反射 線[波長以313nm爲基準，強度爲300mJ/cm2]全面的照射。並 在無塵烘箱中以攝氏220度的溫度加熱30分鐘，形成透明硬 化樹脂圖案5(第1C圖）。 用厚度計測量得到的透明硬化樹脂圖案（5)，它的厚度(T1) 爲 1.8 // m。 可視光線透過率的測定，除了不用步進機進行曝光工程 以外，藉由上述的方法形成透明硬化樹脂膜，並用顯微分光 光度計[OSP-200 (OLYMPUS光學工業(股)製)]對其進行測定。 膜厚用膜厚計(DEKTAK3股份公司製造)來測定。得到的透明 硬化樹脂膜每1 // m厚對波長爲400-750nn的光線的平均透過 率爲99.3%，顯示出很高的透明性，並且無著色。硬化樹脂圖 案斷面與基板所形成的角度0爲54度。然後，讓透明硬化樹 脂圖案在甲基乙基酮與N-吡咯烷酮（攝氏23度)浸泡30分鐘 來對它進行耐溶劑性試驗，結果是試驗前後此基板無變化。 實施例2 (C)SAN-AID SI-100(三新化學工業(股)製）除變更爲以下所 記的鹽之外與實施例1的操作一樣，從而得到感放射線性樹 脂組成物。 12448pif.doc/008 26 200413848 -SbFfi r8 [商品名SAN-AID SM50(三新化學工業（股）製）] 在與實施例1進行同樣操作的基板上形成了透明硬化樹 脂圖案。以實效與靈敏度爲89mJ/cm2顯影出3 // m的接觸孔 圖案。顯影後之圖案的斷面與基板所形成的角度0爲90度。 按照實施例1的同樣操作並測定出的光線透過率爲99.3%，有 高透明度，無著色。熱處理後的硬化樹脂圖案的斷面與基板 所形成的角度Θ爲52度。與實施例1相同的耐溶劑性試驗中， 浸漬前後塗佈沒有發生變化。 實施例3 (C)SAN-AID SI-100(三新化學工業(股)製）除變更爲以下所 記的鹽之外與實施例1的操作一樣，從而得到感放射線性樹 脂組成物。[Brand name: SAN-AID SI-100, manufactured by San Shin Chemical Industry Co., Ltd.] (2 parts by weight) and 2-Isobutyronic acid ester (429 parts by weight), after mixing at a temperature of 23 degrees Celsius, The filter was pressure-filtered through a polytetrafluoroethylene filter cartridge having an inner diameter of m, and the obtained filtrate was a radiation-sensitive resin composition. The radiation-sensitive composition obtained above was spin-coated on a 4-inch silicon wafer (2), and heated on a hot plate at 200 ° C for 2 minutes (pre-baking) to form a radiation-sensitive resin composition layer. (1) The thickness of this film was measured with a film thickness meter [LAMBDA ACE (manufactured by Dainippon SCREEN Co., Ltd.)], and it was 2.6 // m (Figure 1A). After that, the i-ray stepper [NSR-1755i7A (NA = 0.5) nikon Co., Ltd.] irradiates the obtained radiation-sensitive resin composition layer (1) through a positive-type hood (3) to perform exposure (No. Figure 1B). The positive-type hood curtain (3) is to be a positive-type hood curtain (3) that can form a 3 "calendar contact hole pattern when the transparent hardening resin pattern interval m. 12448pif.doc / 008 25 200413848 After exposure ', it was immersed in an aqueous solution of 23 ° C (0.2 parts by weight of tetramethylammonium hydroxide in 100 parts by weight) for 70 seconds, washed with ultrapure water and dried after development. In the pattern after development Taking the contact hole diameter as 3 // m and the exposure amount of the hood as the effective sensitivity, the effective sensitivity is 79mJ / cm2. The angle θ between the measured cross section of the pattern and the substrate is 90 degrees. After drying , Using a DUV tube [VXM-501MD (USHIO (made by))] reflection line [wavelength based on 313nm, intensity 300mJ / cm2] full irradiation. And in a dust-free oven at 220 degrees Celsius for heating 30 Minutes, a transparent hardened resin pattern 5 is formed (Figure 1C). The transparent hardened resin pattern (5) measured with a thickness meter has a thickness (T1) of 1.8 // m. The visible light transmittance is measured without using steps In addition to the exposure process, it is formed by the above method The hardened resin film was measured with a microspectrophotometer [OSP-200 (manufactured by OLYMPUS Optical Industry Co., Ltd.)]