(1) (1)200407667 玖、發明說明 【發明所屬之技術領域】 本發明係有關適合作爲以噴墨方式塗佈有機EL絕緣 膜之輻射敏感性樹脂組成物，使用該組成物所形成之有機 EL顯示元件之絕緣膜、及其製造方法，及具備該絕緣膜 之有機EL顯示元件。 【先前技術】 相較於液晶顯示元件時，有機EL元件係因自行發光 ，因此無視角依存性，且爲固體元件，因而耐衝撃性優異 ’且具有低電壓驅動、低耗電力及低溫域之動作安定性高 等各種優點。有機EL元件具有這些優點，特別是期待適 用於攜帶型終端機或放置在車上使用等之攜帶用之用途， 而積極硏究中。 這種有機EL元件一般係以下述方法製造。在基板上 形成摻雜錫之氧化銦（I T〇）等之透明電極（電洞注入 電極）及電洞輸送層之圖案。接著被動型有機EL元件係 形成絕緣膜之圖案及陰極分隔牆之圖案後，藉由蒸鍍形成 有機EL層、電子輸送層及陰極之圖案。而主動型有機EL 元件係形成I T ◦圖案、成爲有機EL層之分隔牆之絕緣 膜的圖案後，藉由光罩法或噴墨法等形成有機EL層之圖 案，接著形成電子輸送層及陰極（電洞注入電極）。 有機EL層一般係使用在如Alq3、BeBq3之基板母材 (2) i (2) i200407667 上ί爹雜D奎吖酮或香豆素之材料，陰極材料使用如或 Ag之低工作函數之金屬爲主的材料。 上述有機EL絕緣膜之形成方法，以往係將在基板表 面上以噴塗法、輥塗法、旋轉塗佈法、棒塗佈法等方法所 塗佈之輻射敏感性樹脂組成物，利用預烘烤去除溶媒形成 塗膜後，經由所定之圖案的光罩，照射例如g射線（波長 4 3 6nm ) 、i射線（波長3 6 5 nm )等之紫外線' KrF準分子 雷射等之遠紫外線、同步加速輻射線等之X射線、電子線 等之荷粒子線等之輻射線。然後使用顯影液進行顯影處理 得到所要之圖案，此圖案經加熱處理可得到目的之有機EL 絕緣膜。但是這些塗佈法爲了安定塗佈需要絕緣膜形成所 需之輻射敏感性樹脂組成物量以上之大量的樹脂組成物。 因此，經常浪費輻射敏感性樹脂組成物，因此有成本增加 等的問題。 日本特開昭5 9-75 20 5號公報、特開昭6 1 -245 1 06號公報 、特開昭63 -23 5 90 1號公報等揭示具備使用噴墨頭形成彩色 瀘光片之著色層之步驟之噴墨方式之彩色濾光片的製造方 法，此方法具有可容易控制吐出彩色濾光片形成用樹脂組 成物之液滴的位置，且不會浪費樹脂組成物，因此可降低 製造成本的優點。 但是這些公報並未充分檢討有機EL顯不兀件之’絕緣 膜用組成物之適用噴墨方式之組成。 (3) (3)200407667 【發明內容】 [發明欲解決的問題] 本發明係有鑒於這些問題所完成者，本發明係提供可 以輻射線形成圖案，同時最適合以低成本之噴墨方式製造 有機EL顯示元件之絕緣膜形成用輻射敏感性樹脂組成物 ，有機EL顯示元件之絕緣膜及其形成方法。本發明之另 外的目的係提供具備該該絕緣膜之有機EL顯示元件。 [解決問題之方法] 本發明人等詳細檢討以噴墨方式形成有機EL顯示元 件之絕緣膜之步驟，結果發現區分有機EL顯示元件之各 像素圖案的絕緣膜之面積微小，因此，使用之噴墨頭必須 無阻塞，有機EL顯示元件用之絕緣膜形成用輻射敏感性 樹脂組成物液滴順利前進、吐出，因此，必須降低該組成 物吐出時液滴之乾固速度，同時抑制因溶媒蒸發形成液滴 粘度上升太快的情形，且必須防止固形份之析出，遂完成 本發明。 依據本發明時，本發明之上述目的係藉由含有（a) 鹼可溶性樹脂、（b ) 1，2 -醌二疊氮化合物及（c )常壓 之沸點爲1 8〇 °C以上之溶媒爲特徵之以噴墨方式形成有機 EL顯示元件之絕緣膜用的輻射敏感性樹脂組成物來達成 本發明之另外的目的係藉由至少含有下述步驟爲特徵 (4) 4 (4) 4200407667 之形成有機EL顯示元件之絕緣膜的方法來達成， (1 )基板表面上以噴墨裝置形成如申請專利範圍第1 或2項之輻射敏感性樹脂組成物之塗膜的步驟， (2 )對於形成之塗膜之至少一部分照射輻射線的步 驟， (3 )顯影步驟。 本發明之另外的目的係藉由上述輻射敏感性樹脂組成 物所形成之有機EL顯示元件之絕緣膜來達成。 本發明之另外的目的係藉由具有該有機EL顯示元件 之絕緣膜之有機EL顯示元件來達成。 以下說明本發明之以噴墨方式形成有機EL顯示元件 之絕緣膜用的輻射敏感性樹脂組成物之各成分。 (a )鹼可溶性樹脂 本發明使用之（a )鹼可溶性樹脂只要可溶於鹼水溶 液’則無特別限制’可使用藉由含有苯酚性羥基或羧基賦 予鹼可溶性之樹脂。 這種鹼可溶性樹脂例如有含有苯酚性羥基或羧基之自 由基聚合性單體之單獨聚合物或該自由基聚合性單體與其 他之自由基聚合性單體之共聚物。 含有苯酧性經基或羧基之自由基聚合性單體例如有鄰 羥基苯乙;C希、間羥基苯乙烯、對羥基苯乙烯或直接鍵結於 這些芳香環之氫原子之一部分或全部被烷基、烷氧基、鹵 素、歯院基、硝基、氰基、醯胺基、酯基或羧基取代之取 -9- (5) (5)200407667 代物； 乙烯基對苯二酚、5-乙烯基焦掊酚、6-乙烯基焦掊酚 、1-乙烯基氟甘油等之聚羥基乙烯基苯酚類；鄰乙烯基苯 甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸或直接鍵結於這 些芳香環之氫原子之一部分或全部被烷基、院氧基、鹵素 、硝基、氰基、醯胺基或酯取代之取代物；甲基丙烯酸、 丙烯酸及這些之α-位置被鹵烷基、烷氧基、鹵素、硝基 或氰基取代之^ -位置取代物；馬來酸、馬來酸酐、富馬酸 、富馬酸酐、檸康酸、中康酸、衣康酸、1，4-環己烯二 羧酸等之不飽和羧酸或這些其中之一之羧基變成甲基、乙 基、丙基、異丙基、正丁基、第二丁基、第三丁基、苯基 、鄰甲苯基、間曱苯基及對甲苯酸酯基之半酯或其中之一 之羧基變成醯胺基之半醯胺。 這些含有苯酚性羥基或羧基之自由基聚合性單體中， 較佳者爲間羥基苯乙烯、對羥基苯乙烯、丙烯酸、甲基丙 烯酸、馬來酸、馬來酸酐、衣康酸。這些可單獨使用或組 合二種以上使用。 其他之自由基聚合性單體例如有苯乙烯、苯乙烯之 α -甲基、鄰院基、間院基、對院基之取代物、或直接鍵 結於這些芳香環之氫原子之一部分或全部被烷氧基、鹵素 、硝基、氰基、醯胺基或酯取代之取代物； 丁二烯、異戊二烯、氯戊二烯之烯烴類；甲基（甲基 )丙烯酸酯、乙基（甲基）丙烯酸酯、正丙基（甲基）丙 -10- (6) (6)200407667 r 火希酸酯、異丙基（甲基）丙烯酸酯、正丁基（甲基）丙烯 酸醋、第二丁基（甲基）丙烯酸酯、第三丁基（甲基）丙 Μ酸酯、戊基（甲基）丙烯酸酯、新戊基（甲基）丙烯酸 醋、異戊基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯 、金剛院基（甲基）丙烯酸酯、烯丙基（甲基）丙嫌酸酯 、丙快基（甲基）丙烯酸酯、苯基（甲基）丙烯酸酯、萘 基（甲基）丙烯酸酯、蒽基（甲基）丙烯酸酯、蒽醌基（ 甲基）丙烯酸酯、胡椒基（甲基）丙烯酸酯、水楊基（甲 ® 基）丙烯酸酯、環己基（甲基）丙烯酸酯、苄基（甲基） 酸酯、苯乙基（甲基）丙烯酸酯、甲苯基（甲基）丙 少希酸酯、環氧丙基（甲基）丙烯酸酯、1、1、丨_三氟乙基 (甲基）丙烯酸酯、全氟乙基（甲基）丙烯酸酯、全氟正 丙s (甲基）丙烯酸酯、全氟異丙基（甲基）丙烯酸酯、 二苯基（甲基）丙烯酸酯、三環〔5·2.1.02’ 6〕癸烷-8-基 (甲基）丙烯酸酯（該技術領域慣稱爲〔二環戊烯基〕（ 甲基）丙烯酸酯）、枯烯基（甲基）丙烯酸酯、3· ( Ν， ® Ν_二甲基胺基）丙基（甲基）丙烯酸酯、3- (Ν，Ν-二甲 S fl安基）乙基（甲基）丙烯酸酯、呋喃基（甲基）丙烯酸 酉旨、糠基（甲基）丙烯酸酯之（甲基）丙烯酸酯； (甲基）丙烯醯苯胺、（曱基）丙烯醯胺、或（甲基 )丙烯酸，N-二甲基醯胺、（甲基）丙烯酸-N，N-二 乙基醯胺、（甲基）丙烯酸-N，N-二丙基醯胺、（甲基 )丙燒酸-N，N -二異丙基醯胺、（甲基）丙烯酸蒽基醯 -11 - (7) (7)200407667 胺、（甲基）丙烯腈、丙烯醛、氯乙烯、偏氯乙烯、氟乙 烯、偏氟乙烯、N-乙烯基吡咯烷酮、乙烯基吡啶、醋酸乙 烯酯、N-苯基順丁烯二胺、N- ( 4-羥苯基）順丁烯二胺、 N-甲基丙烯醯基酞醯亞胺、N-丙烯醯基酞醯亞胺等。 這些其他之自由基聚合性單體中，較理想者爲苯乙烯 、丁二烯、苯基（甲基）丙烯酸酯、苄基（甲基）丙烯酸 酯、三環〔5.2.1.02 ’ 6〕癸烷-8-基（甲基）丙烯酸酯。這 些可單獨使用或組合兩種以上使用。 這些其他之自由基聚合性單體之共聚比例係因可賦予 鹼可溶性之基的種類而異。具有羥基之自由基聚合性單體 爲具有苯酚性羥基之自由基聚合性單體時，其他之自由基 聚合性單體之共聚比例爲對於具有苯酚性羥基之自由基聚 合性單體與其他之自由基聚合性單體之合計量時，理想爲 0〜30重量％、更理想爲5〜20重量％。具有羥基之自由基 聚合性單體爲具有羧基之自由基聚合性單體時，其他之自 由基聚合性單體之共聚比例係對於具有羧基之自由基聚合 性單體與其他之自由基聚合性單體之合計量時，理想爲0 〜90重量％、更理想爲1〇〜80重量％。這些其他之自由基 聚合性單體之共聚比例係對於具有羥基或羧基之自由基聚 合性單體時，超過前述比例時，有時鹼顯影性不足。 如上述之驗可溶性樹脂中’特別理想者爲聚對經基本 乙烯、鄰甲基對羥基苯乙烯/對羥基苯乙烯共聚物、苯乙 烯/對羥基苯乙烯共聚物、苯乙烯/甲基丙烯酸/甲基丙 -12- (8) (8)200407667 烯酸環氧丙酯共聚物、苯乙烯/曱基丙烯酸/甲基丙烯酸 環氧丙酯/三環〔5· 2_ 1· 〇2’6〕癸烷一 8一基曱基丙烯 酸酯共聚物、甲基丙烯酸/曱基丙烯酸環氧丙酯/三環〔5 ,2 _ 1 · Ο2，6〕癸烷—8 一基甲基丙烯酸酯％丁二烯 共聚物、苯乙烯/曱基丙烯酸/甲基丙烯酸環氧丙酯/三 環〔5· 2·〇2，6〕癸烷一 8基_甲基丙烯酸酯/環己基 馬來醯亞胺/1，3_ 丁二烯共聚物等。 鹼可溶性樹脂（a )合成用之溶媒例如有甲醇、乙醇 、二丙醇等之醇類；四氫呋喃、四氫吡喃、二噁烷等之醚 類；乙二醇單甲醚、乙二醇單乙醚等之乙二醇烷醚類；甲 基溶纖素乙酸酯、乙基溶纖素乙酸酯等之乙二醇烷醚乙酸 酯類；二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲 醚、二乙二醇二乙醚、二乙二醇二乙基甲醚等之二乙二醇 醚類；丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙二醇丁 醚等之丙二醇單烷醚類；丙二醇甲醚醋酸酯、丙二醇乙醚 醋酸酯、丙二醇丙醚醋酸酯、丙二醇丁醚醋酸酯等之丙二 醇烷醚醋酸酯類；丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯 、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等之丙二醇烷醚 丙酸酯類；甲苯、二甲苯等之芳香族烴類；甲基乙基酮、 環己酮、4 -經基-4 -甲基-2-戊酮等之酮類；及醋酸甲酯、 醋酸乙酯、醋酸丙酯、醋酸丁酯、2-羥基丙酸乙酯、2-羥 基-2-甲基丙酸曱酯、2-羥基_2_甲基丙酸乙酯、羥基醋酸 甲酯、羥基醋酸乙酯、羥基醋酸丁酯、乳酸曱酯、乳酸乙 -13- 200407667 r Ο) 酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸 乙酯、3 -羥基丙酸丙酯、3 -羥基丙酸丁酯、2 -羥基-3 -甲基 丁酸甲酯、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋 酸丙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸 乙酯、乙氧基醋酸丙酯、乙氧基醋酸丁酯、丙氧基醋酸甲 酯、丙氧基醋酸乙酯、丙氧基醋酸丙酯、丙氧基醋酸丁酯 、丁氧基醋酸甲酯、丁氧基醋酸乙酯、丁氧基醋酸丙酯、 丁氧基醋酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯 、2 -甲氧基丙酸丙酯、2 -甲氧基丙酸丁酯、2 -乙氧基丙酸 甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基 丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁 氧基丙酸丙酯、2 -丁氧基丙酸丁酯、3 -甲氧基丙酸甲酯、 3 -甲氧基丙酸乙酯、3 -甲氧基丙酸丙酯、3 -甲氧基丙酸丁 酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -乙氧基丙 酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧 基丙酸乙酯、3 -丙氧基丙酸丙酯、3 -丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3 -丁氧基丙酸乙酯、3 -丁氧基丙酸丙酯 、3-丁氧基丙酸丁酯等之酯類。這些溶媒之使用量係對於 反應原料100重量份時，理想爲使用20〜1，000重量份。 製造鹼可溶性樹脂（a )所使用之聚合引發劑可使用 一般自由基聚合引發劑，例如有2，2，-偶氮二異丁腈、2 ，2’-偶氮二·（2，4-二甲基戊腈）、2，2’-偶氮二-(4-曱氧基-2，4-二甲基戊腈）等之偶氮化合物；過氧化苯醯 -14- (10) (10)200407667 、過氧化月桂醯、第三丁基過三甲基乙烯酯、1，l’-雙-(第三丁基過氧）環己烷等之有機過氧化物；及過氧化氫 。自由基聚合引發劑使用過氧化物時，過氧化物與還原劑 一起使用可作爲氧化還原引發劑。 本發明使用之（a )鹼可溶性樹脂之另外的合成法例 如得到相當於含有苯酚性羥基或羧基之自由基聚合性單體 之苯酚性羥基或羧基以烷基、乙醯基、苯醯甲基等適當之 保護基保護之單體之單體單獨聚合物或該相當之單體與其 他單體之共聚物後，以水解等反應去保護，賦予鹼可溶性 之方法來合成。 這種鹼可溶性樹脂中，特別理想爲使用聚對羥基苯乙 烯、鄰甲基對羥基苯乙烯/對羥基苯乙烯共聚物、苯乙烯/ 對羥基苯乙烯共聚物等。 本發明使用之（a )鹼可溶性樹脂例如可使用以氫化 等處理修正透明性或軟化點者。 本發明使用之（a)鹼可溶性樹脂之聚苯乙烯換算重 量平均分子量理想爲2，000〜100，〇〇〇的範圍，更理想爲 3，000〜50，000的範圍，特別理想爲5，〇〇〇〜30，000的 範圍。此範圍內可提供圖案形狀、解像度、顯影性及耐熱 性、顯影性及感度之彼此平衡性優異之輻射敏感性樹脂組 成物。 追些驗可溶丨生樹fl日之巾售品例如有marukarinker-M、 PHM-C (以上爲九善石油化學（股）製）、VP_ 1 500 (日 -15- (11) (11)200407667 本曹達（股）製）等之羥基苯乙烯（共）聚物或其部分氫 化物等。 本發明之（a )鹼可溶性樹脂此外例如可單獨使用酚 醒樹脂等之縮合系樹脂或與前述之鹼可溶性樹脂混合使用 〇 酚醛樹脂係在酸觸媒存在下，苯酚類與醛類進行縮聚 所得。此時使用之苯酚類例如有苯酚、鄰甲酚、間曱酚、 對甲酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基 苯酚、間丁基苯酚、對丁基苯酚、2，二甲酚、2，4_二 甲酚、2，5-二甲酚、3，4-二甲酚、3，5-二甲酚、2，3 ，5-三甲基苯酚、3，4，5_三甲基苯酚、對苯基苯酚、對 苯二酣、兒茶酚、間苯二酚、2-甲基間苯二酚、焦掊酚、 萘酷、/3-萘酚、雙酚A、二羥基苯甲酸酯、沒食子酸 醋、鄰硝基苯酚、間硝基苯酚、對硝基苯酚、鄰氯苯酚、 間氯苯酣、對氯苯酚等。這些中較理想者爲鄰甲酚、間甲 酚、對甲酚、2，3-二甲酚、2，4-二甲酚、2，5-二甲酚 、2’ 3’ 5-三甲基苯酚、間苯二酚、2_甲基間苯二酚等。 胃些苯酣可單獨使用或組合二種以上使用。 又與上述苯酚類縮聚之醛類例如有甲醛、對甲醛、苯 甲醛、乙醛、丙醛、苯醛、α -苯基丙醛、-苯基丙醛、 鄰羥基苯甲醛、間羥基苯甲醛、對羥基苯甲醛、鄰氯苯甲 酉签 '間氣苯甲醛、對氯苯甲酸、鄰硝基苯甲酸、間硝基苯 甲醛、對硝基苯甲醛、鄰甲基苯甲醛、間甲基苯甲醛、對 -16- (12) (12)200407667 曱基苯甲醛、鄰乙基苯甲醛、間乙基苯甲醛、對乙基苯甲 酸、對正丁醛、糠酵、1 -萘醛、2 -萘酸、2 -羥基_ 1 -萘酵等 。反應中生成醛之化合物，例如可與前述醛類同樣使用三 噁院等。這些中特別適甲醛較理想。這些醛類及生成醛之 化合物可單獨使用或組合二種以上使用。醛類係對於酚類 時，通常使用〇.7〜3莫耳，更理想爲〇.7〜2莫耳。 酸觸媒可使用鹽酸、硝酸、硫酸、對苯磺酸、甲酸、 乙酸、草酸等。其使用量係對於酚類1莫耳時，理想爲使 用 lx 10·4 〜5x 10·1莫耳。 縮聚反應時，反應媒質通常使用水，但是縮聚反應所 使用之苯酚類不溶解於醛類之水溶液，反應初期形成不均 一體系時，反應媒質也可使用親水性有機溶媒。此時所用 之溶媒例如有甲醇、乙醇、丁醇之醇類；四氫呋喃、二噁 烷之環狀醚類。這些反應媒質之使用量係對於反應原料 1〇〇重量份時，理想爲使用20〜400重量份。 縮聚之反應溫度可配合反應原料之反應性來適當調節 。通常爲1〇〜200 °C。縮聚反應結束後’爲了除去體系內 之未反應原料、觸媒及反應媒質時，一般是昇溫至13〇〜 2 3 0 °C以上，減壓下餾去揮發成分，回收酚醛樹脂。 這種酚醛樹脂中，特別理想者爲間甲酣/甲醛縮聚物 、間甲酚/對甲酚/曱醛縮聚物、間甲酚/2 ’ 3 -二甲酚/甲醛 縮聚物、間甲酚/2，4-二甲酚/甲醛縮聚物、間甲酚/2，5-二甲酚/甲醛縮聚物等。 -17- (13) 200407667 又酚醛樹脂之聚苯乙烯換算重量平均分子量（以下稱 爲「M w」）理想爲2，0 0 0〜2 0，0 0 0的範圍，更理想爲3 ，000〜15，000的範圍。Mw超過20，000時，有時不易 將組成物均勻塗佈於晶圓上，有時顯影性及感度會降低。 1，2 -醌二疊氮化合物 本發明使用之（b ) 1，2-醌二疊氮化合物可使用具有輻射 疊氮化合物。例如有1，2 - 線照射產生羧酸之功能的1， f 苯醌二疊氮磺酸酯、1，2-萘醌二疊氮磺酸酯、1，2-苯醌 氮磺酸醯胺、1，2-萘醌二疊氮磺酸醯胺等。 這些之具體例有2，3，4-三羥基二苯甲酮-1，2-萘醌二疊 氮-4-磺酸酯、2，3，4-三羥基二苯甲酮-1，2-萘醌二疊氮-5-磺 酸酯、2，4，6-三羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2 ，4，6-三羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯等之三羥基 二苯甲酮之1，2-萘醌二疊氮磺酸酯； 2，2’，4，4’-四羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸 、2，2’，4，4’-四羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、 2，3，4，3’-四羥基二苯甲酮-1，2_萘醌二疊氮-4-磺酸酯、2， 3，4，3’-四羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、2，3, 4，4、四羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，3，4， 4’-四羥基二苯曱酮-1，2-萘醌二疊氮-5-磺酸酯、2，3，4，2’-四羥基-4’-甲基二苯曱酮-1，2-萘醌二疊氮-4-磺酸酯、2，3，4 ，2’-四羥基-4’-曱基二苯甲酮-1，2-萘醌二疊氮-5-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-4-磺酸 -18- (14) 200407667 酯、2，3，4，4’-四羥基- 3’-甲氧基二苯甲酮-1，2-萘醌二疊氮· 5-磺酸酯等之四羥基二苯甲酮之1，2-萘醌二疊氮磺酸酯； 2，3，4，2’，6’-五羥基二苯甲酮-1，2-萘醌二疊氮-4-磺 酸酯、2，3，4，2’，6’-五羥基二苯甲酮-1，2 -萘醌二疊氮-5_ 磺酸酯等之五羥基二苯甲酮之1，2-萘醌二疊氮磺酸酯； t 2，4，6，3’，4’5’-六羥基二苯甲酮-1，2-萘醌二疊氮-4·磺 酸酯、2，4，6，3’，4’5’-六羥基二苯甲酮-1，2-萘醌二疊氮 磺酸酯、3，4，5，3 ’，4 ’ 5 ’ -六羥基二苯甲酮-1，2_萘醌二 氮-4-磺酸酯、3，4，5，3’，4’5’-六羥基二苯甲酮-1，2-萘醌二 疊氮-5-磺酸酯等之六羥基二苯甲酮之1，2-萘醌二疊氮磺酸酯： 雙（2，4_二羥苯基）甲烷-1，2-萘醌二疊氮-4-磺酸酯、雙 (2，4_二羥苯基）甲烷-1，2_萘醌二疊氮-5-磺酸酯、雙（對羥 苯基）甲烷-1，2-萘醌二疊氮-4-磺酸酯、雙（對羥苯基）甲烷-1，2-萘醌二疊氮-5-磺酸酯、三（對羥苯基）甲烷-1，2-萘醌二 疊氮-4-磺酸酯、三（對羥苯基）甲烷-1，2-萘醌二疊氮-5-磺g 酯、1，1，1-三（對羥苯基）乙烷-1，2-萘醌二疊氮-4-磺酸酯 、1，1，1-三（對羥苯基）乙烷-1，2_萘醌二疊氮-5-磺酸酯、 雙（2 (2， 雙（2 3，4_三羥苯基）甲烷d，2-萘醌二疊氮-4-磺酸酯、雙 4-三羥苯基）甲烷-1，2-萘醌二疊氮-5-磺酸酯、2，2-3，4-三羥苯基）丙烷-1，2_萘醌二疊氮-4-磺酸酯、2， 2-雙（2，3，4-三羥苯基）丙烷-1，2-萘醌二疊氮-5-磺酸酯、1 ，1，3-三（2，5-二甲基-4-羥苯基）-3-苯基丙烷-1，2-萘醌二 疊氮-4-磺酸酯、1，1，1-三（2，5-二甲基-4-羥苯基）-3-苯基 -19- (15) (15)200407667 丙烷-1，2 -萘醌二疊氮-5-磺酸酯、4，4，-〔 1_〔 4-〔 1-〔 4 -羥苯 基〕-1-甲基乙基〕苯基〕亞乙基〕雙酚-1，2-萘醒二疊氮-4-磺 酸酯、4，4’-〔 1-〔 4-〔 1-〔 4·羥苯基〕-1-曱基乙基〕苯基〕亞 乙基〕雙酣-1，2 -萘醌二疊氮-5-磺酸酯、雙（2，5 -二甲基-4-羥苯基）-2-羥苯基甲烷_1，2_萘醌二疊氮磺酸醋、雙（2, 5-二甲基-4-羥苯基）-2-羥苯基甲烷-1，2-萘醌二疊氮-5-磺酸酯 、3，3，3，，3’·四甲基-1，1，-螺二茚-5，6，7，5，，6，，7，-己 醇-1，2-萘醌二疊氮-4-擴酸酯、3，3，3’，3’-四甲基-1，ΐΊ 二節-5，6，7，5’，6’，7’-己醇-1，2 -萘 II 二疊氮-5-擴酸酯、2 ，2，4-三甲基-7，2’，4’·三羥基磺烷-1，2-萘醌二疊氮-4-磺酸 酯、2，2，4-三曱基-7，2’，4’-三羥基磺烷-1，2-萘醌二疊氮-5-磺酸酯等之（聚羥苯基）烷之-1，2-萘醌二疊氮磺酸酯。 除了這些化合物外可使用 J.Kosar著、、Light-Sensitive Systems" 339 〜352(1965)，John Wiley & Sons 社（New York)或 W.S.De Fores 著、、Photoresist’’ 50(1975)McGraw-Hill，Inc.(N York)所記載之1，2_醌二疊氮化合物。 這些可使用以其一部分或全量與上述（a )鹼可溶性樹脂反 應形成縮合物的形態。 這些之1，2-醌二疊氮化合物中，理想爲1，1，1-三（2, 5-二甲基-4-羥苯基）-3-苯基丙烷-1，2-萘醌二疊氮磺酸酯、 1，1，1-三（2，5 -二甲基-4-羥苯基）-3 -苯基丙烷-1，2-萘醌二 疊氮-4-礦酸醋、4 ’ 4’-〔 1-〔 4-〔 1_〔 4-經苯基〕-1-甲基乙基 〕苯基〕亞乙基〕雙酚-1，2-萘醌二疊氮-4-磺酸酯、4，4’-〔 -20- (16) (16)200407667 〔4-羥苯基〕-1-甲基乙基〕苯基〕亞乙基〕雙酚-1 ，2·萘醌二疊氮-5-磺酸酯、2，2，4-三甲基-7，2’，4’-三羥基 磺烷-1，2 -萘醌二疊氮-4-磺酸酯、2，2，4 -三甲基-7，2’，4’- 三羥基磺烷-1，2-萘醌二疊氮-5-磺酸酯、1，1’ 1-三（對羥苯 基）乙烷-1，2-萘醌二疊氮·4·磺酸酯、1，1，1-三（對羥苯基 )乙烷-1，2-萘醌二疊氮-5-磺酸酯等。 上述之1，2 -醌二疊氮化合物可單獨使用或混合二種以上使 用。 (b ) 1，2-醌二疊氮化合物之添加量係對於（a )鹼可溶性 樹脂1〇〇重量份時，添加5〜1〇〇重量份，更理想爲10〜50重量份 。此添加量低於5重量份時’有時圖案不易形成，又超過100重 量份時，有時利用由鹼性水溶液所構成之顯影液之顯影困難。 