41834? A7 經濟部中央標準局負工消Φ;合作社印驳 13 7 I 圓 I Μ· ·_Ι ·ην - - ----- - ·ι·^μι ·ιιι ·-·_-·五、發明説明t ) 發明所屬的技術領域 本發明係有關感光性樹脂組成物,更詳細言之,係指 有關不僅優越的靈敏度或解析度,亦兼備良好的耐熱性等 ,較適合用作於T F T (薄膜電晶體)與透明電極之間所 形成的透明絕緣膜等之負片型感光性樹脂組成物,及使用 此組成物之液晶顯示元件及電漿顯示板或L E D發光體等 的顯示元件。 習知技術 近年,液晶顯示器(L CD)之發展係引人注目的’ 正被視作取代C R T (映像管)之下一世代的顯示裝置。 其中,對液晶顯示器之每一像元與薄膜電晶體(T F T ) 組合的有源矩陣型之液晶顯示,係具有高速響應性’高格 調,廣視野角等的優越特性,尤其備受矚目的。因此’至 目前仍蓬勃進展著高開口率化,顯示畫面之大型化等的開 發。 相關的有源矩陣型之液晶顯示器,例如T F T型 '液晶 顯示器,爲擴展其問題點之開口率,長久以來正採取以T 的各種搭配。 藉由半導體膜,閘絕緣膜之膜質提高,縮小使1'11' Τ 特性提高的面積。 •藉由採用自我調準型T F Τ構造,減少寄生容量’ 減少T F Τ及補助容量。 •將電晶部配置於閘配線上。 -------------------- " "4 - 本紙張尺度適用中國國家標準(CNS ) ( 210Χ2(,>7公犮) --;-------- (谛•先i讀背而之注意事項#¾¾本頁) 丁 •Θ 經濟部中央標準局負工消贽合作社印奴 418347 Λ7 ______ B7 五、發明説明4 ) •使液晶之電壓保持特性提高,減少補助容量。 *將補助容量重疊於閘配線之上。 •以透明電極製作補助容量。 •藉由低電阻配線材料之採用,縮小配線寬度。 •於像元電極及閘,源配線之間藉由挾持絕緣膜,使 兩者之間隙狹窄。 •於T F T基片側設置遮光膜,減少與對向基片間之 貼合邊界。 因此,於上述的搭配之中,藉由於像元電極及閘,源 配線之間挾持絕緣膜使兩者之間隙狹窄的方法,近年來更 被視作有希望的。 發明欲解決的課題 然而,相關的被視作有希望的方法所用的絕緣膜,有 採用兼具高靈敏度,高解析度(hole pattern ),透明性, 耐熱性及耐藥品性等特性之感光性樹脂之必要,但在向來 習用的感光性樹脂卻有未存在兼具此種特性者之課題。 又,向來被用於半導體之製造等的含有酚醛淸漆樹脂 及萘醌二疊氮化合物之正片型光阻,雖爲在靈敏度,解析 度方面優越者,但在透明性,耐熱性及耐藥品性等點卻未 能滿足者,因此,兼具高靈敏度,高解析度,透明性,耐 熱性及耐藥品性等所有特性之感光性樹脂乃正被期待出現 著。 再者,上述的課題或要求,不僅液晶顯示元件,即連 —.------0^------1T-----0線 s - (請_先閱讀背而之注意事項孙4舄本頁) 本紙張尺度適用中國國家標準(CNS ) Λ4規松(ΉΟΧ297.公筇) -5- 418347 A7 B7 五、發明説明$ ) 電漿顯示板(PDP)或LED發光體類的顯示元件亦係 共同的。 本發明係有鑑於此種習知技術所具有的課題而完成者 ,其目的係提供靈敏度,高解析度,透明性’耐熱性及耐 藥品性均衡的負片型感光性樹脂組成物,及採用此組成物 之各種顯示元件。 解決課題而採的手段 本發明人 發現經由採用 化合物經共聚 乙烯性不飽和 發劑之感光性 指定的自由基 〕成分成化學 而形成的被膜 亦即,本 有不飽和羧酸 等’爲解決上述問 由〔A〕不飽和羧 合物的鹼可溶性樹 雙鍵鍵結之化合物 樹脂組成物,利用 聚合性化合物之環 鍵結(交聯),並 可達成上述目的, 題點,經 酸與指定 脂,〔B ,及〔C 紫外線, 己烯環之 採用此慼 以至完成 發明之感光性樹脂組成物 (a _ 1 )及下述一般式 各種檢討,結果 的自由基聚合性 〕具有至少一個 〕含有光聚合引 再者熱,使上述 雙鍵鏈結與〔B 光性樹脂組成物 本發明。 其特徵在於:含 1 ) 請 先- 閲-讀 背 而 今. 意 事 項 再 填 J裝 頁 訂 M. 經消部中央糅準局負工消f合作社印製 C 0 K: 0 ο. (式內之Ri〜R3係各自獨立的表示氫原子或碳數1〜5 本紙張尺度適用中國國家標準(CNS ) /\4規柏(2】OX297*iTy -6 - 418347 Λ7 I37 經濟部中央樣準局貝工消费合作社印掣 五、發明説明4 ) 之烷基,R4表示氫原子或碳數1〜5之烷基或烷氧基,以 表示1〜5之整數)表示的自由基聚合性化合物(a — 2 )經予共聚合而得的鹼可溶性樹脂〔A〕具有至少一個乙 烯性不飽和雙鍵鍵結之化合物〔B〕,與光聚合引發劑〔 C〕。 又,本發明之液晶顯示元件,係以採用上述的感光性 樹脂組成物而成者爲特徵,此情形,此感光性樹脂組成物 ,係採用於T F T及透明電極之間形成的透明絕緣膜,於 定膜及透明電極之間形成的透明絕緣膜,及於彩色濾鏡上 形成的保護膜之中之至少一種爲宜。 再者,本發明之電漿顯示板,係採用上述的感光性樹 脂組成物而成的電漿顯示板,上述感光性樹脂組成物,係 以被採用作透明絕緣膜或保護膜爲特徵。 再者又,本發明之L ED發光件,係採用上述的感光 性樹脂組成物而成的L E D發光體,上述感光性樹脂組成 物,係以被採用作保護膜爲特徵。 發明之實施形態 以下,詳細說明本發明。 首先,本發明之感光性樹脂組成物所用的鹼可溶性樹 脂〔A〕爲不飽和羧酸Ci R;、 ~1)及下述一般式(1) -----ot —— - ' (成先閱讀背面之注^>項再填寫本頁) X . -^ G線 C Ο Η ; li Ο t紙張尺度適用中國國家標準(CNS ) Λ4说柏(210 X 297公垃〉 經濟部智慧財產局員工消費合作社印製 ,4 1B 3 4 i A7 ____B7__ 五、發明說明(5 ) (式內之係各自獨立的表示氫原子或碳數1〜5. 之烷基,R4表示氫原子或碳數1〜5之烷基或烷氧基,m 表示1〜5之整數),表示的自由基聚合性化合物(a — 2 )而得的共聚體。 在此,不飽和羧酸之具體例,可舉出有:(甲基)丙 烯酸,丁烯酸,亞甲基丁二酸,順丁烯二酸及反丁烯二酸 等〔以下.(甲基)係表示包含有甲基的情形及無甲基的情 形之兩種化合物〕。此等亦可組合二種以上使用。 又,至於以一般式(1 )表示的自由基聚合性化合物 之具體例,可舉出有:(甲基)丙烯酸(2_環己烯基) 甲酯,(甲基)丙烯酸(2—環己烯基)乙酯,(甲基) 丙烯酸(3 -環己烯基)甲酯及(甲基)丙烯酸(3 -環 己烯基)乙酯等,此等可組合二種以上使用。 且,上述的鹼可溶性樹脂〔A〕,係不飽和羧酸及上 述自由基聚合性化合物,與可與此等共聚合的其他的自由 基聚合性化合物(a — 3 )之共聚體亦可。 呈於相關的其他自由基聚合性化合物之具體例,可舉 出有:苯乙烯,甲基苯乙烯,乙烯基甲苯等之芳香族乙烯 基化合物,(甲基)丙烯酸甲酯,(甲基)丙烯酸乙酯’ (甲基)丙烯酸丁酯,(甲基)丙烯酸2_羥乙酯’(甲 基)丙烯酸苄酯等之不飽和羧酸烷酯及(甲基)丙烯酸縮 水甘油酯等之不飽和羧酸縮水甘油酯等,及此等之任意的 <請先閲讀背面之注意事項再填寫本頁) ^1 19 H ^1-丨, 一言 π 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐〉 -8- 418347 Λ 7 Β7 五、發明説明纟 ) 混合物。 如上述般,鹼可溶性樹脂〔A〕爲以上述各化合物爲 共聚合成分,其會有量,因應所得的感光性樹脂組成物之 特性等,可適當選定,惟不飽和羧酸(a - 1 )成分通常 爲10〜70重量%,宜爲30〜60重量% ’自由基聚 合性化合物(a — 2 )成分通常爲5〜8 0重量% ’宜爲 20〜60重量%。 又,其他的自由基聚合性化合物(a - 3 ) ’可含有 任意成分,惟於鹼可溶性樹脂〔A〕中未滿7 0重量%’ 宜爲含有未滿5 0重量%之量亦可。 不飽和羧酸(a - 1 )成分之含有量若未滿1 〇重量 %時,則對鹼水溶液之溶解性會降低,顯影性變差,又有 靈敏度降低的情形。另一方面,若超過7 0重量%時’則 對鹼水溶液之溶解性變成過大,顯影後之殘膜率降低,塗 膜表面變粗的情形。 經濟部中央棉準局員工消贽合作社印製 ---------i — *- (請A'M讀背而之注意事項芥填耗本頁) 又,自由基聚合性化合物(a 一 2 )成分之含有量若 未滿5重量%時,有交聯密度降低’顯影後之殘膜率降低 ’耐熱性劣化的情形。另一方面若超過8 0重量%時,對 鹼水溶液之溶解性會降低,顯影性變差,靈敏度降低的情 彤。 再者,本發明係依含有不飽和羧酸(a - 1 )成分’ 自由基聚合性化合物(a — 2 )成分’及其他自由基聚合 性化合物(a _ 3 )之比率不同而異,惟至於鹼可溶性樹 脂〔A〕,採用換算成聚苯乙烯之重量平均分子量(Mw 本紙張尺度適用中國國家標準(CNS ) Λ4规格(210X297^^ ) - 9 - 經滴部中央標準局貝工消f合作衽印製 A7 B7___ 五、發明説明ΐ ) )通常爲 1,〇〇〇 〜100 ’ 〇〇〇 ’ 宜爲5 ’ 〇◦〇 〜50,000者較宜。 鹼可溶性樹脂〔A〕之換算成聚苯乙烯之重量平均分 子量(Mw)若未滿1,0 0 0時’則顯影後之殘膜率降 低,有耐熱性劣化的情形。另一方面’若超過1 〇 〇,◦ 0 0時,則顯影性,靈敏度降低,顯影後會殘留殘渣。 且,上述的鹼可溶性樹脂(A),雖然可由習用公知 的聚合方法而得,惟於甲醇,乙醇等醇類,四氫呋喃,二 乙二醇二甲醚等之醚類,N-甲基一2 —吡咯烷酮類之非 質子性極性溶劑等的溶劑中,在2,2 / —偶氮異丁腈等 偶氮化合物類,有機過氧化物等之觸媒(聚合引發劑)之 存在下,使上述各成分共聚合而得爲宜。 其次,具有至少一個乙烯性不飽和雙鍵鍵結之化合物 〔Β〕>可舉出有:(甲基)丙烯酸甲酯,(甲基)丙烯 酸乙酯,(甲基)丙烯酸丁酯,〔甲基)丙烯酸2-乙己 酯,(甲基)丙烯酸苯酯,(甲基)丙烯酸苄酯等之(甲 基)丙烯酸衍生物*(甲基)丙烯酸2—羥基乙酯,(甲 基)丙烯酸2_羥基丙酯,(甲基)丙烯酸2—羥基丁酯 ’(甲基)丙烯酸3-羥基丙酯等之羥基烷酯類,羧 基聚己內酯單(甲基)丙烯酸酯,(甲基)丙烯酸苯二甲 酸單羥基乙酯,(甲基)丙烯酸2—羥基-3—苯氧基丙 酯等之單官能(甲基)丙烯酸酯化合物,(甲基)丙烯酸 1 ’ 4- 丁二醇酯,(甲基)丙烯酸1,6_己二醇酯, 二(甲基)丙烯酸乙二醇酯,(甲基〕丙烯酸新戊二醇酯 (諳先閱讀背而之注意事項再填寫本頁) _裝. 本紙張尺度適用中國國家標準(CNS ) Λ4说柏(2〗0X?97公# ) -10- A7 137 甲基)丙烯酸三乙二 烯酸三 四(甲 異戊四 丙烯酸 (甲基 化雙酚 基)丙 酚S酯 乙二醇 等之多 羥甲基 基)丙 醇酯, 異戊四 )丙烯 A酯, 烯酸乙 ,二( 雙羥基 官能( 基)丙 基酯, 丙烯酸 甲基) 酯,二 氧化氫 二(甲 氧化雙 烯酸二 四醇酯 —41834 了 五、發明説明纟 ) ’二(甲基)丙烯酸二乙二醇 醇酯,二(甲基)丙烯酸聚乙 羥基三甲基乙酸新戊二醇酯, 酯’環氧化三(甲基)丙烯酸 烯酸二三羥甲基丙烷酯,二( 三(甲基)丙烯酸異戊四醇酯 醇酯,六(甲基)丙烯酸二異 酸二環戊基酯,二(甲基)丙 二(甲基)丙烯酸乙氧化雙酚 氧化雙酚F酯,二(甲基)丙 甲基)丙烯酸羥丙基酯,(甲 酯,及三(甲基)丙烯酸單羥 甲基)丙烯酸酯化合物等。 又,此等化合物,可將市 基)丙烯酸酯化合物保持原狀 酯,( 二醇酯 三(甲 三羥甲 甲基) ,四( 戊四醇 烯酸乙 A酯, 烯酸乙 基)丙 基異戊 售品之單官能或多官能(甲 的使用。具體而言,可舉出 經濟部中央摞準局員工消費合作社印製 有:Allonix M—5400,M— 5700,M— 215, Μ— 220,Μ— 245,Μ— 305,Μ— 309,Μ _3 15,Μ— 400,Μ— 450,Μ— 8060,Μ -8 5 6 0 (東亞合成化學工業股份有限公司)製造) ,Biskote 2 9 5,3 0 0 ’ 3 6 0,4 0 0 (大阪有機化學 工業股份有限公司)製造),KAYARADTMPTA,PET-3 0 DPHA ’ DPCA—60 (日本化學股份有限公司 製造)等。 於本發明,上述化合物之中 本紙張尺度適用中國國家標牟(CNS〉八4規格(2〗0X 297公烚 甲基)丙烯酸三 以 -11 - 經濟部中央標準局員Η消费合作社印掣 4183^7 Λ7 ___B7 五、發明説明纟 ) 羥甲基丙烷酯,三(甲基)丙烯酸異戊四醇酯,四(甲基 )丙烯酸異戊四醇酯,六(甲基)丙烯酸二異戊四醇酯, Allonix Μ— 305 !Μ— 400 'Μ— 450 1 Biskote 3 0 〇,4 0 0,KAYARAD TMPTA,DPHA,PET-30 等三官 能以上的多官能(甲基)丙烯酸酯爲較宜採用。 且,此等的化合物可單獨使用或混合2種以上使用。 其次,至於光聚合引發劑〔C〕,可舉出有:硫雜蒽 酮(thioxanthone) ,2,4 —二乙基硫雜蒽酮等硫雜蒽酮 類,4,4 > —二甲基胺基二苯甲酮,4,4 / —二乙基 胺基二苯甲酮等之二苯甲酮類,2,2_二乙氧基苯乙酮 ,2,2 —二甲氧基一2 —苯基苯乙酮,2 —甲基〔4 — (甲基硫代)苯基〕—2_嗎啉基一1 一丙酮,2_苄基 _2_二甲基胺基一 1一(4_嗎啉基苯基)_丁酮—1 —等苯乙酮類,2 — (4 —甲氧基-1—萘基)一4,6 —雙(三氯甲基)—S —三啡等鹵化合物,氧化2,4, 6 -三甲基苯甲醯基二苯基膦等氧化乙醯基膦類及3,3 >,4,4 < —四(第三丁基過氧基羰基)二苯甲酮等的 過氧化物。 