. The film thickness was measured with a film thickness meter (manufactured by DEKTAK3 Co., Ltd.). The obtained transparent hardened resin The film has an average transmittance of 99.3% per 1 // m thickness for light with a wavelength of 400-750nn, showing high transparency and no coloration. The angle formed by the cross section of the hardened resin pattern and the substrate is 54 degrees Then, the transparent hardening resin pattern was immersed in methyl ethyl ketone and N-pyrrolidone (23 degrees Celsius) for 30 minutes to perform a solvent resistance test. As a result, the substrate did not change before and after the test. Example 2 (C) SAN-AID SI-100 (manufactured by Sam Shin Chemical Industry Co., Ltd.) was carried out in the same manner as in Example 1 except that the salt described below was changed to obtain a radiation-sensitive resin composition. 12448pif.doc / 008 26 200413848 -SbFfi r8 [Brand name SAN-AID SM50 (manufactured by San Shin Chemical Industry Co., Ltd.)] A transparent hardened resin pattern was formed on the substrate which was operated in the same manner as in Example 1. 3 was developed with an effect and sensitivity of 89 mJ / cm2 // m contact hole pattern. After development The angle formed by the cross section of the project and the substrate is 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.3%, with high transparency and no coloring. The cross section of the cured resin pattern after heat treatment and The angle Θ formed by the substrate was 52 degrees. In the same solvent resistance test as in Example 1, there was no change in coating before and after immersion. Example 3 (C) SAN-AID SI-100 (Sanxin Chemical Industry Co., Ltd.) The procedure was the same as that of Example 1 except that the salt was changed as described below to obtain a radiation-sensitive resin composition.
[商品名ADEKA Optomer SP-ΠΟ旭電化工業(股）製] 在與實施例1進行同樣操作的基板上形成了透明硬化樹 脂圖案。以實效與靈敏度100 mJ/cm2顯影出3//m的接觸孔圖 案。顯影後，圖案的斷面與基板所形成的角度0爲9〇度。按 12448pif.doc/008 27 200413848 照實施例1的同樣操作並測定出的光線透過率爲99.3%，有高 透明度，無著色。熱處理後的硬化樹脂圖案的斷面與基板所 形成的角度0爲57度。與實施例1相同的耐溶劑性試驗中， 浸漬前後塗佈沒有發生變化。 實施例4 (C)SAN-AID SI-100(三新化學工業(股）製）除變更爲以下所 記的鹽之外與實施例1的操作一樣，從而得到感放射線性樹 脂組成物。[Product name: ADEKA Optomer SP-IIO, manufactured by Asahi Denka Kogyo Co., Ltd.] A transparent hardened resin pattern was formed on a substrate having the same operation as in Example 1. A contact hole pattern of 3 // m was developed with an effect and sensitivity of 100 mJ / cm2. After development, the angle 0 formed by the cross-section of the pattern and the substrate was 90 degrees. According to 12448pif.doc / 008 27 200413848, the light transmittance measured in the same manner as in Example 1 was 99.3%, with high transparency and no coloration. The angle between the cross section of the cured resin pattern after heat treatment and the substrate was 57 degrees. In the same solvent resistance test as in Example 1, the coating was not changed before and after immersion. Example 4 (C) SAN-AID SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was carried out in the same manner as in Example 1 except that the salt was changed as described below to obtain a radiation-sensitive resin composition.