本發明之組成物中，爲了提高感度對於1，2-醌二疊 氮化合物可添加增感劑。增感劑例如有2H-吡啶-(3，2-b )·1，4-噁嗪 _3 ( 4H )-酮類、10H-吡啶-(3，2-b ) - ( 1 · ，4 )-苯並噻嗪類、脲唑類、乙內醯脲類、丙二醯脲類、 甘氨酸酐類、1 -羥基苯並三唑類、阿脲類、順丁醯二胺類 等。這些增感劑之使用量係對於1，2 -醌二疊氮化合物1 〇 〇 重量份時，理想爲使用100重量份以下，更理想爲4〜60重 量份。 (c)常壓之沸點爲180°C以上之溶媒 本發明之溶媒係由常壓（一大氣壓）之沸點（以下僅 稱「沸點」）爲1 80 °C以上之溶媒（以下稱爲「高沸點溶 -21 - (17) (17)200407667 媒」）所構成。高沸點溶媒之沸點理想爲200 °C以上。高 沸點溶媒之沸點的上限只要是由本發明之噴墨用之有機 EL絕緣膜形成用輻射敏感性樹脂組成物，藉由噴墨方式 可製造有機EL絕緣膜時，則無特別限定，但是從樹脂組 成物之調製步驟及有機EL絕緣膜之製造步驟之操作性的 觀點，沸點爲29〇°C以下，理想爲2 80°C以下，且常溫（2〇 °C )下爲較低粘度之液體的高沸點溶媒較佳。因此’本發 明之高沸點溶媒之理想的沸點範圍，具體爲180〜290 °C ’ 更理想爲200〜280°C。 高沸點溶媒例如有以式R^O ( CH2CH20) 2-R2 ( R1及 R2係相互獨立之碳數2〜10之烷基）表示之二乙二醇二烷 醚系溶媒； 以式&3-〇(〇112(：1120)3-尺4(厌3及尺4係相互獨立之 碳數1〜10之烷基）表示之三乙二醇二烷醚系溶媒； 以式R5-〇(CH2CH20) i-R6(R5及R6係相互獨立之 碳數1〜10之烷基、i係2〜30之整數）表示之聚乙二醇二 烷醚系溶媒； 以式r7_0CH ( CH3 ) CH20-R8 ( R7及R8係相互獨立 之碳數2〜10之院基）表示之丙二醇二烷醚系溶媒； 乙二醇單異戊醚、乙二醇單己醚、乙二醇單苯醚等之 乙二醇單烷醚類； 乙二醇單丁醚醋酸酯等之乙二醇單烷醚醋酸酯類； 二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙 -22- (18) (18)200407667 醚、二乙二醇單正丁醚等之二乙二醇單烷醚類； 二乙二醇單甲醚醋酸酯、二乙二醇單乙醚醋酸酯、二 乙二醇單正丙醚醋酸酯、二乙二醇單正丁醚醋酸酯等之二 乙二醇單烷醚醋酸酯類； 丙二醇丁醚醋酸酯等之丙二醇烷醚醋酸酯類； 乙二醇單苯醚醋酸酯、二乙二醇二乙醚、苄基乙醚、 二己醚等之其他醚類； 1 一辛醇、1 一壬醇、苄醇等之醇類； 乙腈丙酮、異佛爾酮等之酮類； 己酸、癸酸等之羧酸類； 乳酸丁酯、苯甲酸乙酯、苯甲酸丁酯、草酸二乙酯、 順丁烯二酸二乙酯、馬來酸二正丁酯、甘油三醋酸酯、富 馬酸二正丁酯、苯甲酸二甲酯、苯甲酸二乙酯、苯甲酸二 正丙酯、苯甲酸二異丙酯、苯甲酸二正丁酯、水楊酸異戊 酯、r -丁內酯、碳酸乙烯酯、碳酸丙烯酯等之酯系溶媒 等。 本發明之理想的高沸點溶媒例如有乙二醇單丁醚醋酸 酯、二乙二醇二乙醚、二乙二醇單乙醚醋酸酯、二乙二醇 單丁醚醋酸酯、二丙二醇、丙二醇丁醚醋酸酯、二乙二醇 二正丁醚、四甘醇二甲醚、五甘醇二曱醚、六甘醇二甲醚 、丙二醇二正丁醚、乳酸丁酯等。 該高沸點溶媒可單獨或混合兩種以上使用。 高沸點溶媒之使用量係對於（a )鹼可溶性樹脂1 00重 -23- (19) (19)200407667 量份時，通常使用10〜10，〇〇〇重量份，理想爲50〜5， 000重量份，更理想爲1〇〇〜2，000重量份。 本發明中，使用高沸點溶媒具有下述效果。 (1)噴墨方式形成圖像圖案時’使噴墨用有機EL 絕緣膜形成用輻射敏感性樹脂組成物吐出，去除溶媒後， 加熱形成格子狀有機EL顯示元件之絕緣膜，此時適度抑 制高沸點溶媒之蒸發速度，吐出之該樹脂組成物在溶媒去 除時或加熱時不會劇烈變化，因此，提高形成有機EL顯 示元件之絕緣膜時的作業效率。 (2 )噴墨方式形成有機EL絕緣膜時，因溶媒蒸發 ，使有機EL絕緣膜形成用輻射敏感性樹脂組成物漸漸變 粘稠，若溶媒之沸點較低時，粘度變化大，因此，在有機 EL絕緣膜塗佈過程之初期與終了之吐出之該樹脂組成物 的變化大，影響有機EL絕緣膜之塗佈，而採用高沸點溶 媒可抑制降低此粘度變化，使所要之有機EL絕緣膜之塗 佈容易。 (3 )可防止使有機EL絕緣膜形成用輻射敏感性樹 脂組成物吐出之噴墨頭因組成物之乾涸而阻塞’藉此可防 止該組成物吐出時之飛行彎曲，可確保良好之直線性’提 高有機EL絕緣膜形成用輻射敏感性樹脂組成物之利用效 率及有機EL顯示元件之絕緣膜製造裝置之洗淨效率。 本發明中，沸點爲1 8 〇 °C以下之溶媒（以下稱爲「低 沸點溶媒」）可與高沸點溶媒倂用。 -24- (20) (20)200407667 這種低沸點溶媒例如有乙二醇單甲醚、乙二醇單乙醚 、乙二醇單丙醚、乙二醇單丁醚等之乙二醇單烷醚類； 曱基溶纖素醋酸酯、乙基溶纖素醋酸酯等之乙二醇烷醚醋 酸酯類； 乙二醇單甲醚醋酸酯、乙二醇單乙醚醋酸酯、乙二醇單丙 醚醋酸酯等之乙二醇單烷醚醋酸酯類； 丙二醇單曱醚醋酸酯、丙二醇單乙醚醋酸酯等之丙二醇單 烷醚醋酸酯類； · 二乙二醇二甲醚、四氫呋喃等其他醚類； 丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙二醇丁醚等之 丙二醇單烷醚類； 丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、丙二醇丙醚醋酸 酯、丙二醇丁醚醋酸酯等之丙二醇單烷醚醋酸酯類； 甲醇、乙醇等之醇類； 甲苯、二甲苯等之芳香族烴類； 甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、2-庚酮、^ 庚酮、甲基異戊酮等之酮類；及 醋酸甲酯、醋酸乙酯、醋酸丙酯、醋酸丁酯、醋酸異丁酯 、甲酸正戊酯、醋酸異戊酷、乙醯醋酸甲酯、乙醯醋酸乙酯、 2 -羥基丙酸甲酯、2 -羥基丙酸乙酯、2 -羥基_2_甲基丙酸甲酯、 2 -羥基-2 -甲基丙酸乙酯、羥基醋酸甲酯、羥基醋酸乙酯、羥基 醋酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、3_羥基丙酸甲酯 、3 _羥基丙酸乙酯、3 -羥基丙酸丙酯、2 _羥基_ 3 _甲基丁酸甲酯 -25- (21) (21)200407667 、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丙酯、甲氧 基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸 丙酯、丙氧基醋酸甲酯、丙氧基醋酸乙酯、丁氧基醋酸甲酯、 丁氧基醋酸乙酯、2 -甲氧基丙酸甲酯、2 -甲氧基丙酸乙酯、2-乙氧基丙酸甲酯、2_乙氧基丙酸乙酯' 2_丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、3 -甲氧基丙酸甲酯、3_甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、乙氧基丙酸乙酯、3_丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、丁氧基丙酸甲酯、3 -丁氧基丙酸乙酯等f 酯類。 這些溶媒中，較理想者爲二乙二醇類、丙二醇單烷醚醋酸 酯類、丙二醇烷基醋酸酯類、酯類，特別理想爲二乙二醇二甲 醚、二乙二醇乙基甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯、丙 二醇乙醚醋酸酯、3 _曱氧基丙酸甲酯、3 -乙氧基丙酸乙酯、乳 酸甲酯、乳酸乙酯。 這些低沸點溶媒可單獨一種或組合2種以上來使用。 0 低沸點溶媒之使用比例係對於高沸點溶媒與低沸點溶媒之 合計量，通常使用50重量％以下，理想爲30重量％以下。此時 低沸點溶媒之使用比例超過50重量％時，有時會影響高沸點溶 媒之使用效果。 本發明之有機EL絕緣膜形成用輻射敏感性樹脂組成物中 ’使用（d)分子內含有兩個以上之環氧基之化合物及（e)三 聚氰胺化合物中之至少一種的化合物，由該組成物所形成之絕 緣膜係對於用於被動型液晶顯示元件之陰極形成時所使用之光 -26- (22) (22)200407667 阻剝離液之耐性特別高，且即使於光阻剝離液中絕緣膜也不會 剝離。 (d)分子內含有兩個以上之環氧基之化合物 本發明使用之（d)分子內含有兩個以上之環氧基之化合物 例如有 Epycoat 1001、 1002、 1003、 1004、 1007、 1009、 1010 、8 28 (以上爲油化Shell Epox (股）製）等之雙酚A型環氧樹 脂市售品，Epycoat 8 07 (以上爲油化Shell Epox (股）製） 等之雙酚F型環氧樹脂市售品，Epycoat 152、154 (以上爲f 化Shell Epox (股）製）、EP PN 2 01、2 0 2 (以上爲曰本化藥（ 股）製）等之苯酚酚醛型環氧樹脂市售品，EOCN-102、103S 、1 04S、1 020、1 025、1 027 (以上爲日本化藥（股）製）、 Epycoat 180S75(以上爲油化Shell Epox (股）製）等之甲階酣 醛型環氧樹脂市售品， CY-175、177、179 (以上爲 Ciba gaigy (公司）製）、ERL-4234、4299、422 1、4206 (以上爲 U.C.C (股）製）、Shodine 5 09 (昭和電工（股）製）_ Aldalite CY-182、192、184(以上爲 Ciba Geigy (公司）製） 、Epyclone 200、400 (以上爲大日本油墨（股）製）'Epycoat 871、872(以上爲油化 Shell Epox (股）製）、ED-5661、5662 (以上爲Ceraneedscoating (股）製）等之環脂肪族環氧樹脂 市售品，Epolite 1 00MF、200E、400E (以上爲共榮社油脂化 學工業（股）製）、Epyol TMP (日本油脂（股）製）等之脂 肪族聚縮水甘油醚市售品。 這些化合物中，從顯影性及反射凹凸之形狀之控制的觀點 -27- (23) (23)200407667 ，可使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、甲階酚醛型 環氧樹脂、脂肪族聚縮水甘油醚類。 _ 除上述環氧化合物外，也可使用例如雙酚A、雙酚F之縮 水甘油醚之化合物。 本發明之組成物含有這些（d)分子內含有兩個以上之環氧 基之化合物時，其添加量係對於（a )鹼可溶性樹脂1 〇 〇重量份 時，添加1 〇 〇重量份以下，更理想爲1〜1 〇 0重量份，特別理想爲 5〜50重量份。由含有此範圍之分子內含有兩個以上之環氧基ί 化合物的組成物所構成之硬化物，其耐熱性或密著性優異。分 子內含有兩個以上之環氧基之化合物之添加量低於1重量份時， 硬化反應無法充分進行，由這種組成物所構成之硬化膜有時耐 熱性、耐溶劑性差。又超過1 00重量份時，組成物整體之軟化點 降低，形成用於光擴散反射膜之圖案時之加熱處理中，形狀不 易保持。 前述（a )鹼可溶性樹脂中，使用共聚單體之含環氧基部g 和單體時，可稱爲「分子內含有兩個以上之環氧基之化合物」 ，但是在具有鹼可溶性方面與（d )成分不同。 (e )三聚氰胺化合物 本發明使用之（e)三聚氰胺係以下述一般式（1)表示之 化合物。 -28- (24) 200407667 RVR1。(1) (1) 200407667 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive resin composition suitable for coating an organic EL insulating film by an inkjet method, and an organic substance formed by using the composition An insulating film of an EL display element, a method for manufacturing the same, and an organic EL display element including the insulating film. [Previous technology] Compared with liquid crystal display elements, organic EL elements emit light by themselves, so they have no viewing angle dependence, and are solid elements, so they have excellent shock resistance, and have low voltage drive, low power consumption, and low temperature range. Various advantages such as high movement stability. The organic EL element has these advantages, and is particularly expected to be used in portable terminals or portable applications such as being used in a car, and is actively being investigated. Such an organic EL element is generally manufactured by the following method. A pattern of a transparent electrode (hole injection electrode) such as indium oxide (ITO) doped with tin and a hole transport layer is formed on the substrate. Next, a passive organic EL element is formed with a pattern of an insulating film and a pattern of a cathode partition wall, and then a pattern of an organic EL layer, an electron transport layer, and a cathode is formed by evaporation. The active organic EL element is formed with an IT pattern, an insulating film that becomes a partition wall of the organic EL layer, and then a pattern of the organic EL layer is formed by a photomask method or an inkjet method, and then an electron transport layer and a cathode are formed. (Hole injection electrode). The organic EL layer is generally used on a substrate base material (2) i (2) i200407667 such as Alq3, BeBq3, and d-Dacridone or coumarin. The cathode material is a metal with a low work function such as or Ag. Based material. The method for forming the above-mentioned organic EL insulating film has conventionally used a radiation-sensitive resin composition coated on the substrate surface by a spraying method, a roll coating method, a spin coating method, a rod coating method, or the like, using pre-baking. After the solvent is removed to form a coating film, ultraviolet rays such as g-rays (wavelength 4 36 nm) and i-rays (wavelength 36 5 nm) are irradiated with far-ultraviolet rays such as g-rays (wavelength 4 36 nm) and i-rays (wavelength 36 5 nm). Accelerated radiation, such as X-rays, electron rays, and charged particle rays. Then, a developing solution is used to perform a developing process to obtain a desired pattern, and the pattern is heated to obtain a desired organic EL insulating film. However, these coating methods require a large amount of a resin composition having a radiation-sensitive resin composition amount more than that required for the formation of an insulating film for stable coating. Therefore, the radiation-sensitive resin composition is often wasted, and there is a problem that the cost is increased. Japanese Patent Application Laid-Open No. 5 9-75 20 5; Japanese Patent Application Laid-Open No. 6 1-245 1 06; Japanese Patent Application Laid-Open No. 63 -23 5 90 1; etc. discloses that the coloration is provided by the use of an inkjet head to form a color phosphor film. The method of manufacturing a color filter using an inkjet method in the step of a layer. This method can easily control the position at which the droplets of the resin composition for forming a color filter are discharged, and the resin composition is not wasted. Therefore, manufacturing can be reduced. Cost advantage. However, these publications have not sufficiently reviewed the composition of an inkjet system suitable for a composition for an 'insulating film of an organic EL display device. (3) (3) 200407667 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention is made in view of these problems. The present invention provides a pattern that can be formed by radiation, and is most suitable for manufacturing with a low-cost inkjet method. Radiation-sensitive resin composition for forming an insulating film of an organic EL display element, an insulating film of an organic EL display element, and a method for forming the same. Another object of the present invention is to provide an organic EL display element including the insulating film. [Methods to Solve the Problem] The present inventors reviewed the process of forming an insulating film of an organic EL display element by an inkjet method in detail, and found that the area of the insulating film that distinguishes each pixel pattern of the organic EL display element is small. The ink head must be non-blocking, and the droplets of the radiation-sensitive resin composition for forming an insulating film for an organic EL display element can be smoothly advanced and ejected. Therefore, the drying speed of the droplets must be reduced when the composition is ejected, and the evaporation of the solvent must be suppressed. The situation where the viscosity of the droplets rises too fast and the precipitation of solids must be prevented, has led to the completion of the present invention. According to the present invention, the above object of the present invention is to use a solvent containing (a) an alkali-soluble resin, (b) a 1,2-quinonediazide compound, and (c) a boiling point of 180 ° C or more at normal pressure. It is characterized in that a radiation-sensitive resin composition for forming an insulating film of an organic EL display element is formed by an inkjet method to