又,上述化合物可將市售品之光聚合引發劑保持原狀 的使用,具體而言,可舉出有:Irgacure 6 5 1,1 8 4, 500,907,369,261( Ciba Geigy 公司)製 造〕,KAYARAD-DETX (日本化藥股份有限公司)製造) ,LucirinTPO(BASF Japan股份有限公司)製造)等。 如上述般,本發明之感光性樹脂組成物,係含有上述 本紙張尺度適用中國國家標準(CNS ) Λϋ?, ( 210Χ^97公^ ) _ ~γΐ_ 一 (請先閱讀背面之注意事項再填,:*?本頁) 0裝. ,5Τ A7 B7 —___ 五、發明説明彳〇 ) 成分〔A〕,〔3〕及〔〇〕者,惟成分〔八〕〜〔(:〕 之含有比率,爲對鹼可溶性樹脂〔A〕1 〇 〇重量份’以 具有至少一個乙烯性不飽和雙鍵鍵結之化合物〔B〕爲2 0〜1 50重量份,宜爲40〜1 00重暈份’及光聚合 引發劑〔C〕爲0.1〜50重量份,宜爲1〜25重量 份爲佳,且具有至少一個以上全乙烯性不飽和雙鍵鍵結之 化合物1 0 0重量份中,以具有至少三個乙烯性不飽和雙 鍵鍵結之多官能(甲基)丙烯酸酯化合物之含有量爲5 0 重量份以上較宜。 對鹼可溶性樹脂〔A〕1 0 0重量份,具有至少一個 乙烯性不飽和雙鍵鍵結之化合物〔B〕若未滿2 0重量份 時,則感光性樹脂之光硬化不足夠,對顯影液之溶解性會 增加,顯影後之塗膜表面上有生成塗膜粗糙的現象。另一 方面,超過1 5 0重量份之情形,塗膜表面之指觸性亦變 成過大,硬化後所得的被膜會生成塗膜粗糙的現象。 經濟部中央標準局負工消費合作社印製 ,------—— -. - (諳先閱讀背面之注意事項再填寫本頁) ο線 又,對驗可溶性樹脂〔A〕1 0 0重量份,光聚合引 發劑〔C〕若未滿0 . 1重量份時,則具有至少一個乙烯 性不飽和雙鍵鍵結之化合物未能充分進行交聯(硬化)反 應,另一方面,若超過5 0重量份時,則有顯影性降低的 情形。 本發明之感光性樹脂組成物,在不損及本發明之目的 的範圍內,視必要時亦可含有上述成分以外的成分。至於 此種其他成分,可舉出有:增感劑’偶合劑及界面活性劑 等。 本紙張尺度適用中國國家標隼(CNS )六4规格(210X297,;>f ) -13- i 4'1 . A 7 _ B7 五、發明説明彳1 ) 增感劑,係使感光性樹脂組成物之靈敏度提高使用者 ,對光聚合引發劑1 0 0重量份,添加1〜2 0重量份使 用著。至於增感劑,以加熱時較不易著色的萘噻唑啉類及 苯並噻唑啉類等較宜採用。 具體而言,可舉出有:1-甲基-2 —苯甲醯亞甲基 —/3 —萘噻唑啉,2 — (泠一萘甲醯基亞甲基)一3 -甲 基苯並噻唑啉等。 偶合劑,係爲使與基片間之附著性提高而使用者,對 由上述感光性樹脂組成物除溶劑外的殘餘部分(以下簡稱 爲「固形分」100重量份可添加10重量份以下並予使 用。 偶合劑,可使用矽烷系,鋁系及鈦酸酯系之化合物。 具體而言,可舉出有:3-環氧丙烷基丙基二甲基乙氧基 矽烷,3 —環氧丙烷基丙基甲基二乙氧基矽烷,3 -環氧 丙烷基丙基三甲氧基矽烷等矽烷系,乙醯烷氧基鋁二異丙 酯等之鋁系,四異丙基雙(二辛基膦)鈦酸酯等鈦酸酯系 化合物。 經濟部中央標牟局負工消費合作社印製 界面活性劑,係爲使對底材基片之濕濡性,均展性, 塗布性提高而使用者,對上述感光性樹脂組成物,添加0 •01〜1重量份並使用。 至於界面活性劑,可使用矽氧系界面活性劑,丙烯酸 酯系界面活性劑,氟系界面活性劑等。具體而言,可舉出 有:Byk — 300,Byk-306,Byk-335 'Byk-310 5 Byk-341 ' Byk-344 -14 - 本紙張尺度適用中國國家標準(CNS ) Λ4規枯(21〇X?y7公益) 經濟部中央標隼局負工消於合作社印t 4^8347 Λ7 Β7 五、發明説明彳2 ) B y k — 3 7 ◦(以上商品名,Byk chemie股份有限公司 製造)等矽氧系,Byk — 354,Byk-358,B y k — 3 6 1 (以上商品名,Bykchemie股份有限公司) 製造)等之丙烯酸酯系,S C - 1 0 1 (旭硝子股份有限 公司)製造),EF — 351,EF — 352 (以上商品 名,Tochem Product公司)製造)等之氟系界面活性劑。 本發明之感光性樹脂組成物,通常係溶解於適當的溶 劑內,以溶液狀態被使用著。此溶液,係將鹼可溶性樹脂 〔A〕投入溶劑中使完全溶解後,於該溶液中以指定的比 例混合具有至少一個以上的乙烯性不飽和雙鍵鍵結之化合 物〔B〕光聚合引發劑〔C〕及視必要時增感劑,偶合劑 ,界面活性劑等,製備使固形分濃度成2 0〜4 0重量% ,其後,攪拌使完全溶解而得。 至於該時際所使用的溶劑,可舉出有:甲氧基二乙醇 ,乙氧基乙醇,2_乙氧乙醇,2 — 丁氧乙醇,二乙二醇 單甲醚,二乙二醇單乙醚等醇類,乙酸一 2_甲氧乙酯, 乙酸一2_乙氧乙酯,乳酸乙酯等酯類外,二乙二醇二甲 基醚,N —甲基_2 —吡咯烷酮,N,N_二甲基乙醯胺 等,此等的溶劑可單獨使用或混合二種以上使用。 將上述配製的感光性樹脂組成物塗布於基片表面上, 若利用加熱去除溶劑’則可形成塗膜。 感光性樹脂組成物之塗布於基片表面上,可採用旋塗 法,輥塗法,浸塗法等習用公知的方法進行。 其次,此塗膜則以熱板,烤箱等予以加熱(以下簡稱 —;------^裝— - (請先閱讀背而之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標率(CNS ) Λ4规将(210X297公垃) -15 - 418347 經濟部中央標準局貝工消费合作社印取 A7 B7 五、發明説明仿) 爲「預烘烤」),預烘烤條件係依各成分之種類,配合比 例之不同而異,惟通常爲70〜1 10 °C,若爲熱板,爲 1〜5分鐘,若爲烤箱則爲5〜1 5分鐘。 其後,於經予預烘烤的塗膜上介由指定圖型之掩膜, 照射紫外線等之後,利用顯影液顯影,去除不要的部分, 形成圖型狀之被膜。 至於顯影液,可舉出有:碳酸鈉,氫氧化鈉,氫氧化 鉀等無機鹼類,及氫氧化四甲基銨,氫氧化四甲基銨等有 機鹼類等之水溶液。又,於上述鹼水溶液內適當量添加甲 醇,乙醇,界面活性劑等亦可使用。 顯影方法•探用浸漬法,淋浴法,噴灑法等之任一種 均可,顯影時間通常爲3 0〜4 0秒*顯影後,藉由以流 水淸洗,使乾燥可形成圖型。 其後,藉由在熱板,烤箱等加熱此圖型(以下簡稱爲 「後烘法」,再使具有至少一個以上的乙烯性不飽和雙鍵 鍵結之化合物的未反應成分進行交聯,同時完全去除溶劑 ,可得指定的被膜圖型。 後烘烤條件係依多成分之種類’配合比例之不同而異 ,惟通常爲1 80〜220 °C ’若爲熱板’則爲5〜30 分鐘,若爲烤箱則爲3 0〜9 0分鐘。 奮施例 以下,以實施例進—步詳細說明本發明,惟本發明並 非受此等實施例所限定者。 --:------裝^-- ~ - ("-先閱讀背而之注意事項再填寫本頁} -11 本紙張尺度適用中國國家栋準(CNS ) A4C格(2! 0 X 297公玷) -16 - 經濟部中央標丰局負工消費合作社印製 418342 , A f _____ B7 五、發明説明<4 ) (鹼可溶性樹脂合成例1 ) 將甲基丙烯酸(3 —環己烯基)甲基50g,甲基丙 烯酸50g,2,2一一偶氮雙異丁腈1 . 5g,甲醇2 8 0 g饋入附有攪拌機,冷凝管,氮氣導入管及溫度計之 燒瓶內,用氮氣沖洗3 0分鐘後,將燒瓶浸入油浴內,在 內溫6 5 °C,進行5 . 5小時聚合反應。 其後,冷卻燒瓶至室溫爲止,將反應液滴入醋酸乙酯 2 8 0 〇 g及環己烷1 4 0 0 g之混合液內,減壓乾燥只 析出的沈澱,而得換算成聚苯乙烯之平均分子量3 3 0 0 ◦之鹼可溶性樹脂9 0 g。 (鹼可溶性樹脂合成例2 ) 將甲基丙烯醆(3 —環己烯基)甲酯2 5 g,苯乙烯 25g,甲基丙烯酸50g,2,2<-偶氮雙異丁腈0 .5g,四氫呋喃200g饋入附有攪拌機,冷凝管,氮 氣導入管及溫度計之燒瓶內,用氮氣沖洗3 0分鐘後,將 燒瓶浸入油浴內,在內溫74 °C,進行5 . 5小時聚合反 應。 其後,冷卻燒瓶至室溫爲止,將反應液滴入醋酸乙酯 1 5 0 0 g及環己烷1 5 0 0 g之混合液內,減壓乾燥已 析出的沈澱,而得換算成聚苯乙烯之平均分子量1 5 6 0 0之鹼可溶性樹脂7 0 g。 本紙張尺度適用中國國家標準(CNS ) Λ4規梠(210X29:?公及) -17 - --.------装-- ί - (#.先閱讀背面之注意事項¢4¾本I) -s 經濟部中央標準局員工消f合作社印製 ^18347 A7 B7 五、發明説明彳5 ) (鹼可溶性樹脂合成例3 ) 將苯乙烯50g,甲基丙烯酸50g,2,2 > —偶 氮雙異丁腈0 . 1 g,四氫呋喃2 0 0 g饋入附有攪拌機 ,冷凝管,氮氣導入管及溫度計之燒瓶內,用氮氣沖洗3 0分鐘後,將燒瓶浸入油浴內,在內溫7 4 °C,進行5 . 5小時聚合反應。其後,冷卻燒瓶至室溫爲止,將反應液 滴入醋酸乙酯1 5 0 0 g及環己烷1 5 0 0 g之混合液內 ,減壓乾燥已析出的沈澱,而得換算成聚苯乙烯之平均分 子量2 6 5 0 0之鹼可溶性樹脂7 ◦ g。 實施例1 於附有攪拌葉之已氮氣取代的可分離式燒瓶內,饋入 N,N —二甲基乙醯胺160g,2- 丁氧乙醇40g, 上述合成例1而得的鹼可溶性樹脂44 g,攪拌使均勻的 溶解後,加入Allonix M305 (商品名:東西合成化學工業 股份有限公司)製造)2 6 . 4 g,Irgacure 907 (商品名 :CIBA-GEIGY 公司)製造)4 4g,2 —( 泠一萘甲醯亞甲基)一3 —甲基苯並噻唑啉〇 · 22g使 溶解成均勻後,投入Byk — 344 ( Byk chemic股份有 限公司製造)0 · 14g,在室溫攪拌1小時,以孔徑◦ .2 2 /zm之薄膜過濾器過濾,而得感光性樹脂組成物之 溶液。 其次,將上述製得的感光性樹脂組成物溶液如下述方 法形成圖型,進行評估,且’此評估法’與後述的實施例 I !!— I.M. ΓΓ·— —· —- »· ··_,— . -- I I II | | | 本紙張尺度適用中國國家標準(CNS ) Λ4规栝(210X29'7公# ) -18 - --;------0^ — -- (請『先閱讀背而之注意事項#填寫本頁)41834? A7 Work load elimination of the Central Standards Bureau of the Ministry of Economic Affairs Φ; Cooperatives rebutted 13 7 I round I Μ ·· _Ι · ην--------· ι · ^ μι · ιιι ·-· _- ·· 5, Description of the invention t) The technical field to which the invention belongs The present invention relates to a photosensitive resin composition, and more specifically, it relates to not only superior sensitivity or resolution, but also good heat resistance, etc., and is suitable for use in TFT ( A negative-type photosensitive resin composition such as a transparent insulating film formed between a thin film transistor) and a transparent electrode, and a display element such as a liquid crystal display element, a plasma display panel, or an LED light emitting body using the composition. Known technology In recent years, the development of liquid crystal displays (LCDs) has attracted attention 'and is being seen as a replacement for the next generation of display devices under CRT (picture tube). Among them, an active matrix type liquid crystal display in which each pixel of a liquid crystal display is combined with a thin film transistor (T F T) has excellent characteristics such as high-speed responsiveness, high style, wide viewing angle, and the like, and