[商品名ADEKA Optomer SP-172旭電化工業(股)製] 顯影後，除了使用超高壓水銀燈[USIO(股）製的USH-250D] 全面放射(以波長365nm爲基準的強度爲300mJ/cm2)全面曝光 以外，在和實施例1進行同樣操作的基板上形成了透明硬化 樹脂圖案，以實效靈敏度150 mJ/cm2顯影出3//m接觸孔圖案， 用薄膜厚度計測量所得到的透明硬化樹脂圖案（5)的厚度（T1) 爲 2.0 // m 〇 顯影後之圖案的斷面與基板所形成的角度Θ爲90度。按 照實施例1的同樣操作並測定出的光線透過率爲99.3%，有高 透明度，無著色。熱處理後的硬化樹脂圖案的斷面與基板所 形成的角度0爲56度。與實施例1相同的耐溶劑性試驗中， 12448pif.doc/008 28 200413848 浸漬前後塗佈沒有發生變化。 實施例5 除把(A)樹脂Al(100重量份)變更爲(A)樹脂A2(100重量 份）之外，其操作與實施例4一樣，從而得到了感放射線性樹 脂組成物。 顯影後，除了與實施例4相同的條件進行全面曝光以外， 在和實施例1進行同樣操作的基板上形成了透明硬化樹脂圖 案，以實效靈敏度120 mJ/cm2顯影出3//m接觸孔圖案，用薄 膜厚度計測量所得到的透明硬化樹脂圖案（5)的厚度（T1)爲2.1 // m。 顯影後之圖案的斷面與基板所形成的角度0爲90度。按 照實施例1的同樣操作並測定出的光線透過率爲99.5%，有高 透明度，無著色。熱處理後的硬化樹脂圖案的斷面與基板所 形成的角度Θ爲66度。與實施例1相同的耐溶劑性試驗中， 浸漬前後塗佈沒有發生變化。 實施例6 除把(A)樹脂Al(100重量份)變更爲(A)樹脂A3(100重量 份）之外，其操作與實施例4一樣，從而得到了感放射線性樹 脂組成物。 顯影後，除了在與實施例4相同的條件下進行全面曝光 以外，在和實施例1進行同樣操作的基板上形成了透明硬化 樹脂圖案，以實效靈敏度150 mJ/cm2顯影出3//m接觸孔圖案， 用薄膜厚度計測量所得到的透明硬化樹脂圖案（5)的厚度（T1) 爲 2.0 μ m。 顯影後之圖案的斷面與基板所形成的角度0爲90度。按 照實施例1的同樣操作並測定出的光線透過率爲99.3%，有高 12448pif.doc/008 29 200413848 透明度，無著色。熱處理後的硬化樹脂圖案的斷面與基板所 形成的角度0爲72度。與實施例1相同的溶劑性試驗中，浸 漬前後塗佈沒有發生變化 比較例1 除把（C)SAN-AID SI— 110(三新化學工業（股）製）變更爲以 下記錄的鹽，[Brand name: ADEKA Optomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd.] After development, it uses a high-pressure mercury lamp [USH-250D manufactured by USIO Co., Ltd.] and emits light in full (with an intensity of 300mJ / cm2 based on a wavelength of 365nm) Except for full exposure, a transparent hardened resin pattern was formed on the substrate that was operated in the same manner as in Example 1. A 3 // m contact hole pattern was developed with an effective sensitivity of 150 mJ / cm2. The obtained transparent hardened resin was measured with a film thickness meter. The thickness (T1) of the pattern (5) is 2.0 // m. The angle Θ formed by the cross section of the pattern after development and the substrate is 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.3%, and it had high transparency and no coloring. The angle between the cross section of the cured resin pattern after heat treatment and the substrate was 56 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating before and after immersion in 12448pif.doc / 008 28 200413848. Example 5 The same operation as in Example 4 was performed except that (A) resin Al (100 parts by weight) was changed to (A) resin A2 (100 parts by weight), thereby obtaining a radiation-sensitive resin composition. After development, except for full exposure under the same conditions as in Example 4, a transparent hardened resin pattern was formed on the substrate that was operated in the same manner as in Example 1, and a 3 // m contact hole pattern was developed with an effective sensitivity of 120 mJ / cm2. The thickness (T1) of the obtained transparent hardened resin pattern (5) measured with a film thickness meter is 2.1 // m. The angle 0 formed by the cross section of the developed pattern and the substrate was 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.5%, and had high transparency and no coloring. The angle Θ formed by the cross-section of the cured resin pattern after heat treatment and the substrate was 66 degrees. In the same solvent resistance test as in Example 1, the coating was not changed before and after immersion. Example 6 The operation was the same as in Example 4 except that (A) resin Al (100 parts by weight) was changed to (A) resin A3 (100 parts by weight), and a radiation-sensitive resin composition was obtained. After development, except that the entire exposure was performed