achieve the other object of the present invention by including at least the following steps (4) 4 (4) 4200407667 To achieve the method of forming an insulating film of an organic EL display element, (1) a step of forming a coating film of a radiation-sensitive resin composition such as the item 1 or 2 of the scope of patent application by an inkjet device on the substrate surface, (2) for A step of irradiating at least a part of the formed coating film with radiation, (3) a developing step. Another object of the present invention is achieved by an insulating film of an organic EL display element formed of the radiation-sensitive resin composition. Another object of the present invention is achieved by an organic EL display element having an insulating film of the organic EL display element. Hereinafter, each component of the radiation-sensitive resin composition for forming an insulating film of an organic EL display element by an inkjet method according to the present invention will be described. (a) Alkali-soluble resin (a) The alkali-soluble resin used in the present invention is not particularly limited as long as it is soluble in an aqueous alkali solution '. A resin that is rendered alkali-soluble by containing a phenolic hydroxyl group or a carboxyl group can be used. Such an alkali-soluble resin is, for example, a separate polymer containing a phenolic hydroxyl group or a carboxyl group-free polymerizable monomer or a copolymer of the radical polymerizable monomer and another radical polymerizable monomer. Free-radically polymerizable monomers containing a phenyl amido group or a carboxyl group, such as o-hydroxystyrene; C, C, m-hydroxystyrene, p-hydroxystyrene, or a part or all of hydrogen atoms directly bonded to these aromatic rings Alkyl, alkoxy, halogen, fluorenyl, nitro, cyano, fluorenyl, ester or carboxyl substituted -9- (5) (5) 200407667 Substitute; vinyl hydroquinone, 5 -Vinyl pyrophenol, 6-vinyl pyrophenol, 1-vinyl fluoroglycerol and other polyhydroxy vinyl phenols; o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid or direct bond Some or all of the hydrogen atoms attached to these aromatic rings are substituted with alkyl, oxo, halogen, nitro, cyano, amido or ester; methacrylic acid, acrylic acid and the α-position of these are Haloalkyl, alkoxy, halogen, nitro or cyano substituted ^ -position substitutes; maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid Unsaturated carboxylic acids such as 1,4-cyclohexene dicarboxylic acid, or the carboxyl group of one of these becomes methyl, ethyl Propyl, propyl, isopropyl, n-butyl, second butyl, third butyl, phenyl, o-tolyl, m-phenyl, and p-toluate half-esters or one of the carboxyl groups becomes Hemiamidamine. Among these radically polymerizable monomers containing a phenolic hydroxyl group or a carboxyl group, preferred are m-hydroxystyrene, p-hydroxystyrene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid. These can be used alone or in combination of two or more. Other free-radically polymerizable monomers are, for example, styrene, α-methyl of styrene, adjacent radicals, intermediate radicals, substituents to radicals, or a part of hydrogen atoms directly bonded to these aromatic rings, or Substituents all substituted with alkoxy, halogen, nitro, cyano, amido or esters; olefins of butadiene, isoprene, chloroprene; methyl (meth) acrylates, Ethyl (meth) acrylate, n-propyl (meth) propane-10- (6) (6) 200407667 r Phenyl ester, isopropyl (meth) acrylate, n-butyl (meth) Acrylic acid vinegar, second butyl (meth) acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, adamantine (meth) acrylate, allyl (meth) propanoate, propionyl (meth) acrylate, phenyl ( (Meth) acrylate, naphthyl (meth) acrylate, anthracene (meth) acrylate, anthraquinone (meth) acrylate Piperonyl (meth) acrylate, salicyl (methyl) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, tolyl (Meth) acrylic acid ester, epoxypropyl (meth) acrylate, 1, 1, 丨 _trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, all Fluoro-n-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, diphenyl (meth) acrylate, tricyclic [5 · 2. 1. 02 '6] decane-8-yl (meth) acrylate (commonly known in the technical field as [dicyclopentenyl] (meth) acrylate), cumenyl (meth) acrylate, 3 · (Ν, ® Ν-dimethylamino) propyl (meth) acrylate, 3- (N, N-dimethyl S fl anthryl) ethyl (meth) acrylate, furyl (methyl) Acrylic purpose, (meth) acrylate of furfuryl (meth) acrylate; (meth) acrylic acid aniline, (fluorenyl) acrylamide, or (meth) acrylic acid, N-dimethylammonium amine , (Meth) acrylic acid-N, N-diethylphosphoniumamine, (meth) acrylic acid-N, N-dipropylphosphoniumamine, (meth) propionic acid-N, N-diisopropylfluorene Amine, Anthracene (meth) acrylate-11-(7) (7) 200407667 Amine, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl Pyrrolidone, vinylpyridine, vinyl acetate, N-phenylcis butylene diamine, N- (4-hydroxyphenyl) cis butylene diamine, N-methacryl fluorenyl phthalimide, N-propylene Fluorenylphthalimide and so on. Among these other radically polymerizable monomers, styrene, butadiene, phenyl (meth) acrylate, benzyl (meth) acrylate, and tricyclic [5. 2. 1. 02 '6] decane-8-yl (meth) acrylate. These can be used alone or in combination of two or more. The copolymerization ratio of these other radically polymerizable monomers varies depending on the kind of the base that can impart alkali solubility. When the radically polymerizable monomer having a hydroxyl group is a radically polymerizable monomer having a phenolic hydroxyl group, the copolymerization ratio of other radically polymerizable monomers is such that the radically polymerizable monomer having a phenolic hydroxyl group and other When the total amount of the radical polymerizable monomer is 0 to 30% by weight, more preferably 5 to 20% by weight. When the radically polymerizable monomer having a hydroxyl group is a radically polymerizable monomer having a carboxyl group, the copolymerization ratio of other radically polymerizable monomers is such that the radically polymerizable monomer having a carboxyl group is radically polymerizable with other radically polymerizable monomers. When the total amount of the monomers is 0 to 90% by weight, more preferably 10 to 80% by weight. The copolymerization ratio of these other radically polymerizable monomers is such that when the ratio exceeds the aforementioned ratio for a radically polymerizable monomer having a hydroxyl group or a carboxyl group, alkali developability may be insufficient. As shown in the above-mentioned soluble resins, 'particularly desirable ones are poly-para-basic ethylene, o-methyl-p-hydroxystyrene / p-hydroxystyrene copolymer, styrene / p-hydroxystyrene copolymer, styrene / methacrylic acid / Methylpropane-12- (8) (8) 200407667 propylene glycol acrylate copolymer, styrene / fluorenyl acrylic acid / propylene glycol methacrylate / tricyclic [5 · 2_ 1 · 〇2'6] Decane-8-based fluorenyl acrylate copolymer, methacrylic acid / fluorenyl propylene oxide acrylate / tricyclic [5, 2 — 1 · 〇2, 6] decane-8-based methacrylate% butyl Diene copolymer, styrene / fluorenyl acrylic acid / glycidyl methacrylate / tricyclo [5 · 2.0 · 2,6] decane-8-methacrylate / cyclohexylmaleimide / 1,3_ butadiene copolymer and so on. Alkali-soluble resins (a) are synthesized with solvents such as alcohols such as methanol, ethanol, and dipropanol; ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; ethylene glycol monomethyl ether and ethylene glycol monoether Glycol alkyl ethers such as diethyl ether; Glycol alkanoate acetates such as methyl lysin acetate, ethyl lysone acetate; diethylene glycol monomethyl ether, diethylene glycol Diethylene glycol ethers such as monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl methyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether Propylene glycol monoalkyl ethers, etc .; propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and the like; propylene glycol methyl ether propionate, propylene glycol ether propionic acid Esters, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, and other propylene glycol alkyl ether propionates; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-mer -4-Ketones such as methyl-2-pentanone; and methyl acetate, ethyl acetate, acetic acid Ester, butyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, Butyl glycol acetate, ethyl lactate, ethyl lactate-13-200407667 r 〇) ester, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate Esters, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate , Methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, Propoxy butyl acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy Propyl propionate, 2-ethoxy butyl propionate, 2-butoxy Methyl propionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propyl propionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like. The amount of these solvents used is preferably 20 to 1,000 parts by weight for 100 parts by weight of the reaction raw material. As the polymerization initiator used in the production of the alkali-soluble resin (a), a general radical polymerization initiator can be used, such as 2,2, -azobisisobutyronitrile, 2,2'-azobis · (2,4- Dimethylvaleronitrile), 2,2'-Azobis- (4-Methoxy-2,4-dimethylvaleronitrile) and other azo compounds; Phenylhydrazone-14- (10) ( 10) Organic peroxides such as 200407667, lauryl peroxide, third butyl pertrimethyl vinyl ester, 1, 1′-bis- (third butyl peroxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide can be used together with a reducing agent as a redox initiator. (A) Another method for synthesizing an alkali-soluble resin used in the present invention is to obtain, for example, a phenolic hydroxyl group or a carboxyl group corresponding to a radically polymerizable monomer containing a phenolic hydroxyl group or a carboxyl group. After the monomer alone polymer of the monomer protected by an appropriate protecting group or the copolymer of the equivalent monomer and other monomers is synthesized, it is deprotected by a reaction such as hydrolysis to impart alkali solubility. Among such alkali-soluble resins, it is particularly preferable to use polyparahydroxystyrene, o-methylparahydroxystyrene / parahydroxystyrene copolymer, styrene / parahydroxystyrene copolymer, and the like. The (a) alkali-soluble resin used in the present invention can be used, for example, one having a transparency or a softening point corrected by a treatment such as hydrogenation. (A) The polystyrene equivalent weight average molecular weight of the (a) alkali-soluble resin used in the present invention is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 50,000, and particularly preferably 5, 〇〇〇〜30,000。 