has attracted particular attention. Therefore, to this day, development of high aperture ratios and enlargement of display screens has been vigorously progressed. Related active-matrix liquid crystal displays, such as the TFT LCD display, have been adopting various combinations of T for a long time in order to expand the aperture ratio of their problem points. With the semiconductor film, the film quality of the gate insulating film is improved, and the area for improving the 1'11'T characteristics is reduced. • By adopting a self-aligning T F TT structure, reducing parasitic capacity ’reduces T F TT and subsidized capacity. • Place the transistor section on the gate wiring. -------------------- " " 4-This paper size applies to Chinese National Standards (CNS) (210 × 2 (, >7mm)-;- ------- (谛 • Read and read the first note # ¾¾this page) Ding Θ The Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives, Cooperative Innu 418347 Λ7 ______ B7 V. Description of Invention 4) The voltage holding characteristics of the liquid crystal are improved, and the auxiliary capacity is reduced. * Superimpose the supplementary capacity on the gate wiring. • Make auxiliary capacity with transparent electrodes. • Reduce the wiring width by using low-resistance wiring materials. • By holding the insulating film between the pixel electrode, the gate, and the source wiring, the gap between the two is narrowed. • Set a light-shielding film on the T F T substrate side to reduce the bonding boundary between the substrate and the opposing substrate. Therefore, in the above-mentioned combination, a method of narrowing the gap between the source electrode and the wiring by holding the insulating film between the pixel electrode and the gate and the source wiring has been regarded as more promising in recent years. Problems to be Solved by the Invention However, related insulating films that are considered to be promising methods employ a photosensitivity that has characteristics such as high sensitivity, high resolution (hole pattern), transparency, heat resistance, and chemical resistance. Resin is necessary, but conventionally used photosensitive resins do not have the problem of having such characteristics. In addition, positive photoresists containing phenolic varnish resins and naphthoquinonediazide compounds have been used in semiconductor manufacturing and the like. Although they are superior in sensitivity and resolution, they are transparent, heat resistant, and chemical resistant. Those who cannot meet the requirements such as sensitivity, etc., therefore, a photosensitive resin that has all the characteristics of high sensitivity, high resolution, transparency, heat resistance, and chemical resistance is being expected. In addition, the above-mentioned problems or requirements are not only for liquid crystal display elements, that is, even —.------ 0 ^ ------ 1T ----- 0 lines s-(please read first and back Note Sun 4 舄 This page) This paper size is applicable to Chinese National Standards (CNS) Λ4 gauge loose (ΉΟ × 297. 公 筇) -5- 418347 A7 B7 V. Description of the invention $) Plasma display panel (PDP) or LED light emitter Class display elements are also common. The present invention has been made in view of the problems of such a conventional technology, and its object is to provide a negative-type photosensitive resin composition having a balance of sensitivity, high resolution, transparency, heat resistance, and chemical resistance, and the use thereof Various display elements of the composition. Means for Solving the Problem The present inventors have discovered that a film formed by chemically forming a compound through the photosensitive designated radical of a copolyethylene unsaturated hair rinse] component, that is, a film having an unsaturated carboxylic acid and the like, is intended to solve the above problem. Question [A] An alkali-soluble tree double bond-bonded compound resin composition of an unsaturated carboxylate can use the ring bonding (crosslinking) of a polymerizable compound to achieve the above purpose. Grease, [B, and [C ultraviolet rays, the use of the hexene ring and the completion of the invention of the photosensitive resin composition (a _ 1) and the following general formula various reviews, the results of radical polymerizability] have at least one] Containing photopolymerization and heat, the above-mentioned double bond and the [B optical resin composition of the present invention. It is characterized by: Including 1) Please-read-read back to the present day. Please fill in the J items and set the pages M. The items printed by the Ministry of Economic Affairs and the Central Bureau of Standards and Quarantine, printed by the cooperative F 0 K: 0 ο. Ri ~ R3 are independent and indicate hydrogen atom or carbon number 1 ~ 5. The paper size is applicable to Chinese National Standard (CNS) / \ 4 regulations. (2) OX297 * iTy -6-418347 Λ7 I37 Central Bureau of Standards, Ministry of Economic Affairs Pakko Consumer Co., Ltd. 5. Description of the Invention 4) An alkyl group, R4 represents a hydrogen atom or an alkyl or alkoxy group having 1 to 5 carbon atoms, and an integer of 1 to 5) a-2) The alkali-soluble resin [A] obtained by pre-copolymerization has at least one compound [B] having an ethylenically unsaturated double bond, and a photopolymerization initiator [C]. The liquid crystal display element of the present invention is characterized by using the above-mentioned photosensitive resin composition. In this case, the photosensitive resin composition is a transparent insulating film formed between a TFT and a transparent electrode. At least one of a transparent insulating film formed between the fixed film and