under the same conditions as in Example 4, a transparent hardened resin pattern was formed on the substrate that was operated in the same manner as in Example 1, and 3 // m contact was developed with an effective sensitivity of 150 mJ / cm2. The hole pattern, and the thickness (T1) of the obtained transparent hardened resin pattern (5) measured with a film thickness meter was 2.0 μm. The angle 0 formed by the cross section of the developed pattern and the substrate was 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.3%, and had a high transparency of 12448 pif.doc / 008 29 200413848 and no coloration. The angle between the cross section of the cured resin pattern after heat treatment and the substrate was 72 degrees. In the same solvent test as in Example 1, there was no change in coating before and after immersion. Comparative Example 1 Except that (C) SAN-AID SI—110 (manufactured by Sanxin Chemical Industry Co., Ltd.) was changed to the following recorded salt,
[商品名：SAN-AID SI—11〇，三新化學工業(股)製]其操 作與實施例2相同，從而得到感放射線性樹脂組成物。 在和實施例1進行同樣操作的基板上形成了透明硬化樹 脂圖案。當實效靈敏度爲75 mJ/cm2時’顯影出3//m接觸孔 圖案，顯影後雖然圖案的斷面和基板所形成的角度0爲90度， 但熱處理後圖案溶解，不能形成透明樹脂圖案。按照實施例2 操作並測定的光線透過率爲99.3%，無著色。在與實施例1相 同的耐溶劑性實驗中，浸漬後在塗膜層上看到增加了 5%的膜 厚。 本發明的感放射線性樹脂組成物，因爲無著色，所以對 可見光的透過率很高，並且可以形成具有很好耐溶性以及對 輪廓有很好控制性的透明硬化樹脂圖案。本發明的感放射線 性樹脂組成物還能使TFT基板形成很好的生產性。 【圖式簡單說明】 第1A圖至第1C圖表示運用放射線性樹脂組成物而形成 的透明硬化樹脂圖案的工程模式圖。 12448pif.doc/008 30 200413848 第2圖表示爲了解釋說明0而顯示的圖案基板垂直斷面 的模式圖。 【圖式標示說明】 1 :感放射線性樹脂組成物層 2 :基板 3:正型遮光罩幕 4 :放射線 5:透明硬化樹脂圖案 11 :放射線未照射領域 12 :放射線照射領域 0 :對於圖案的基板來說，在垂直的斷面上，斷面 的棱線和基板面形成角度[Trade name: SAN-AID SI-11, manufactured by Sanxin Chemical Industry Co., Ltd.] The operation was the same as in Example 2 to obtain a radiation-sensitive resin composition. A transparent hardened resin pattern was formed on the substrate which was operated in the same manner as in Example 1. When the effective sensitivity is 75 mJ / cm2, a 3 // m contact hole pattern is developed. Although the angle 0 formed by the cross section of the pattern and the substrate after development is 90 degrees, the pattern is dissolved after heat treatment and a transparent resin pattern cannot be formed. The light transmittance measured and measured in accordance with Example 2 was 99.3%, and there was no coloration. In the same solvent resistance experiment as in Example 1, a 5% increase in film thickness was observed on the coating film layer after dipping. Since the radiation-sensitive resin composition of the present invention has no coloration, it has a high transmittance to visible light, and can form a transparent hardened resin pattern having good solvent resistance and good controllability to the contour. The radiation-sensitive resin composition of the present invention can also form a TFT substrate with good productivity. [Brief description of the drawings] Figs. 1A to 1C show process pattern diagrams of a transparent hardened resin pattern formed by using a radiation resin composition. 12448pif.doc / 008 30 200413848 FIG. 2 is a schematic view showing a vertical cross-section of a pattern substrate for explanation of 0. [Schematic description] 1: Radiation-sensitive resin composition layer 2: Substrate 3: Positive hood curtain 4: Radiation 5: Transparent hardened resin pattern 11: Radiation unirradiated area 12: Radiation irradiated area 0: For patterned For a substrate, the ridgeline of the section forms an angle with the substrate surface on a vertical section.
12448pif.doc/008 3112448pif.doc / 008 31