The range. Within this range, a radiation-sensitive resin composition having excellent balance among pattern shape, resolution, developability and heat resistance, developability and sensitivity can be provided. Follow up on some of the towels that are soluble, such as the raw tree fl. Examples include marukarinker-M, PHM-C (the above is made by Jiushan Petrochemical Co., Ltd.), VP_ 1 500 (Day -15- (11) (11) 200407667 Made by Ben Tso (shares)) and other hydroxystyrene (co) polymers or their partial hydrides. The (a) alkali-soluble resin of the present invention can be used alone, for example, as a condensation resin such as a phenol resin or in combination with the aforementioned alkali-soluble resin. A phenol resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst . Examples of phenols used at this time include phenol, o-cresol, m-phenol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol. Phenol, 2, xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol , 3,4,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, naphthol, / 3- Naphthol, bisphenol A, dihydroxybenzoate, gallic vinegar, o-nitrophenol, m-nitrophenol, p-nitrophenol, o-chlorophenol, m-chlorobenzene, p-chlorophenol, etc. Among these, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2 '3' 5-trimethylol Phenol, resorcinol, 2-methylresorcinol, etc. Some phenylhydrazones can be used alone or in combination of two or more. Examples of aldehydes that are polycondensed with the phenols include formaldehyde, p-formaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, α-phenylpropanal, -phenylpropanal, o-hydroxybenzaldehyde, and m-hydroxybenzaldehyde , P-hydroxybenzaldehyde, o-chlorobenzaldehyde, 'm-benzaldehyde, p-chlorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methyl Benzaldehyde, p--16- (12) (12) 200407667 fluorenylbenzaldehyde, o-ethylbenzaldehyde, m-ethylbenzaldehyde, p-ethylbenzoic acid, p-n-butyraldehyde, furfural, 1-naphthaldehyde, 2-naphthoic acid, 2-hydroxy-1-naphthyl ferment, etc. Compounds that generate aldehydes during the reaction can be used in the same manner as the aldehydes described above. Of these, formaldehyde is particularly suitable. These aldehydes and aldehyde-forming compounds can be used alone or in combination of two or more. For aldehydes, phenols are usually used. 7 ~ 3 moles, more preferably 〇. 7 to 2 moles. As the acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, p-benzenesulfonic acid, formic acid, acetic acid, and oxalic acid can be used. When the amount is 1 mol for phenol, it is ideal to use lx 10.4 to 5x 10.1 mol. During the polycondensation reaction, water is usually used as the reaction medium. However, when the phenols used in the polycondensation reaction are not dissolved in an aldehyde solution in the aqueous solution, and a heterogeneous system is formed at the beginning of the reaction, a hydrophilic organic solvent may be used as the reaction medium. Solvents used at this time include, for example, alcohols of methanol, ethanol, and butanol; cyclic ethers of tetrahydrofuran and dioxane. When the reaction medium is used in an amount of 100 parts by weight with respect to the reaction raw material, it is desirable to use 20 to 400 parts by weight. The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials. It is usually 10 ～ 200 ° C. After the completion of the polycondensation reaction, in order to remove unreacted raw materials, catalysts, and reaction media in the system, the temperature is generally raised to 130 ° C to 230 ° C or higher, and the volatile components are distilled off under reduced pressure to recover the phenolic resin. Among these phenol resins, particularly preferred are m-cresol / formaldehyde polycondensate, m-cresol / p-cresol / formaldehyde polycondensate, m-cresol / 2 '3-xylenol / formaldehyde polycondensate, and m-cresol. / 2,4-xylenol / formaldehyde polycondensate, m-cresol / 2,5-xylenol / formaldehyde polycondensate, and the like. -17- (13) 200407667 The polystyrene-equivalent weight-average molecular weight of the phenolic resin (hereinafter referred to as "M w") is preferably in the range of 2,000 to 2000, and more preferably 3,000. Range of ~ 15,000. When the Mw exceeds 20,000, it may be difficult to uniformly apply the composition to the wafer, and the developability and sensitivity may decrease. 1,2-quinonediazide compound (b) As the 1,2-quinonediazide compound used in the present invention, a compound having radiation can be used. For example, 1, f benzoquinonediazidesulfonate, 1,2-naphthoquinonediazidesulfonate, 1,2-benzoquinonediazidesulfonamide, which have the function of generating carboxylic acids by 1,2-ray irradiation. , 1,2-naphthoquinonediazidesulfonamide and the like. Specific examples of these include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, and 2,3,4-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxy 1,2-naphthoquinonediazide sulfonate such as benzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4,4 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3'-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4, tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,2'-tetrahydroxy-4'-form Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2'-tetrahydroxy-4'-fluorenylbenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2, 3, 4, 4 '_Tetrahydroxy_3'_methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid-18- (14) 200407667 ester, 2,3,4,4'-tetrahydroxy -3'-methoxybenzophenone-1,2-naphthoquinonediazide, 5-sulfonate and other 1,2-naphthoquinonediazide sulfonate; 2 , 3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2', 6'-pentahydroxydibenzene 1,2-naphthoquinonediazidesulfonate of pentahydroxybenzophenone, such as methanone-1,2-naphthoquinonediazide-5_sulfonate; t 2,4,6,3 ', 4 '5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4 · sulfonate, 2,4,6,3', 4'5'-hexahydroxybenzophenone-1, 2-naphthoquinonediazidesulfonate, 3,4,5,3 ', 4'5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 3,4 , 5,3 ', 4'5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc. Nitrosulfonate: Bis (2,4_dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,4_dihydroxyphenyl) methane-1,2_ Naphthoquinonediazide-5-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2 Naphthoquinonediazide-5-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2 Naphthoquinonediazide-5-sulfog ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1- Tris (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonate, bis (2 (2, bis (2 3,4_trihydroxyphenyl) methane d, 2-naphthalene Quinonediazide-4-sulfonate, bis4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-3,4-trihydroxyphenyl) Propane-1,2-naphthoquinonediazide-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonate Acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1, 1,1-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenyl-19- (15) (15) 200407667 propane-1,2-naphthoquinonediazide-5-sulfonate Acid ester, 4, 4,-[1_ [4- [1- [4 -hydroxyl Phenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthyldiazide-4-sulfonate, 4,4 '-[1- [4- [1- [4-Hydroxyphenyl] -1-fluorenylethyl] phenyl] ethylene] bisfluorene-1,2-naphthoquinonediazide-5-sulfonate, bis (2,5-dimethyl 4-hydroxyphenyl) -2-hydroxyphenylmethane1,2-naphthoquinonediazidesulfonic acid vinegar, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3,, 3 '· tetramethyl-1,1, -spirobiindene-5,6,7,5 ,, 6,7, -hexanol-1,2-naphthoquinonediazide-4-propanoate, 3,3,3 ', 3'-tetramethyl-1, fluorene , 5 ', 6', 7'-hexanol-1,2-naphthalene II diazide-5-propanoate, 2,2,4-trimethyl-7,2 ', 4' · trihydroxysulfonic acid 1,2-naphthoquinonediazide-4-sulfonate, 2,2,4-trifluorenyl-7,2 ', 4'-trihydroxysulfane-1,2-naphthoquinonediazide 1,2-naphthoquinonediazide sulfonate of (polyhydroxyphenyl) alkane such as -5-sulfonate. In addition to these compounds, J. Kosar, Light-Sensitive Systems " 339 ~ 352 (1965), John Wiley & Sons (New York) or W. S. De Fores, Photoresist ’’ 50 (1975) McGraw-Hill, Inc. (N York) The 1,2-quinonediazide compound. These can be used in the form of forming a condensate by reacting with a part or the whole of the alkali-soluble resin (a). Of these 1,2-quinonediazide compounds, 1,1,1-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone is preferable. Diazide sulfonate, 1,1,1-tris (2,5-dimethyl-4-hydroxyphenyl) -3 -phenylpropane-1,2-naphthoquinonediazide-4-mine acid Vinegar, 4 '4'-[1- [4- [1- [4-Ethylphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide- 4-sulfonate, 4,4 '-[-20- (16) (16) 200407667 [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1, 2 · Naphthoquinonediazide-5-sulfonate, 2,2,4-trimethyl-7,2 ', 4'-trihydroxysulfane-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxysulfane-1,2-naphthoquinonediazide-5-sulfonate, 1,1' 1-tri (p Hydroxyphenyl) ethane-1,2-naphthoquinonediazide · 4 · sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5 -Sulfonates and the like. The above 1,2-quinonediazide compounds can be used alone or in combination of two or more. (b) The amount of the 1,2-quinonediazide compound added to (a) 100 parts by weight of the alkali-soluble resin is 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight. When the added amount is less than 5 parts by weight, the pattern may not be easily formed, and when it exceeds 100 parts by weight, development with a developing solution composed of an alkaline aqueous solution may be difficult. In the composition of the present invention, a sensitizer may be added to the 1,2-quinonediazide compound in order to improve the sensitivity. Sensitizers include, for example, 2H-pyridine- (3,2-b) · 1,4-oxazine-3 (4H) -ones, and 10H-pyridine- (3,2-b)-(1,4) -Benzothiazines, ureazols, hydantoin, malondicarbazone, glycine anhydride, 1-hydroxybenzotriazoles, urea ureas, cis butane diamines and the like. When these sensitizers are used in an amount of 1,000 parts by weight with respect to the 1,2-quinonediazide compound, it is preferably 100 parts by weight or less, and more preferably 4 to 60 parts by weight. (c) Solvents with a boiling point of 180 ° C or higher at normal pressure The solvent of the present invention is a solvent with a boiling point (hereinafter simply referred to as "boiling point") of 1 80 ° C or higher (hereinafter referred to as "high The boiling point is -21-(17) (17) 200407667 medium "). The boiling point