the transparent electrode, and a protective film formed on the color filter is preferable. The plasma display panel of the present invention is a plasma display panel using the above-mentioned photosensitive resin composition, and the above-mentioned photosensitive resin composition is characterized by being used as a transparent insulating film or a protective film. Furthermore, the LED light emitting device of the present invention is an LED light emitting body using the above-mentioned photosensitive resin composition, and the above-mentioned photosensitive resin composition is characterized by being used as a protective film. Embodiments of the Invention The present invention will be described in detail below. First, the alkali-soluble resin [A] used in the photosensitive resin composition of the present invention is an unsaturated carboxylic acid Ci R ;, ~ 1) and the following general formula (1) ----- ot ——-'(成First read the note on the back ^ > and then fill out this page) X.-^ G line C Ο; li Ο t Paper size is applicable to Chinese National Standards (CNS) Λ4 Shuobai (210 X 297 public waste) Ministry of Economic Affairs Intellectual Property Printed by the Bureau ’s consumer cooperative, 4 1B 3 4 i A7 ____B7__ V. Description of the invention (5) (In the formula, each independently represents a hydrogen atom or a carbon number of 1 to 5. An alkyl group, R4 represents a hydrogen atom or carbon number An alkyl or alkoxy group of 1 to 5, m is an integer of 1 to 5), and a copolymer obtained by a radical polymerizable compound (a-2). Here, specific examples of the unsaturated carboxylic acid may be Examples include: (meth) acrylic acid, butenoic acid, methylene succinic acid, maleic acid, fumaric acid, etc. [Hereinafter, the (meth) -based group indicates a case where a methyl group is included and no Two kinds of compounds in the case of a methyl group]. These may be used in combination of two or more kinds. Moreover, as for the properties of the radical polymerizable compound represented by the general formula (1), Examples include: (2-cyclohexenyl) methyl (meth) acrylate, (2-cyclohexenyl) ethyl (meth) acrylate, (3-cyclohexene) (meth) acrylate Methyl) and (3-cyclohexenyl) ethyl (meth) acrylate, etc., and these can be used in combination of two or more. In addition, the above-mentioned alkali-soluble resin [A] is an unsaturated carboxylic acid and the above-mentioned free Interpolymers of the radical polymerizable compound and other radical polymerizable compounds (a-3) which can be copolymerized therewith. Specific examples of other radical polymerizable compounds that are related to this include: Aromatic vinyl compounds such as styrene, methylstyrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate '(butyl) (meth) acrylate, 2_ Unsaturated carboxylic acid alkyl esters such as benzyl (meth) acrylate and unsaturated carboxylic acid glycidyl esters of glycidyl (meth) acrylate, etc., and any of these < read first Note on the back, please fill out this page) ^ 1 19 H ^ 1- 丨, a word π paper The Zhang scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm> -8- 418347 Λ 7 Β7 V. Description of the invention 纟) Mixture. As described above, the alkali-soluble resin [A] is composed of each of the above-mentioned compounds as a copolymerization component, and may have a certain amount. It may be appropriately selected according to the characteristics of the obtained photosensitive resin composition, but the unsaturated carboxylic acid (a-1 ) The component is usually 10 to 70% by weight, preferably 30 to 60% by weight. The component of the radical polymerizable compound (a-2) is usually 5 to 80% by weight, and preferably 20 to 60% by weight. Further, the other radical polymerizable compound (a-3) 'may contain an optional component, but it is preferable that the content is less than 50% by weight in the alkali-soluble resin [A]. When the content of the unsaturated carboxylic acid (a-1) component is less than 10% by weight, the solubility in an alkaline aqueous solution will be reduced, the developability will be deteriorated, and the sensitivity may be reduced. On the other hand, when it exceeds 70% by weight, the solubility in an alkaline aqueous solution becomes too large, the residual film rate after development decreases, and the surface of the coating film becomes coarse. Printed by the Consumers ’Cooperative of the Central Cotton Barber Bureau of the Ministry of Economic Affairs --------- i — *-(Please read the note of A'M and fill in this page) Also, radical polymerizable compounds ( a-2) If the content of the component is less than 5% by weight, the crosslink density may decrease, and the residual film rate after development may decrease. On the other hand, if it exceeds 80% by weight, the solubility in an alkaline aqueous solution is lowered, the developability is deteriorated, and the sensitivity is lowered. In addition, the present invention varies depending on the ratio of the radical polymerizable compound (a-2) component containing the unsaturated carboxylic acid (a-1) and other radical polymerizable compounds (a_3). As for the alkali-soluble resin [A], the weight-average molecular weight converted to polystyrene (Mw This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 ^^)-9-via the Ministry of Standards, Bureau of Standards and Technology, Fong Cooperate with printing A7 B7___ V. Description of the invention))) It is usually 10,000 ~ 100 ′ 〇〇〇 ′, preferably 5 ′ 〇◦〇 ~ 50,000. If the weight-average molecular weight (Mw) of the alkali-soluble resin [A] converted to polystyrene is less than 1, 000 ', the residual film rate after development may decrease and the heat resistance may deteriorate. On the other hand, if it exceeds 100, ◦ 0 0, the developability and sensitivity are reduced, and residues remain after development. In addition, the above-mentioned alkali-soluble resin (A) can be obtained by a conventionally known polymerization method, but it is only alcohols such as methanol, ethanol, tetrahydrofuran, diethylene glycol dimethyl ether, and the like, N-methyl-1 2 —Pyrrolidone solvents such as aprotic polar solvents, etc., in the presence of catalysts (polymerization initiators) such as 2,2 / —azo compounds such as azoisobutyronitrile, and organic peroxides, etc. It is preferable to copolymerize each component. Next, the compound [B] having at least one ethylenically unsaturated double bond is exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, [ (Meth) acrylic acid derivatives such as 2-ethylhexyl methacrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. * 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl ester, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and other hydroxyalkyl esters, carboxy polycaprolactone mono (meth) acrylate, (methyl ) Monofunctional ethyl methacrylate, monohydroxy (meth) acrylic acid, 2-hydroxy-3-phenoxypropyl, etc., monofunctional (meth) acrylate compounds, (meth) acrylic acid 1 '4-butanediol Esters, 1,6-hexanediol (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol (meth) acrylate (谙 Read the precautions before filling in this page ) _Package. This paper size applies Chinese National Standards (CNS) Λ4 said Bai (2〗 0X? 97 公 #) -1 0- A7 137 Methacrylic acid Triethylene diacrylic acid Tritetrakis (methylisoprenetetraacrylic acid (methylated bisphenol group) Propanol S ester Polyol methyl group) propanol ester, etc. 4) Propylene A ester, ethyl enoate, bis (dihydroxy-functional (propyl) propyl ester, methyl acrylate) ester, hydrogen dioxide bis (methoxydienoate ditetraol ester) 41834 5. Explanation of the invention 纟) 'Diethylene glycol alcohol di (meth) acrylate, neopentyl glycol diethylene glycol trimethylacetate, ester' epoxy tris (meth) acrylate ditrimethylol Propylpropane ester, isopentaerythritol di (tri (meth) acrylate), dicyclopentyl hexa (meth) acrylate diisoacid, ethoxylated di (meth) propane (meth) acrylate Phenol-oxidized bisphenol F esters, hydroxypropyl di (meth) propylmethyl) acrylate, (methyl ester, and tri (meth) acrylic monomethylol) acrylate compounds, etc. In addition, these compounds can retain the acrylate compound as the original ester, (diol ester tris (methyltrimethylol), tetrakis (pentaerythritol ethanoate, ethyl enoate) propyl Monofunctional or polyfunctional isoprene products (the use of A. Specifically, examples include the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs printed by: Allonix M-5400, M-5700, M-215, M- 220, M-245, M-305, M-309, M_3 15, M_400, M_450, M_8060, M -8 5 6 0 (manufactured by Toa Synthetic Chemical Industry Co., Ltd.), Biskote 2 9 5, 3 0 0 '3 6 0, 4 0 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARADTMPTA, PET-3 0 DPHA' DPCA-60 (manufactured by Japan Chemical Co., Ltd.), etc. In the present invention, among the above-mentioned compounds, the paper size of this compound is applicable to Chinese national standard (CNS> 8-4 specification (2〗 0X 297 g 烚 methyl) acrylic acid three to -11-member of the Central Standards Bureau of the Ministry of Economic Affairs Η Consumer Cooperative Cooperative Press 4183 ^ 7 Λ7 ___B7 V. Description of the Invention 纟) Methylmethylpropane ester, isopentaerythritol tri (meth) acrylate, isopentaerythritol tetra (meth) acrylate, diisopentaerythritol (meth) acrylate As the ester, Allonix M—305! M—400'M—450 1 Biskote 300, 400, KAYARAD TMPTA, DPHA, PET-30 and other trifunctional polyfunctional (meth) acrylates are more suitable for use. Moreover, these compounds can be used individually or in mixture of 2 or more types. Next, as for the photopolymerization initiator [C], thioxanthones such as thioxanthone, 2,4-diethylthioxanthone and the like, 4,4 > -dimethyl Aminobenzophenone, 4,4 / -diethylaminobenzophenone and other benzophenones, 2,2-diethoxyacetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholinyl-1 monoacetone, 2-benzyl-2-dimethylamino-1 Mono (4-morpholinylphenyl) _butanone-1-isoacetophenones, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -S —Thalorphine and other halogen compounds, 2,4,6-trimethylbenzylidene diphenylphosphine and other ethynylphosphine oxides and 3,3 >, 4,4 < Peroxycarbonyl) peroxides such as benzophenone. Moreover, the said compound can use the photoinitiator of a commercial item as it is, and specifically, Irgacure 6 5 1, 1, 8 4, 500, 907, 369, 261 (made by Ciba Geigy) ], KAYARAD-DETX (manufactured by Nippon Kayaku Co., Ltd.), Lucirin TPO (manufactured by BASF Japan Co., Ltd.), etc. As mentioned above, the photosensitive resin composition of the present invention contains the above-mentioned paper standards applicable to the Chinese National Standard (CNS) Λϋ ?, (210 × ^ 97 公 ^) _ ~ γΐ_ (Please read the precautions on the back before filling ,: *? This page) 0 pack., 5T A7 B7 —___ 5. Description of the invention 彳 〇) Ingredients [A], [3] and [〇], but the content ratio of ingredients [eight] to [(:] For the alkali-soluble resin [A], 100 parts by weight, the compound [B] having at least one ethylenically unsaturated double bond is 20 to 150 parts by weight, preferably 40 to 100 parts by weight. 