of the high boiling point solvent is preferably above 200 ° C. The upper limit of the boiling point of the high-boiling-point solvent is not particularly limited as long as it is a radiation-sensitive resin composition for forming the organic EL insulating film for inkjet of the present invention, and the organic EL insulating film can be manufactured by the inkjet method, but the resin From the viewpoint of operability of the composition preparation step and the manufacturing step of the organic EL insulating film, the boiling point is 29 ° C or lower, preferably 2 80 ° C or lower, and the liquid is of a lower viscosity at normal temperature (20 ° C). High boiling point solvents are preferred. Therefore, the desirable boiling point range of the high boiling point solvent of the present invention is specifically 180 to 290 ° C, and more preferably 200 to 280 ° C. High boiling point solvents include, for example, diethylene glycol dialkyl ether solvents represented by the formula R ^ O (CH2CH20) 2-R2 (R1 and R2 are independent alkyl groups having 2 to 10 carbon atoms); -〇 (〇112 (: 1120) 3-three 4 (three and four are independent alkyl groups of 1 to 10 carbon atoms) triethylene glycol dialkyl ether based solvent; Formula R5-〇 ( CH2CH20) i-R6 (R5 and R6 are independent alkyl groups of 1 to 10 carbon atoms, i is an integer of 2 to 30) polyethylene glycol dialkyl ether system solvent; with the formula r7_0CH (CH3) CH20- R8 (R7 and R8 are independent radicals with a carbon number of 2 to 10) propylene glycol dioxane ether type solvents; ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, etc. Ethylene glycol monoalkyl ethers; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-propyl ether -22- (18) (18) 200407667 Diethylene glycol monoalkane ethers such as ethers, diethylene glycol mono-n-butyl ether; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate Diethylene glycol monoalkyl ether acetates, etc .; Propylene glycol alkyl ether acetates, such as propylene glycol butyl ether acetate; ethylene glycol monophenyl ether acetate, diethylene glycol diethyl ether, benzyl ether, and dihexyl ether Other ethers; 1-octanol, 1-nonanol, benzyl alcohol; alcohols such as acetonitrile, acetone, isophorone; carboxylic acids such as hexanoic acid, capric acid; butyl lactate, benzene Ethyl formate, butyl benzoate, diethyl oxalate, diethyl maleate, di-n-butyl maleate, triacetin, tri-n-butyl fumarate, dimethyl benzoate, Esters of diethyl benzoate, di-n-propyl benzoate, di-isopropyl benzoate, di-n-butyl benzoate, isoamyl salicylate, r-butyrolactone, ethylene carbonate, propylene carbonate, etc. Based solvents, etc. The ideal high boiling point solvents of the present invention include, for example, ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and Propylene glycol, propylene glycol butyl ether acetate, diethylene glycol di-n-butyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol Dimethyl ether, propylene glycol di-n-butyl ether, butyl lactate, etc. The high boiling point solvent can be used singly or in combination of two or more. The amount of the high boiling point solvent is based on (a) alkali-soluble resin 100 weight -23- (19 ) (19) 200,407,667 parts by weight, usually 10 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 10,000 to 2,000 parts by weight. In the present invention, the use of high The boiling point solvent has the following effects: (1) When the image pattern is formed by the inkjet method, the radiation-sensitive resin composition for forming the organic EL insulating film for inkjet is ejected, and after removing the solvent, it is heated to form a grid-shaped organic EL display element. Insulating film, at this time, moderately suppresses the evaporation rate of the high-boiling-point solvent, and the discharged resin composition does not change drastically when the solvent is removed or when heated. Therefore, the working efficiency when forming the insulating film of the organic EL display element is improved. (2) When the organic EL insulating film is formed by the inkjet method, the radiation-sensitive resin composition for forming the organic EL insulating film gradually becomes thick due to the evaporation of the solvent. If the boiling point of the solvent is low, the viscosity changes greatly. The resin composition discharged at the beginning and the end of the organic EL insulating film has a large change, which affects the coating of the organic EL insulating film. The use of a high boiling point solvent can suppress the reduction of this viscosity change and make the desired organic EL insulating film. Easy to apply. (3) Preventing the inkjet head from ejecting the radiation-sensitive resin composition for forming the organic EL insulating film from being blocked by the drying of the composition, thereby preventing flying flexion when the composition is ejected, and ensuring good linearity 'Improve the utilization efficiency of the radiation-sensitive resin composition for forming an organic EL insulating film and the cleaning efficiency of an insulating film manufacturing apparatus for an organic EL display element. In the present invention, a solvent having a boiling point of 180 ° C or lower (hereinafter referred to as a "low boiling point solvent") can be used with a high boiling point solvent. -24- (20) (20) 200407667 Such low boiling point solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethers; glycol alkyl ether acetates such as fluorenyl cellulose solvin acetate, ethyl cellulose lysin acetate, etc .; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoether Ethylene glycol monoalkyl ether acetates such as propyl ether acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; etc. · Diethylene glycol dimethyl ether, tetrahydrofuran, etc. Ethers; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ether, propylene glycol propyl ether, and propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and other propylene glycol Monoalkyl ether acetates; Alcohols such as methanol and ethanol; Aromatic hydrocarbons such as toluene and xylene; Methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, Ketones such as 2-heptanone, ^ heptanone, methyl isopentanone; and methyl acetate, ethyl acetate Ester, propyl acetate, butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-hydroxypropionate, 2-hydroxypropionate Ethyl ester, 2-hydroxy-2-methyl propionate, 2-hydroxy-2-methyl propionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate Ester, propyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 2-hydroxy-3-methyl butyrate-25- (21) (21 200407667, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxypropyl acetate Ester, methyl propoxyacetate, ethyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate 'methyl 2-butoxypropionate, ethyl 2-butoxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethoxylate F-esters such as ethyl propionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, methyl butoxypropionate, and ethyl 3-butoxypropionate. Among these solvents, diethylene glycol, propylene glycol monoalkyl ether acetate, propylene glycol alkyl acetate, and ester are more preferable, and diethylene glycol dimethyl ether and diethylene glycol ethyl methyl are particularly preferable. Ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate. These low boiling point solvents may be used alone or in combination of two or more. 0 The proportion of the low-boiling solvent is based on the total amount of the high-boiling solvent and the low-boiling solvent. It is usually 50% by weight or less, and preferably 30% by weight or less. In this case, when the proportion of the low-boiling-point solvent exceeds 50% by weight, the effect of using the high-boiling-point solvent may be affected. In the radiation-sensitive resin composition for forming an organic EL insulating film of the present invention, a compound containing at least one of (d) a compound containing two or more epoxy groups and (e) a melamine compound is used from the composition The formed insulating film is particularly resistant to the light used in the formation of the cathode of a passive liquid crystal display element. -26- (22) (22) 200407667 Resistive peeling liquid is particularly high, and the insulating film is even in the resistive peeling liquid It will not peel off. (d) Compounds containing two or more epoxy groups in the molecule (d) Compounds containing two or more epoxy groups in the molecule include, for example, Epycoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 Bisphenol A type epoxy resins, such as 8 28 (the above is made of oiled Shell Epox (stock)), bisphenol F-rings such as Epycoat 8 07 (the above is made of oiled shell Epox (stock)) Oxygen resin commercially available products, phenol novolac epoxy such as Epycoat 152, 154 (the above are manufactured by Shell Chemicals Epox Co., Ltd.), EP PN 2 01, 2 0 2 (the above are manufactured by Japan Chemical Co., Ltd.) Resin commercially available products, such as EOCN-102, 103S, 1 04S, 1 020, 1 025, 1 027 (the above are manufactured by Nippon Kayaku Co., Ltd.), Epycoat 180S75 (the above are made by Petrochemical Shell Epox (Co. A commercially available formaldehyde formaldehyde epoxy resin, CY-175, 177, 179 (above are made by Ciba Gaigy (Company)), ERL-4234, 4299, 422 1, 4206 (above are U. C. C (stock) system, Shodine 5 09 (Showa Denko (stock) system) _ Aldalite CY-182, 192, 184 (above are made by Ciba Geigy (company)), Epyclone 200, 400 (above are Dainippon Ink (stock) )) Cycloaliphatic epoxy resin commercially available products such as' Epycoat 871, 872 (the above are made by Petrochemical Shell Epox (stock)), ED-5661, 5662 (the above are made by Ceraneedscoating (stock)), Epolite 1 00MF , 200E, 400E (the above are Kyoeisha Oil Chemical Industry Co., Ltd.), Epyol TMP (Japan Oil Co., Ltd.) and other aliphatic polyglycidyl ether commercially available products. Among these compounds, bisphenol A epoxy resin, bisphenol F epoxy resin, and resole phenolic ring can be used from the viewpoint of controlling the developability and the shape of the reflective irregularities. 27- (23) (23) 200407667 Oxygen resins, aliphatic polyglycidyl ethers. _ In addition to the aforementioned epoxy compounds, compounds such as glycidyl ethers of bisphenol A and bisphenol F can also be used. When the composition of the present invention contains these (d) compounds containing two or more epoxy groups in the molecule, the addition amount is 1,000 parts by weight or less with respect to (a) the alkali-soluble resin, It is more preferably 1 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight. A hardened product composed of a composition containing two or more epoxy groups in the molecule in this range is excellent in heat resistance or adhesion. When the addition amount of the compound containing two or more epoxy groups is less than 1 part by weight, the curing reaction cannot proceed sufficiently, and a cured film composed of such a composition may have poor heat resistance and solvent resistance. When it exceeds 100 parts by weight, the softening point of the entire composition decreases, and the shape is difficult to maintain during the heat treatment when forming a pattern for a light-diffusing reflection film. In the aforementioned (a) alkali-soluble resin, when an epoxide-containing portion g and a monomer of a comonomer are used, it may be referred to as a "compound containing two or more epoxy groups in the molecule", but it is equivalent to ( d) the components are different. (e) Melamine compound (e) The melamine compound used in the present invention is a compound represented by the following general formula (1). -28- (24) 200407667 RVR1.