'And the photopolymerization initiator [C] is 0.1 to 50 parts by weight, preferably 1 to 25 parts by weight, and has at least one 100 parts by weight of a compound having at least one fully ethylenically unsaturated double bond, in which The content of the polyfunctional (meth) acrylate compound having at least three ethylenically unsaturated double bonds is preferably 50 parts by weight or more. For alkali-soluble resin [A] 100 parts by weight, having at least one If the ethylenically unsaturated double-bonded compound [B] is less than 20 parts by weight, the photosensitivity The resin is not sufficiently light-cured, and its solubility in the developer will increase, and the surface of the coating film after development may become rough. On the other hand, when it exceeds 150 parts by weight, the touch of the coating film surface The property also becomes too large, and the coating obtained after hardening will produce a rough coating film. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, -------------.-(谙 Read the precautions on the back before (Fill in this page) ο In addition, if the soluble resin [A] is 100 parts by weight and the photopolymerization initiator [C] is less than 0.1 part by weight, it has at least one ethylenically unsaturated double bond. The compound does not sufficiently undergo a crosslinking (hardening) reaction. On the other hand, if it exceeds 50 parts by weight, the developability may be reduced. The photosensitive resin composition of the present invention does not impair the object of the present invention. Within the range, if necessary, components other than the above-mentioned components may be contained. As for such other components, sensitizers, coupling agents, surfactants, etc. may be mentioned. This paper applies the Chinese National Standard (CNS) Six 4 specifications (210X297 ,; > f ) -13- i 4'1. A 7 _ B7 V. Description of the invention 彳 1) Sensitizer, which improves the sensitivity of the photosensitive resin composition to the user. For 100 parts by weight of the photopolymerization initiator, add 1 ~ 20 parts by weight. As the sensitizer, naphthalothiazolines and benzothiazolines, which are less likely to be colored when heated, are more preferably used. Specific examples include: 1-methyl-2 -benzylidenemethylene-3 / 3-naphthothiazoline, 2-(linganaphthylmethylene) -3-methylbenzo Thiazoline and so on. The coupling agent is used by the user to improve the adhesion to the substrate. For the remaining portion of the photosensitive resin composition except for the solvent (hereinafter referred to as "solid content"), 10 parts by weight or less can be added and Coupling agents include silane-based, aluminum-based and titanate-based compounds. Specific examples include 3-glycidylpropyldimethylethoxysilane and 3-epoxy. Silanes such as propalkylpropylmethyldiethoxysilane, 3-glycidylpropyltrimethoxysilane, aluminum series such as acetoxy aluminum diisopropyl ester, tetraisopropylbis (di Octylphosphine) Titanate and other titanate-based compounds. Surface active agent printed by the Ministry of Economic Affairs, Central Standardization Bureau, and Consumer Cooperatives to improve the wettability, uniformity and spreadability of substrates. The user can add 0.01 to 1 part by weight to the photosensitive resin composition and use it. As the surfactant, a siloxane-based surfactant, an acrylate-based surfactant, or a fluorine-based surfactant can be used. Specific examples include: Byk — 300, Byk-306 Byk-335 'Byk-310 5 Byk-341' Byk-344 -14-This paper size applies Chinese National Standards (CNS) Λ4 Regulations (21〇X? Y7 Public Welfare) The Central Bureau of Standards of the Ministry of Economic Affairs has lost the work to the cooperatives India t 4 ^ 8347 Λ7 B7 V. Description of the invention 彳 2) B yk — 3 7 ◦ (The above product name, manufactured by Byk Chemie Co., Ltd.) and other silicon based systems, Byk — 354, Byk-358, Byk — 3 6 1 (above the brand name, manufactured by Bykchemie Co., Ltd.) and other acrylic esters, SC-101 (made by Asahi Glass Co., Ltd.), EF — 351, EF — 352 (above the brand name, Tochem Product) ) And other fluorine-based surfactants. The photosensitive resin composition of the present invention is usually dissolved in an appropriate solvent and used in a solution state. This solution is prepared by dissolving an alkali-soluble resin [A] in a solvent to completely dissolve it, and mixing the compound [B] photopolymerization initiator having at least one ethylenically unsaturated double bond at a specified ratio in the solution. [C] and, if necessary, a sensitizer, a coupling agent, a surfactant, etc., to prepare a solid content concentration of 20 to 40% by weight, and then obtain it by stirring to completely dissolve it. As for the solvent used at this time, methoxydiethanol, ethoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, and diethylene glycol monoamine Ethyl alcohol and other alcohols, mono-2-methoxyethyl acetate, mono-2-ethoxyethyl acetate, ethyl lactate and other esters, diethylene glycol dimethyl ether, N-methyl_2-pyrrolidone, N , N-dimethylacetamide, etc. These solvents can be used alone or in combination of two or more. The photosensitive resin composition prepared as described above is applied on the surface of a substrate, and the solvent is removed by heating 'to form a coating film. The coating of the photosensitive resin composition on the surface of the substrate can be performed by a conventionally known method such as a spin coating method, a roll coating method, or a dip coating method. Secondly, this coating is heated by hot plate, oven, etc. (hereinafter referred to as "; -------- ^ 装"-(please read the precautions on the back before filling this page). Standard rate (CNS) Λ4 regulation (210X297). -15-418347 A7 B7 printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of the invention is "pre-baking"), and the pre-baking conditions are based on The type of each component and the mixing ratio vary, but it is usually 70 ~ 1 10 ° C, if it is a hot plate, it is 1 ~ 5 minutes, if it is an oven, it is 5 ~ 15 minutes. After that, the pre-baked coating film is irradiated with ultraviolet rays through a mask of a specified pattern, and then developed with a developing solution to remove unnecessary portions to form a patterned film. Examples of the developing solution include aqueous solutions of inorganic bases such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and organic bases such as tetramethylammonium hydroxide and tetramethylammonium hydroxide. Further, methanol, ethanol, a surfactant and the like may be added to the above-mentioned alkali aqueous solution in an appropriate amount. Development method • Any of dipping method, shower method, spray method, etc. can be used. The development time is usually 30 to 40 seconds. * After development, it can be dried to form a pattern by washing with running water. Thereafter, by heating this pattern (hereinafter referred to as "post-baking method") on a hot plate, an oven, etc., and then crosslinking unreacted components of the compound having at least one ethylenically unsaturated double bond, At the same time, the solvent is completely removed to obtain the specified coating pattern. Post-baking conditions vary depending on the type of multi-components' blending ratio, but usually 1 80 ~ 220 ° C 'If it is a hot plate', it is 5 ~ 30 minutes, or 30 to 90 minutes if it is an oven. The following examples, the present invention will be further described in detail with the examples, but the present invention is not limited by these examples.-: --- --- Installation ^-~-(" -Read the back notice first and then fill out this page} -11 This paper size is applicable to China National Building Standard (CNS) A4C grid (2! 0 X 297 mm)- 16-Printed by the Consumer Standards Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs 418342, A f _____ B7 V. Description of the invention < 4) (Synthesis example of alkali soluble resin 1) Methacrylic acid (3-cyclohexenyl) methyl 50g, methacrylic acid 50g, 2,2-azobisisobutyronitrile 1.5g, methanol 280 g is fed with a mixer, The condenser tube, nitrogen introduction tube and thermometer flask were flushed with nitrogen for 30 minutes, then the flask was immersed in an oil bath, and the internal temperature was 65 ° C, and the polymerization reaction was performed for 5.5 hours. Thereafter, the flask was cooled to a room So far, the reaction solution was dropped into a mixed solution of 2800 g of ethyl acetate and 1 400 g of cyclohexane, and only the precipitate precipitated was dried under reduced pressure to obtain an average molecular weight of 3 converted to polystyrene. 0 0 ◦ Alkali-soluble resin 90 g. (Alkali-soluble resin synthesis example 2) 25 g of methacrylic acid (3-cyclohexenyl) methyl ester, 25 g of styrene, 50 g of methacrylic acid, 2, 2 & lt 0.5 g of azobisisobutyronitrile and 200 g of tetrahydrofuran were fed into a flask equipped with a stirrer, a condensation tube, a nitrogen introduction tube and a thermometer. After flushing with nitrogen for 30 minutes, the flask was immersed in an oil bath and the internal temperature Polymerization was carried out at 74 ° C for 5.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was dropped into a mixed solution of ethyl acetate 1 500 g and cyclohexane 1 500 g. The precipitate that has been precipitated is dried under pressure to obtain an alkali-soluble resin with an average molecular weight of 1 560 0 0 converted to polystyrene 70 g The paper size applies to the Chinese National Standard (CNS) Λ4 Regulations (210X29:? Public and) -17---.------ installation-ί-(# .Read the precautions on the back first) I) -s Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs, printed by a cooperative ^ 18347 A7 B7 V. Description of the invention 彳 5) (Synthesis example of alkali-soluble resin 3) 50g of styrene, 50g of methacrylic acid, 2, 2 > — 0.1 g of azobisisobutyronitrile and 200 g of tetrahydrofuran were fed into a flask equipped with a stirrer, a condensation tube, a nitrogen introduction tube and a thermometer. After flushing with nitrogen for 30 minutes, the flask was immersed in an oil bath and placed in an oil bath. The internal temperature was 7 4 ° C, and the polymerization was carried out for 5.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was dropped into a mixed solution of 1 500 g of ethyl acetate and 15 0 g of cyclohexane, and the precipitate that had precipitated was dried under reduced pressure to obtain a polymer. Alkali-soluble resin with an average molecular weight of styrene of 2 650 7 g. Example 1 In a separable nitrogen-substituted separable flask with a stirring blade, 160 g of N, N-dimethylacetamide and 40 g of 2-butoxyethanol were fed. The alkali-soluble resin obtained in the above Synthesis Example 1 was fed. 44 g, after stirring to dissolve uniformly, add Allonix M305 (trade name: Dongxi Synthetic Chemical Industry Co., Ltd.) 26.4 g, Irgacure 907 (trade name: CIBA-GEIGY company) 4 4g, 2 — (Ling-naphthalenemethylene) —3-methylbenzothiazoline 0.22 g to dissolve homogeneously, put Byk — 344 (manufactured by Byk Chemic Co., Ltd.) 0. 14 g, and stir at room temperature for 1 After hours, it was filtered through a membrane filter having a pore size of. 2 2 / zm to obtain a solution of a photosensitive resin composition. Next, the photosensitive resin composition solution prepared as described above was patterned and evaluated as follows, and the "this evaluation method" and Example I described later !! — IM ΓΓ · — — — — — »··· _, —.-II II | | | This paper size applies Chinese National Standards (CNS) Λ4 Regulations (210X29'7 公 #) -18--; ------ 0 ^ —-(Please 『Please read the back of the note # Fill in this page)