(式中R R可相同或不同，分別爲氫原子或-CH2〇R基 ，R係氣原子或Ci〜C6之院基）。 · 這種化合物例如有六淫甲基三聚氨胺、六經丁基三聚氯胺 、部分羥甲基化二聚氰胺及其烷基化物等。 追種化5物巾售TO例如有Simel 300、301、303、370、325 、325、 701、 266、 267、 238、 1141、 272、 202、 1156、 1158( 以上爲二井 Sianzmid (股）製）、Nikalac Mx-750、-032、-706 、-708、·40、-31、-45、Nikalac Ms_ll、-001、Nikalac Mw-30 、-22(以上爲三和Chemical公司製）等。 本發明之組成物含有（e )成分時，其添加量係對於（a ) 鹼可溶性樹脂1 0 0重量份時，添加1 〇 〇重量份以下，更理想爲1〜 1〇〇重量份，特別理想爲5〜50重量份。此範圍之添加量可形成 良好形狀之粗糙面，可得到對於鹼具有適當之溶解性之組成物 其他之添加劑 本發明之有機EL絕緣膜形成用輻射敏感性樹脂組成物中 -29 - (25) (25)200407667 ’在不影響本發明之目的的範圍內，可添加其他之添加劑，例 如增感劑、界面活性劑、接著助劑、保存安定劑、消泡劑等。 上述增感劑係爲了提高本發明之有機EL絕緣膜形成用輻 射敏感性樹脂組成物對輻射線之感度。增感劑例如有2H-吡啶-(3，2-b ) ·1，4-噁嗪-3 ( 4H)-酮類、10H-吡啶-(3，2-1〇_ (1，4 )-苯並噻嗪類、脲唑類、乙內醯脲類、丙二醯脲類、甘 氨酸酐類、1 -羥基苯並三唑類、阿脲類、順丁醯二胺類等。這 些增感劑之使用量係對於（b ) 1，2 -醌二疊氮化合物1 〇 〇 ¥ 量份時，理想爲使用1 〇 〇重量份以下，理想爲1〜5 0重量份。 前述界面活性劑係改良塗怖性、例如條紋或乾燥塗膜形成 後之輻射線照射部之顯影性。 界面活性劑例如有聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚 氧乙烯油醚之聚氧乙烯烷醚類、聚氧乙烯辛基苯醚、聚氧乙烯 壬基苯醚之聚氧乙烯芳醚類、聚乙二醇二月桂酸酯、聚乙二醇 二硬脂酸酯之聚乙二醇二烷酯等之非離子系界面活性劑；F T(^ EF301、303、352(新秋田化成（股）製）、Mega fa c F171、 172、173(大日本油墨（股）製）、Florad FC430、431(住友 3M (株）製）、Asahi Guard AG710、Surflone S-3 82、SC-101 、102、103、104、105、106(旭硝子（股）製）等之氟系界面 活性劑：有機矽氧烷聚合物 KP341 (信越化學工業（股）製） 、丙烯酸系或甲基丙烯酸系（共）聚物p〇iyflow Νο.57、95( 共榮公司化學（株）製）等。這種界面活性劑之配合量係對於 組成物之固形份時’理想爲配合2重量份以下’更理想爲1重量 -30- (26) (26)200407667 份以下。 上述接著助劑可用於改良由本發明之有機EL絕緣膜形成 用輻射敏感性樹脂組成物所形成之絕緣膜與基板之密著性。 這種接著助劑可使用官能性矽烷偶合劑，例如具有羧基、 甲基丙烯醯基、異氰酸酯基、環氧基等之反應性取代基之矽烷 偶合劑。具體例有三甲氧基矽烷基苯甲酸、r -甲基丙烯醯氧基 丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基 矽烷、r·異氰酸酯基丙基三乙氧基矽烷、r-縮水甘油氧基胃 基三甲氧基矽烷、/3-(3，4-環氧基環己基）乙基三甲氧基矽 院等。這種界面活性劑之配合量係對於組成物之固形份1 0 0重量 份時，理想爲配合1 5重量份以下，更理想爲1 0重量份以下。 本發明之有機EL絕緣膜形成用輻射敏感性樹脂組成物係 依據使用的目的可採用適當之固形份濃度，例如固形份濃度可 爲10〜40重量％ 。 如上述調製之組成物溶液係使用孔徑〇.2μιη之微孔過濾j 等過濾後，再使用。 有機EL顯示元件之絕緣膜的形成方法 本發明之形成有機EL顯示元件之絕緣膜的方法，其 特徵係至少含有下述步驟， (1 )以噴墨裝置基板表面上形成上述之輻射敏感性 樹脂組成物之塗膜的步驟， (2 )對於形成後之塗膜之至少一部分照射輻射線的 步驟， -31 - (27) (27)200407667 (3 )顯影步驟。 (1 )以噴墨裝置基板表面上形成上述之輻射敏感性樹脂組 成物之塗膜的步驟 本發明之有機EL絕緣膜形成用輻射敏感性樹脂組成物係 以噴墨裝置塗佈在底層基板表面上’理想爲藉由預烘烤去除溶 媒，可形成塗膜。 預烘烤之條件係因各成分之種類、使用比例等而異，理想 爲60〜130。。，〇·5〜15分鐘之條件。· 預烘烤後之膜厚可藉由有機EL絕緣膜形成用輻射敏感性 樹脂組成物之固形份濃度或塗怖條件得到所要之數値，例如 0.2 5 〜4 μιη 0 (2 )對於形成後之塗膜之至少一部分照射輻射線的步驟 接著對於形成後之塗膜之至少一部分照射輻射線。此時例 如經由所定之圖案之光罩，照射輻射線，然後對於形成後之塗 膜之至少一部分照射輻射線。此處所使用之放射線例如有g g (波長436nm) 、i線（波長365nm)等之紫外線、KrF準分子 雷射等之返紫外線、问步輪射射線等之X光線、電子射線等之 帶電粒子線。這些當中較理想爲g線及i線。 這些輻射線之曝光量通常爲50〜10，〇〇〇j/m2、理想爲1〇〇 〜5，000J7m2 〇 (3 )顯影步驟 照射輻射線後，使用顯影液進行顯影處理，除去輻射線之 -32- (28) (28)200407667 照射部分可得到所要之圖案。此處使用之理想的顯影液可使用 例如將氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨 水等之無機鹼類；乙胺、正丙胺等之一級胺類；二乙胺、二正丙 胺等之二級胺類；三乙胺、甲基二乙胺等之三級胺類；二甲基乙 醇胺、三乙醇胺等之醇胺類；四甲基氫氧化銨、四乙基氫氧化銨 、膽鹼等之四級銨鹽或吡咯、哌啶、1，8 -二氧雜二環-(5.4,0 )-7-十一烯、1，5_二氧雜二環-(4.3.0) -5-壬烷等之環狀胺溶 解於水中之鹼水溶液。該顯影液中可添加適量之水溶性有機# 媒、例如甲醇、乙醇等之醇類或界面活性劑。溶解本發明之組 成物之各種有機溶媒也可作爲顯影液。 顯影方法可利用攪拌法、浸漬法、搖動浸漬法等。 顯影處理後，對於形成圖案的膜例如可藉由流水洗淨之洗 淨處理。 再以高壓水銀燈等之輻射線全面照射，也可分解處理該膜 中所殘留之1，2 -醌二疊氮化合物。 | 然後，此膜使用加熱盤•烤箱等之加熱裝置加熱進行硬化 處理爲佳。此硬化處理之加熱溫度例如15〇〜280 °C，若在加熱 盤上進行燒結時，加熱時間爲5〜3 0分鐘，若在烤箱內進行燒結 時，加熱時間爲30〜90分鐘。 有機EL顯示元件之製造 本發明之有機EL元件具備如前述所形成之絕緣膜。 本發明之有機EL元件例如由下述方式製造。 -33- (29) (29)200407667 在玻璃基板上以濺鍍形成I T ◦等之透明電極，其上形成 絕緣膜圖案。接著例如以鹽酸系蝕刻劑鈾刻I τ ◦膜，將光阻 膜剝離使透明電極形成圖案，例如形成長條狀之圖案。在具有 形成此圖案之透明電極之基板上，如上述方法形成本發明之絕 緣膜的圖案。接著形成電子輸送層、倒圓錐狀之陰極分隔牆， 然後依序形成電洞輸送層、有機EL發光層、陰極層。 電洞輸送層例如可使用如CuPc、H2Pc之酞菁系材料、或 芳香族胺。有機EL發光材料可使用在如Alq3、BeBq3之基材 體上摻雜喹吖酮或香豆素之材料，即所謂的低分子有機EL材 料，或聚苯乙烯系、芴系之高分子有機EL材料。陰極材料可 使用 Mg-Al、Al-Li、Al-Li20、Al-LiF 等。 其次以環氧樹脂等之封裝材料將中空結構之SUS罐與上述 基板後，組裝成模組可作爲有機EL元件。 【實施方式】 [實施例] 1 以下藉由實施例詳細說明本發明，但是本發明不受這些y 施例所限制。下述所測定之分子量係以日本東曹（股）製GPe 色譜分析儀HLC-8020之聚苯乙烯換算重量平均分子量，^ 爲「重量％」。 合成例1 (樹脂a-1之合成） 將第二丁氧基苯乙嫌176g ( O.lmol)及偶氮雙丁腈 5.8g ( 〇. (Mmol )投入具備冷卻管、攪拌機及溫度計之燒 -34- (30) (30)200407667 瓶內，添加丙二醇單甲醚2 5 0ml溶解之，以75 °C聚合4小 時。將5重量％硫酸水溶液5 0g與製得之聚第三丁氧基苯 乙烯溶液混合，以100 °C進行水解反應3小時。接著添加丙 二醇單甲醚乙酸酯5 00ml後，使用去離子水1 000ml洗淨3 次。其後將有機層減壓去溶劑，真空乾燥得到Mw24， 〇〇〇之鹼可溶性樹脂（聚羥基苯乙烯）。此鹼可溶性樹脂 爲「樹脂a -1」。 合成例2 (樹脂a-2之合成） 將間甲酚 57g ( 0.6mol )、對甲酚 38g ( 0.4mol ) 、37 重量％甲醛水溶液75.5g (甲醛〇.93mol)、草酸二水合物 0.63g ( 0.00 5 mol )、甲基異丁酮26 4g投入具備冷卻管、 攪拌機及溫度計之燒瓶內，然後將燒瓶浸漬於油浴中，將 反應液回流、攪拌下進行縮聚4小時。接著以3小時使油浴 溫度上升，然後燒瓶內減壓至3〇〜50mmHg除去揮發成分 ，將熔融之樹脂降至室溫回收。此樹脂溶解於醋酸乙酯中 ，使樹脂成分成爲3 0 %後，添加此溶液重量之1 . 3倍量之 甲醇與0.9倍量之水，攪拌後放置。接著取出分離成兩層 之下層予以濃縮、乾燥得到Mw8，000之鹼可溶性樹脂（ 酚醛樹脂）。此鹼可溶性樹脂爲「樹脂a-2」。 合成例3 (共聚物（a-3 )之合成） 將2，2’-偶氮雙（2，4_二甲基戊腈）8重量份及二乙 -35- (31) (31)200407667 二醇乙基甲醚2 2 0重量份投入具備冷卻管及攪拌機之燒瓶 內。接著添加苯乙烯10重量份、甲基丙烯酸20重量份、甲 基丙烯酸環氧丙酯4 0重量份、甲基丙烯酸酯1 5重量份及環 己基順丁醯二胺1 0重量份，再以氮取代後，添加1，3 - 丁 二烯5重量份，開始緩慢攪拌。使溶液溫度上升至70 °C， 此溫度保持4小時得到含有共聚物「a-3」之聚合物溶液。 製得之聚合物溶液之固形份濃度爲3 1.0重量％ 、Mw8， 200 〇 實施例1 混合（a)成分之樹脂a-1 100重量份，（b)成分之1 ，1，3·三（2，5·二甲基-4-羥苯基）-3-苯基丙烷（lmol )與1，2-萘醌二疊氮-5-磺酸氯（1.9mol)之縮合物（1， 1，3-三（2，5-二甲基-4-羥苯基）-3-苯基丙烷-1，2-萘 醌二疊氮-5-磺酸酯）30重量份，（c)成分之二乙二醇單 丁醚醋酸酯400重量份及界面活性劑Megafac F172 (大日 本油墨（股）製）〇.〇1重量份後，以二乙二醇甲基乙醚稀 釋、溶解使整體之固形份濃度成爲20%後，以孔徑〇. 2 μπι 之薄膜過濾器過濾調製本發明之組成物溶液。 絕緣膜之形成 使用噴墨裝置將上述組成物塗佈於玻璃基板上’形成 1μ m之膜厚後，在加熱板以8〇°C進行1·5分鐘預烘烤’形 -36- (32) (32)200407667 成塗膜。然後經由30μιη之絕緣膜圖案光罩以Canon (股 )製分析儀PLA-501F進行曝光後，以四曱基氫氧化銨 2.3 8重量％水溶液進行25 °C、1分鐘顯影。然後以水進行 流水洗淨，乾燥在晶圓上形成圖案。此圖案再於烤箱中以 2 3 0 °C加熱6 0分鐘，形成絕緣膜圖案。 (1 )感度之評價 如上述調查可形成30μηι之圖案之最低曝光量。此數 値如表1所示。此數値爲200mJ/cm2以下時，輻射敏感性良 好。 (2 )斷面形狀之評價 以掃描型電子顯微鏡（（股）日立製作所製、形式「S_ 42 00」）硏究分析上述形成之絕緣膜圖案之斷面形狀，測定斷 面形狀之圓錐角（圖案之斷面形狀之底邊與邊緣部之切線所g 的角，以下相同）。結果如表1所示。此數値爲50°以下時’表 示圖案之斷面形狀良好。 (3 )顯影殘留之有無 在蒸鍍ITO之玻璃基板上與上述相同形成絕緣膜圖案後’ 藉由以下2種方法確認顯影殘留之有無。 (1)使用 Green lamp ((股）Funatek公司製）以目視觀 察0 •37- (33) (33)200407667 (2 )使用掃描型電子顯微鏡（（股）日立製作所製、形式 S-4200」）以40，〇〇〇倍觀察。 觀察結果如表1所示。 (4 )耐熱性之評價 如上述形成絕緣膜時，於烘箱中以23 0 °C加熱處理60 分鐘之前後之膜厚之變化率如表1所示。此値之絕對値在 加熱前後爲5%以內時，評價爲耐熱性良好。 ® (5 )耐溶劑性之評價 將上述形成之絕緣膜圖案浸漬於溫度控制爲70 °C之二甲_ 亞硕中2〇分鐘後，測定因浸漬所產生之膜厚變化率。結果如_ i 所示。此値之絕對値在5 %以內時，評價耐溶劑性良好。 (6 )耐鹼性之評價 將上述形成之絕緣膜圖案浸漬於溫度控制爲25 °C之1 % NaOH水溶液中2〇分鐘，測定浸漬所產生之膜厚變化率。結果 如表1所示。此値之絕對値在5 %以內時，評價耐鹼性良好。 (7 )噴墨塗佈性之評價 使用噴墨裝置將上述組成物塗佈於玻璃基板上，形成1.2 μηι 之膜厚後，在加熱板上以8〇°C預烘烤1.5分鐘形成塗膜。使用接 觸式膜厚測定裝置a -step ( Tencol Japan (股）製）以測定長2 -38- (34) (34)200407667 ，ΟΟΟμιη ， Μ 定範圍 2 ， 000μΓη><2 ， ΟΟΟμιη 正方，領!| 定黑占數 η = 5 測定該塗膜表面之凹凸。各測定之最高部與最低部之高低差之 平均値（nm )如表1所示。此數値爲3 00nm以下時，表示噴墨 塗佈性良好。 (8 )乾固特性之評價 以固定針型微量注射器（Hamilton微量注射器、型號701、 針內徑〇. 13mm )吸引上述組成物，針朝下，微量注射器保持Ϊ 直，觀察由針前端擠壓Ιμΐ之上述組成物的狀態下，25 °C之室內 放置24小時後之組成物的狀態。結果如表1所示。針前端若無組 成物乾固時，評價爲「良好」，若有乾固、針孔阻塞時，評價 爲「不佳」。 實施例2、3、4、5 除了將實施例1之（a)成分、（b)成分及（c)成分 之種類與添加量及其他之溶媒之種類改爲如表1所示者外 ，其餘與實施例1相同調製組成物溶液，然後進行評價。 但是僅有實施例3之顯影液之四甲基氫氧化銨水溶液之濃 度改爲〇 . 4重量％ ，其他實施例與實施例1相同使用2.3 8重 量％水溶液。結果如表1所示。 表1中，各成分之添加量爲重量份，表中之「-」表示 未添加該成分。（b )成分、（c )成分及其他之溶媒之簡 稱如下。 -39- (35) (35)200407667 b-1: 1，1，3 -三（2，5 -二曱基-4-羥苯基）-3_本基 丙烷（l.Omol)與1，2-萘醌二疊氮-5-磺酸氯（l.9m〇1) 之縮合物（1，1，3 -三（2，5 -二甲基-4-羥苯基）-本基 丙烷-1，2-萘醌二疊氮-5-磺酸酯） b-2: 4，4，-〔1-〔4-〔1-〔4-羥苯基〕-卜甲基乙基〕 苯基〕亞乙基〕雙酚（1.〇 mol)與1，2_萘醌二疊氮擴 酸酯（2.0mol)之縮合物（4，4，-〔1-〔4-〔卜〔4-經本 基〕-1-甲基乙基〕苯基〕亞乙基〕雙酚-1’ 2_萘_二疊 氮-5-磺酸酯） b-3: 2，3，4-羥基二苯甲酮（l.Omol)與1’ 2-萘醒 二疊氮-5-磺酸氯（2.0 mol)之縮合物（2，3，4-羥基二本 甲酮-1，2-萘醒二疊氮-5-磺酸酯） c-1 :二乙二醇單丁醚醋酸酯 c-2 :二乙二醇單乙醚醋酸酯 c-3 :二乙二醇二甲醚 S-2 :二乙二醇乙基甲醚 實施例6、7、8、9 除了在實施例2中添加如表1所記載之（d )成分或（e )成分之種類與添加量外，其餘同實施例2相同調製組成 物溶液，然後進行評價。結果如表1所示。 (d)成分或（e)成分之簡稱如下。 d-Ι ：油化 Shellepox (股）製、「Epycoat 152」 -40- (36) (36)200407667 d-2 ：油化 Shellepox (股）製、「Epycoat 828」 e_l :三井 Sianzmid (股）製、「Simel 300」 e-2 :三井 Sianzmid (股）製、「Simel 3 03」 比較例1、2 除了在實施例2中未添加（c)成分，以S-l、S-2爲溶 劑外，其餘同實施例2相同調製組成物溶液，然後進行評 價。結果如表1所示。 由表1得知使用未添加（C )成分之組成物的實驗例， 其噴墨塗佈性差。(In the formula, R and R may be the same or different, and are respectively a hydrogen atom or a -CH2OR group, R is a gas atom or a Ci ~ C6 group). Examples of such compounds include hexamethylolamine, hexamethylenebutylmelamine, partially methylolated melamine, and alkylates thereof. For example, Simel 300, 301, 303, 370, 325, 325, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158 (these are made by Nitsui Sinzmid (stock)) , Nikalac Mx-750, -032, -706, -708, · 40, -31, -45, Nikalac Ms_ll, -001, Nikalac Mw-30, -22 (the above are manufactured by Sanwa Chemical Co., Ltd.) and the like. When the composition of the present invention contains the component (e), the amount added is 100 parts by weight or less, and more preferably 1 to 100 parts by weight when the (a) alkali-soluble resin is 100 parts by weight. It is preferably 5 to 50 parts by weight. The addition amount within this range can form a rough surface with a good shape, and can obtain a composition having an appropriate solubility in alkali. Other additives In the radiation-sensitive resin composition for forming an organic EL insulating film of the present invention, -29-(25) (25) 200407667 'As long as the purpose of the present invention is not affected, other additives such as a sensitizer, a surfactant, an adjuvant, a storage stabilizer, and an antifoaming agent may be added. The sensitizer is for improving the sensitivity of the radiation-sensitive resin composition for forming an organic EL insulating film of the present invention to radiation. Sensitizers include, for example, 2H-pyridine- (3,2-b) · 1,4-oxazine-3 (4H) -ones, 10H-pyridine- (3,2-1〇_ (1,4)- Benzothiazines, ureaazoles, hydantoin ureas, malondiurea ureas, glycine anhydrides, 1-hydroxybenzotriazoles, urea ureas, cis butane diamines, etc. These sensitizations The amount of the agent used is 100 parts by weight of the (b) 1,2-quinonediazide compound, preferably 100 parts by weight or less, and preferably 1 to 50 parts by weight. Improves paintability, such as the development of streaks or radiation-irradiated parts after the formation of a dry coating film. Surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene aryl ethers, polyethylene glycol dilaurate, polyethylene glycol distearate Non-ionic surfactants such as alkyl esters; FT (^ EF301, 303, 352 (made by Shin Akita Kasei Co., Ltd.), Mega fa c F171, 172, 173 (made by Dainippon Ink Co., Ltd.), Florad FC430, 431 (Sumitomo 3M ( ), Asahi Guard AG710, Surflone S-3 82, SC-101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants: organosiloxane polymer KP341 ( Shin-Etsu Chemical Industry Co., Ltd.), acrylic or methacrylic (co) polymer poiyflow No.57, 95 (by Kyoei Chemical Co., Ltd.), etc. The compounding amount of this surfactant is As for the solid content of the composition, it is desirable to mix 2 parts by weight or less, and more preferably 1 to 30 to (26) (26) 200,407,667 parts. The above-mentioned adhesion promoter can be used to improve the formation of the organic EL insulating film of the present invention. Adhesion between the insulating film formed by the radiation-sensitive resin composition and the substrate. A functional silane coupling agent such as a reaction having a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and the like can be used as the adhesion assistant. Silane coupling agents with specific substituents. Specific examples include trimethoxysilylbenzoic acid, r-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, r · isocyanatepropyltriethyl Silyl, r-glycidyloxy gastric trimethoxysilane, / 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilicone, etc. The compounding amount of this surfactant is for the composition When the solid content of the material is 100 parts by weight, it is preferably blended with 15 parts by weight or less, and more preferably 10 parts by weight or less. The radiation-sensitive resin composition for forming an organic EL insulating film of the present invention may be used according to the purpose of use. The appropriate solid content concentration is adopted, for example, the solid content concentration may be 10 to 40% by weight. The composition solution prepared as described above is filtered using a microporous filter j having a pore size of 0.2 μm, and then used. Method for forming an insulating film of an organic EL display element The method for forming an insulating film of an organic EL display element of the present invention is characterized by including at least the following steps: (1) forming the above-mentioned radiation-sensitive resin on the surface of a substrate of an inkjet device The step of coating the composition, (2) a step of irradiating at least a part of the formed coating film with radiation, -31-(27) (27) 200407667 (3) a developing step. (1) Step of forming the above-mentioned coating film of the radiation-sensitive resin composition on the surface of the substrate of the inkjet device The radiation-sensitive resin composition for forming the organic EL insulating film of the present invention is coated on the surface of the base substrate by an inkjet device It is desirable to remove the solvent by pre-baking to form a coating film. The conditions for pre-baking vary depending on the type of each component, the ratio of use, and the like, and are preferably 60 to 130. . The condition of 0.5 ~ 15 minutes. · The film thickness after pre-baking can be obtained from the solid content concentration or coating conditions of the radiation-sensitive resin composition for forming an organic EL insulating film, for example, 0.2 5 to 4 μm 0 (2). The step of irradiating at least a part of the coating film with radiation is followed by irradiating at least a part of the formed coating film with radiation. At this time, for example, a predetermined pattern of mask is used to irradiate radiation, and then at least a part of the formed coating film is irradiated with radiation. The radiation used here includes, for example, ultraviolet rays such as gg (wavelength 436 nm), i rays (wavelength 365 nm), returned ultraviolet rays such as KrF excimer laser, X-ray rays such as stepping rays, and charged particle rays such as electron rays. . Among these, the g-line and the i-line are preferable. The exposure of these radiations is usually 50 ~ 10,000j / m2, ideally 1000 ~ 5,000J7m2. (3) After the radiation is irradiated in the developing step, a developing solution is used for developing treatment to remove the radiation. -32- (28) (28) 200407667 Irradiated part can get the desired pattern. The ideal developing solution used here can be, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc .; primary amines such as ethylamine, n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, Tetraethylammonium hydroxide, choline and other quaternary ammonium salts or pyrrole, piperidine, 1,8-dioxabicyclo- (5.4,0) -7-undecene, 1,5-dioxane An aqueous alkali solution in which a cyclic amine such as bicyclo- (4.3.0) -5-nonane is dissolved in water. An appropriate amount of a water-soluble organic solvent such as an alcohol or a surfactant such as methanol or ethanol can be added to the developing solution. Various organic solvents that dissolve the composition of the present invention can also be used as the developer. As the development method, a stirring method, a dipping method, a shaking dipping method, or the like can be used. After the development process, the patterned film can be cleaned by, for example, washing with running water. It can also be fully irradiated with radiation from a high-pressure mercury lamp or the like to decompose and treat the 1,2-quinonediazide compound remaining in the film. This film is then hardened by heating it with a heating device such as a hot plate or oven. The heating temperature for this hardening process is, for example, 15 to 280 ° C. If sintering is performed on a heating plate, the heating time is 5 to 30 minutes. If sintering is performed in an oven, the heating time is 30 to 90 minutes. Production of Organic EL Display Element The organic EL element of the present invention includes the insulating film formed as described above. The organic EL element of the present invention is produced, for example, as follows. -33- (29) (29) 200407667 A transparent electrode such as I T ◦ is formed on a glass substrate by sputtering, and an insulating film pattern is formed thereon. Then, for example, a film of I τ ◦ is etched with a hydrochloric acid-based etchant, and the photoresist film is peeled to form a pattern of the transparent electrode, for example, a long pattern is formed. On the substrate having the transparent electrodes forming the pattern, the pattern of the insulating film of the present invention is formed as described above. Next, an electron transport layer and an inverted conical cathode partition wall are formed, and then an electrode transport layer, an organic EL light emitting layer, and a cathode layer are sequentially formed. As the hole transporting layer, for example, a phthalocyanine-based material such as CuPc or H2Pc, or an aromatic amine can be used. Organic EL light-emitting materials can use materials such as Alq3, BeBq3 doped with quinacridone or coumarin, so-called low-molecular organic EL materials, or polystyrene-based, fluorene-based high-molecular organic EL material. As the cathode material, Mg-Al, Al-Li, Al-Li20, Al-LiF, etc. can be used. Secondly, a hollow structured SUS can and the above-mentioned substrate are assembled with a packaging material such as epoxy resin, and then assembled into a module that can be used as an organic EL element. [Embodiments] [Examples] 1 Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited by these y examples. The molecular weights measured below are based on the polystyrene-equivalent weight average molecular weight of GPE chromatographic analyzer HLC-8020 made by Tosoh Corporation, and ^ is "wt%". Synthesis Example 1 (Synthesis of Resin a-1) 176 g (0.1 mol) of second butoxystyrene and 5.8 g (0.1 (Mmol)) of azobisbutyronitrile were charged into a burner equipped with a cooling tube, a stirrer, and a thermometer. -34- (30) (30) 200407667 In a bottle, 250 ml of propylene glycol monomethyl ether was added to dissolve it, and polymerized at 75 ° C for 4 hours. 50 g of a 5% by weight sulfuric acid aqueous solution was prepared with the obtained polytert-butoxy The styrene solution was mixed and subjected to a hydrolysis reaction at 100 ° C for 3 hours. Then, 500 ml of propylene glycol monomethyl ether acetate was added, and then washed 3 times with 1 000 ml of deionized water. After that, the organic layer was depressurized to remove the solvent, and vacuumed. Drying to obtain an alkali-soluble resin (polyhydroxystyrene) of Mw 24, 000. This alkali-soluble resin is "Resin a -1". Synthesis Example 2 (Synthesis of Resin a-2) 57 g (0.6 mol) of m-cresol 38 g (0.4 mol) of p-cresol, 75.5 g of 37% by weight aqueous formaldehyde solution (0.93 mol of formaldehyde), 0.63 g (0.00 5 mol) of oxalic acid dihydrate, and 26 4 g of methyl isobutyl ketone Inside the flask of the thermometer, then immerse the flask in an oil bath, and conduct the polycondensation under reflux with stirring for 4 hours. The temperature of the oil bath was raised for 3 hours, and then the pressure in the flask was reduced to 30-50 mmHg to remove volatile components, and the molten resin was recovered to room temperature. This resin was dissolved in ethyl acetate to make the resin content 30 After adding 1.3% of the solution, 1.3 times the amount of methanol and 0.9 times the amount of water were added, and they were stirred and allowed to stand. Then, they were separated into two lower layers and concentrated and dried to obtain Mw 8,000 alkali-soluble resin (phenol resin). This alkali-soluble resin is "Resin a-2". Synthesis Example 3 (Synthesis of Copolymer (a-3)) 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) And diethyl-35- (31) (31) 200407667 2 parts by weight of glycol ethyl methyl ether was put into a flask equipped with a cooling tube and a stirrer. Then 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, and 40 parts by weight of glycidyl acrylate, 15 parts by weight of methacrylate and 10 parts by weight of cyclohexyl cis butane diamine, and then substituted with nitrogen, and then added 5 parts by weight of 1,3-butadiene, Start stirring slowly. Let the temperature of the solution rise to 70 ° C and keep this temperature for 4 hours to obtain Polymer solution of polymer "a-3". The solid content concentration of the prepared polymer solution was 3 1.0% by weight, Mw 8,200. Example 1 100 parts by weight of resin a-1 with component (a) mixed, ( b) Components of 1,1,3 · tris (2,5 · dimethyl-4-hydroxyphenyl) -3-phenylpropane (lmol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate of chlorine (1.9mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5- 30 parts by weight of sulfonic acid ester, 400 parts by weight of diethylene glycol monobutyl ether acetate as the component (c) and 0.01 parts by weight of Megafac F172 (made by Dainippon Ink Co., Ltd.). Ethylene glycol methyl ether was diluted and dissolved so that the overall solid content concentration became 20%, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare the composition solution of the present invention. Formation of Insulating Film The above composition was coated on a glass substrate using an inkjet device to 'form a film thickness of 1 μm, and then pre-baked at 80 ° C for 1.5 minutes on a hot plate' -36- (32 ) (32) 200407667 into a coating film. Then, it was exposed to an analyzer PLA-501F made by Canon Inc. through an insulating film pattern mask of 30 μm, and then developed at 25 ° C. for 1 minute with a tetramethylammonium hydroxide 2.3 8 wt% aqueous solution. It was then washed with water under running water and dried to form a pattern on the wafer. This pattern is then heated in an oven at 230 ° C for 60 minutes to form an insulation film pattern. (1) Evaluation of sensitivity As mentioned above, the minimum exposure to form a 30μm pattern can be formed. This number is shown in Table 1. When the number is 200 mJ / cm2 or less, the radiation sensitivity is good. (2) Evaluation of cross-sectional shape A scanning electron microscope (formation "S_ 42 00" manufactured by Hitachi, Ltd.) was used to analyze the cross-sectional shape of the insulating film pattern formed above, and measure the cone angle of the cross-sectional shape ( The angle between the bottom edge of the cross-sectional shape of the pattern and the tangent to the edge is the same as the following). The results are shown in Table 1. When the number 値 is 50 ° or less, 'indicates that the cross-sectional shape of the pattern is good. (3) Presence or absence of development residue After forming an insulating film pattern on the glass substrate on which ITO was vapor-deposited, the presence or absence of development residue was confirmed by the following two methods. (1) Visual observation using a green lamp (manufactured by Funatek Co., Ltd.) 37-(33) (33) 200407667 (2) Scanning electron microscope (manufactured by Hitachi, Form S-4200 ") Observed at 40,000 times. The observation results are shown in Table 1. (4) Evaluation of heat resistance When the insulating film is formed as described above, the rate of change in film thickness before and after heat treatment at 23 ° C for 60 minutes in an oven is shown in Table 1. When this absolute value is within 5% before and after heating, it is evaluated that the heat resistance is good. ® (5) Evaluation of Solvent Resistance After immersing the insulating film pattern formed as described above at 90 ° C for two minutes in A_Ashuo, the change rate of film thickness due to immersion was measured. The result is shown in _ i. When the absolute value is less than 5%, the solvent resistance is evaluated to be good. (6) Evaluation of Alkali Resistance The insulating film pattern formed as described above was immersed in a 1% NaOH aqueous solution at a temperature of 25 ° C for 20 minutes, and the change rate of the film thickness resulting from the immersion was measured. The results are shown in Table 1. When the absolute value is within 5%, the alkali resistance is evaluated to be good. (7) Evaluation of inkjet coating property The above composition was coated on a glass substrate using an inkjet device to form a film thickness of 1.2 μm, and then pre-baked on a hot plate at 80 ° C for 1.5 minutes to form a coating film. . A contact-type film thickness measuring device a-step (manufactured by Tencol Japan) was used to measure the length of 2 -38- (34) (34) 200407667, ΟΟΟμιη, Μ fixed range 2, 000μΓη > < 2, 〇ΟΟΟμιη square, collar ! | Fixed black occupation number η = 5 Measure the unevenness on the surface of the coating film. Table 1 shows the average 値 (nm) of the height difference between the highest part and the lowest part of each measurement. When the number is not more than 300 nm, the inkjet coating property is good. (8) Evaluation of dry-solid characteristics A fixed needle-type microinjector (Hamilton microinjector, model 701, needle inner diameter 0.13mm) was used to attract the above composition, with the needle facing downward, and the microinjector kept straight, and observed to be squeezed by the tip of the needle The state of the composition above 1 μΐ, the state of the composition after being left in a room at 25 ° C for 24 hours. The results are shown in Table 1. The needle was evaluated as "good" when there was no solid matter at the tip of the needle, and "poor" when it was dry and the pinhole was blocked. Examples 2, 3, 4, and 5 except that the types and addition amounts of components (a), (b), and (c) in Example 1 and the types of other solvents were changed to those shown in Table 1, The rest was prepared in the same manner as in Example 1 and then evaluated. However, only the concentration of the tetramethylammonium hydroxide aqueous solution in the developing solution of Example 3 was changed to 0.4% by weight, and the other examples were the same as those used in Example 1. A 2.38% by weight aqueous solution was used. The results are shown in Table 1. In Table 1, each component is added in parts by weight, and "-" in the table indicates that the component is not added. The abbreviations of (b) component, (c) component and other solvents are as follows. -39- (35) (35) 200 407 667 b-1: 1,1,3-tris (2,5-difluorenyl-4-hydroxyphenyl) -3-benzylpropane (1.0 mol) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonic acid chloride (1.99mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -benzylpropane 1,2-naphthoquinonediazide-5-sulfonate) b-2: 4,4,-[1- [4- [1- [4-hydroxyphenyl] -bumethylethyl] phenyl] Ethylene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide condensate (2.0 mol) condensate (4,4,-[1- [4- [卜 [4- 经 本Group] -1-methylethyl] phenyl] ethylene] bisphenol-1 '2-naphthalene_diazide-5-sulfonate) b-3: 2,3,4-hydroxybenzoyl A condensate of ketone (1.0 mol) and 1 '2-naphthyldiazide-5-sulfonic acid chloride (2.0 mol) (2,3,4-hydroxydimethanone-1,2-naphthalene) Nitrogen-5-sulfonate) c-1: diethylene glycol monobutyl ether acetate c-2: diethylene glycol monoethyl ether acetate c-3: diethylene glycol dimethyl ether S-2: diethyl ether Glycol ethyl methyl ether Examples 6, 7, 8 and 9 The same procedures as in Example 2 were performed except that the type and amount of component (d) or (e) described in Table 1 were added to Example 2. The composition solution was prepared in the same manner as in Example 2 and then evaluated. The results are shown in Table 1. The abbreviation of (d) component or (e) component is as follows. d-1: Petrochemical Shellepox (stock) system, "Epycoat 152" -40- (36) (36) 200407667 d-2: Petrochemical Shellepox (stock) system, "Epycoat 828" e_l: Mitsui Sinzmid (stock) system "Simel 300" e-2: Mitsui Sinzmid Co., Ltd. "Simel 3 03" Comparative Examples 1 and 2 Except that component (c) was not added in Example 2, and Sl and S-2 were used as solvents, the rest A composition solution was prepared in the same manner as in Example 2 and then evaluated. The results are shown in Table 1. From Table 1, it is known that the experimental example using the composition without the (C) component has poor inkjet coating properties.
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【ίΜ 比較例 CNJ 100 I CN 1 i 1 1 1 1 1 CNJ ώ 1600 00 T— 壊 1〇 T— o CO LO CO 460 不佳 T— I loo | 1 LO CM 1 1 1 1 1 I 1 ώ 1600 CD T— 壊 CD τ— 00 c\i CO CO 510 I不佳I 實施例 ⑦ 100 1 LO CNJ 1 I 400 1 1 1 1 1 ΙΟ ώ 1200 00 壊 CO c\i CD τ— G) T— I 190 I良好I CO I 100 I 1 l〇 CNJ 1 1 400 1 1 1 1 Τ— 1 (/) I 1200 I 卜 壊 m c\i T— CNJ | 180 j I良好I 卜 I loo I I m CNJ 1 400 1 1 CO 1 ώ I 1400 I 寸 T— 摧 CO 〇si 00 CN | 180 | I良好I CD 100 1 uo CNJ 1 400 睡 CNJ 1 1 \— 1 CO I 1400 I m T— 壊 CD τ— c\i O) csi I 170 I I良好I LO 100 1 1 1 1 450 1 1 1 1 ώ | 1100 | 00 壊 T— 〇 cd CD cd 190 I良好I 寸 100 1 l〇 CNJ 1 1 1 450 1 1 1 1 CN ώ | 1500 I 00 T— 鹿 T— 00 c\i 寸 cd 180 I良好I CO 1 100 in CNJ 1 1 1 500 1 1 1 1 CSJ ώ 1000 CD 壊 CNJ t— CN cd | 160 | I良好I CN 1 loo | 1 in CNI 1 400 1 1 1 1 ώ I 1500 I 卜 壊 iq 卜 c\i LO cd …170…. I良好I T— 100 1 置 1 裡 1 400 1 1 1 1 1 τ ι CO I 1700 | CN 壊 〇 csi l〇 csi CN cd 180 I良好I τ ι CD Csl ω CO ά τ— Δ CNJ A CO η τ- Ο CNJ ώ 〇 CNJ 〇 Τ Ι φ CNI ώ 固形分濃度(％) c^s g 圓錐角(° ) 顯影殘留 耐熱性(％) 耐溶劑性(％) 耐鹼®%) 噴墨塗布丨生(nm) 乾固特性 鹼可溶I 件樹脂 1,2-醌二 疊氮化 合物(b) 黑占 溶劑⑹ 環氧化 1合物⑼1 三聚氰1 胺化合 物⑹ 駿 Η -42- (38) (38)200407667 【發明之效果】 依據本發明可得到適合作爲以噴墨方式塗佈有機EL 顯示元件之絕緣膜之輻射敏感性樹脂組成物，有機EL顯 示元件之絕緣膜及其形成方法，及具備該絕緣膜之有機 EL顯示元件。[ΊΜ Comparative Example CNJ 100 I CN 1 i 1 1 1 1 1 1 CNJ FREE 1600 00 T— 壊 1〇T— o CO LO CO 460 Poor T—I loo | 1 LO CM 1 1 1 1 1 I 1 FREE 1600 CD T— 壊 CD τ— 00 c \ i CO CO 510 I Poor I Example ⑦ 100 1 LO CNJ 1 I 400 1 1 1 1 1 ΙΟ FREE 1200 00 壊 CO c \ i CD τ— G) T— I 190 I Good I CO I 100 I 1 l CNJ 1 1 400 1 1 1 1 Τ— 1 (/) I 1200 I BU mc \ i T— CNJ | 180 j I Good I BU I loo II m CNJ 1 400 1 1 CO 1 FREE I 1400 I Inch T—Destroy CO 〇si 00 CN | 180 | I Good I CD 100 1 uo CNJ 1 400 Sleep CNJ 1 1 \ — 1 CO I 1400 I m T— 壊 CD τ— c \ i O) csi I 170 II Good I LO 100 1 1 1 1 450 1 1 1 1 Royalty free | 1100 | 00 壊 T— 〇cd CD cd 190 I Good I inch 100 1 l CNJ 1 1 1 450 1 1 1 1 CN FREE | 1500 I 00 T— Deer T— 00 c \ i inch cd 180 I Good I CO 1 100 in CNJ 1 1 1 500 1 1 1 CSJ FREE 1000 CD 壊 CNJ t— CN cd | 160 | I Good I CN 1 loo | 1 in CNI 1 400 1 1 1 1 Royalty-free I 1500 I bu 壊 iq c \ i LO cd… 170… .IGood IT— 100 1 1 Mile 1 400 1 1 1 1 1 τ ι CO I 1700 | CN 壊 〇csi l〇csi CN cd 180 IGood I τ ι CD Csl ω CO τ— Δ CNJ A CO η τ- 〇 CNJ FREE 〇CNJ 〇 Τ Ι φ CNI (Free solid content concentration (%) c ^ sg Cone angle (°) Residual heat resistance during development (%) Solvent resistance (%) Alkali resistance®%) Inkjet coating (nm) Dry solid properties Alkali Solvent I resin 1,2-quinonediazide compound (b) Black accounts for solvent ⑹ Epoxidation 1 compound ⑼ 1 melamine 1 amine compound Η Jun Η -42- (38) (38) 200407667 [Effect of the invention] According to the present invention, a radiation-sensitive resin composition suitable as an insulating film for coating an organic EL display element by an inkjet method, an insulating film for an organic EL display element and a method for forming the same, and an organic EL display element including the same can be obtained. .
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