-1T 經濟部中央榡隼局員工消f合作杜印製 ^ 183 47 A7 ______ 五、發明説明切) 2及比較例1亦係共同的。 〔感光性樹脂組成物之評估〕 •圖型之形成方法 將實施例及比較例所得的感光性樹脂組成物之溶液旋 塗於玻璃基片上後,在烤箱內於8 0 °C預烘烤1 0分鐘1 使形成塗膜。其後,以掩膜對準器(Mask Aligner )(茼 品名:Canon公司)製造)使曝光時間變化,曝光(全線 ,無過濾器)後,採用0.02wt%氫氧化四甲基錢水 溶液,在2 3 °C對實施例1及比較例1者噴灑1分鐘,對 實施例2者噴灑9 0秒鐘。 其後,以純水淸洗,乾燥。因此,藉由在烤箱內於2 0 0°C加熱3 0分鐘,進一步使塗膜中之具有至少一個以 上的乙烯性不飽和雙鍵鍵結之化合物的未反應成分進行交 聯,同時完全去除溶劑,形成膜厚3 /zm之塗膜。 就如此而得的塗膜,對靈敏度,解析度,殘膜率,透 明性,耐熱性及耐藥品性,評估下述的特性。此等評估結 果示於表1。 〔評估方法〕 介由第1圖所示的掩膜,進行曝光,於所得的圖型求 取以掩膜圖型1 0 y m而得的高解析度底部之尺寸成爲1 0以m之曝光量(「適當曝光量」或「靈敏度」)。 $紙張尺度適用中國國家標準(CNS ) ( 210X2<J7.»^ ) _ 19 _ (讀先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標麥局员工消汾合作社印顰 Α\834ί A7 ΙΪ7 五、發明説明V ) •解析度: 以掃瞄型電子顯微鏡測定以適當曝光量解析時最小高 解析度底部之尺度。 •殘膜率: 求取(顯影後之膜厚/預烘烤後之膜厚)X 1 0 0, 以9 0%以上爲〇,以未滿9 0%爲X。 •透明性: 於附有所得的圖型之玻璃基片,利用分光光度計(商 品名:U — 3 2 1 0,股份有限公司日立製作所製造)測 定僅塗膜在4 0 0〜8 0 0 nm之透過率。此時之最低透 過率(亦即在波長4 0 0 nm之透過率)在9 5%以上的 情形爲〇,在未滿9 5 %的情形爲X。 •耐熱性 將附有所得的圖型之玻璃基片,在2 2 0 °C再加熱1 小時後,測定加熱後對加熱前的膜厚(後烘烤後之膜厚) 之殘膜率及加熱後之透過率(波長4 0 0 nm之透過率)-1T Co-production by the Central Government Bureau of the Ministry of Economic Affairs ^ 183 47 A7 ______ 5. Invention Description 2) and Comparative Example 1 are also common. [Evaluation of the photosensitive resin composition] • Method for pattern formation After the solution of the photosensitive resin composition obtained in the examples and comparative examples was spin-coated on a glass substrate, it was pre-baked at 80 ° C in an oven 1 0 minutes 1 to make a coating film. Thereafter, the exposure time was changed with a Mask Aligner (produced by Canon), and after exposure (full line, no filter), a 0.02 wt% tetramethyl hydroxide aqueous solution was used. 2 3 ° C was sprayed for 1 minute on Example 1 and Comparative Example 1, and 90 seconds on Example 2. Thereafter, it was rinsed with pure water and dried. Therefore, by heating in an oven at 200 ° C for 30 minutes, the unreacted components of the compound having at least one ethylenically unsaturated double bond bond in the coating film are further crosslinked and completely removed at the same time. Solvent to form a coating film with a film thickness of 3 / zm. The coating film thus obtained was evaluated for the following characteristics with respect to sensitivity, resolution, residual film rate, transparency, heat resistance, and chemical resistance. The results of these evaluations are shown in Table 1. [Evaluation method] Exposure is performed through the mask shown in FIG. 1, and a high-resolution bottom dimension obtained by using the mask pattern 10 μm is obtained from the obtained pattern to an exposure amount of 10 to m. ("Appropriate exposure" or "sensitivity"). $ Paper size applies to Chinese National Standard (CNS) (210X2 < J7. »^) _ 19 _ (Read the precautions on the back before filling this page) Order the staff of the Central Standard Wheat Bureau of the Ministry of Economic Affairs, Xiaofen Cooperative Co., Ltd. 颦 Α \ 834ί A7 ΙΪ7 V. Description of the invention V) • Resolution: Scanning electron microscope is used to measure the minimum high resolution bottom dimension when analyzed with proper exposure. • Residual film rate: Calculate (film thickness after development / film thickness after pre-baking) X 1 0 0, 90% or more as 0, and less than 90% as X. • Transparency: On the glass substrate with the obtained pattern, use a spectrophotometer (trade name: U — 3 2 1 0, manufactured by Hitachi, Ltd.) to measure only the coating film at 4 0 to 8 0 0 Transmission in nm. At this time, the minimum transmittance (that is, the transmittance at a wavelength of 400 nm) is more than 95%, and 0, and less than 95% is X. • Heat resistance After heating the glass substrate with the obtained pattern for another hour at 220 ° C, measure the residual film rate and the film thickness before heating (film thickness after post-baking) after heating and Transmittance after heating (transmittance at wavelength 400 nm)
D 加熱後之殘膜率在9 5 %以上的情形爲〇,未滿9 5 %的情形爲X。 加熱後之透過率在9 5 %以上的情形爲〇,未滿9 5 本紙張尺度適用中國國家標隼(ϋ ) λ^Μ ίίοχζϋϋΤ- - 20 - (請先閱讀背面之注意事項"填寫本頁) 裝 訂 ο線 經濟部智慧財產局員工消費合作社印製 418347 A7 _ B7 五、發明說明(18 ) %的情形爲X。 •耐藥品性: 對附有所有的圖型之玻璃基片上,分別施以2 w t % 氫氧化鈉水溶液於4 0 °C 1 5分鐘浸漬處理(以下簡稱爲 NaOH處理),l〇wt%鹽酸水溶液於40°C30分 鐘浸漬處理(以下簡稱爲H C1處理),Ν —甲基吡咯烷 酮中於4 0°C 3 0分鐘浸漬處理(以下簡稱爲ΝΜΡ處理 ),及異丙醇中4 0°C 3 0分鐘浸漬處理(以下簡稱爲1 P A處理)後,測定各處理前後的膜厚之變心率,各處理 前後的透過率之變化率,及觀察塗膜表面之變化。 以各處理前後的透過率之變化率未滿1 %之情形爲〇 ,在1 %以上的情形爲X。 以觀察塗膜表面而未變化的情形爲〇,有塗膜粗糙等 之變化的情形爲X。 y施例2 於附有攪拌葉之已氮氣取代的可分離式5 0 〇m 1燒 瓶內,饋入N,N-二甲基乙醯胺16 0g,2 — 丁氧乙 醇4 0 g,上述合成例2而得的驗可溶性樹脂4 4 g,攪 拌使均勻的溶解後,加入Allonix M305 (商品名:東亞合成 化學工業股份有限公司)製造)26 . 4g,Ingacure 907 ( 商品名:CIBA GEIGY公司)製造)8 . 8g,2 一 /3 —萘甲醯亞甲基)一3 —甲基苯並噻唑啉0. 22g ^纸張尺度適用中國國家標準(CNS>A4規格(210 X 297公釐) -21 - —:---------^3 裝--------:訂 ---------碌:)' -(請先閱讀背面之注意事項再填寫本頁) 418347 經濟部中央樣率局員工消费合作社印製 A7 B7 一______________ 五、發明説明仿 ) 使溶解成均勻後’投入Byk — 3 44 ( Byk Chemie股份 有限公司)製造)Ο . 1 4 g,在室溫攪拌1小時’以孔 徑0 . 2 2 // m之薄膜過濾器過濾,而得感光性樹脂組成 物之溶液。 其後,與實施例1同法形成圖型’進行評估。評估結 果示於表1。 (比較例1 ) 於附有攪拌葉之已氮氣取代的可分離式5 0 0 m 1燒 瓶內,饋入N,N —二甲基乙醯胺1 6 0 g > 2 — 丁氧乙 醇4 0 g,上述合成例3而得的鹼可溶性樹脂4 4 g ’攪 拌使均勻的溶解後,加入Allonix M305(商品名:東亞合成 化學工業股份有限公司)製造)26 . 4g,Irgacure 9 07 ( 商品名:CIBA GEIGY 公司)製造)8.8g, 2 —(/5 -萘甲醯亞甲基)一3 —甲基苯並噻唑啉0 . 2 2g,使溶解成均勻後,投入Byk — 344 (Byk Chemic股份有限公司)製造)◦ . 14g,在室溫攪拌1 小時,以孔徑0 · 2 2 M m之薄膜過濾器過濾,而得感光 性樹脂組成物之溶液。 其後,與實施例1,2同步,形成圖型,進行評估。 評估結果示於表1。 (#.先閱讀背而之注意事項存填寫本頁)D: When the residual film rate after heating is 95% or more, it is 0, and when it is less than 95%, it is X. The case where the transmittance after heating is above 95% is 0, and the paper size is less than 95. The Chinese national standard 隼 (适用) λ ^ Μ ίίχχϋϋ--20-(Please read the precautions on the back first and fill in this Page) Binding ο Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 418347 A7 _ B7 V. Description of invention (18)% of cases are X. • Chemical resistance: On the glass substrate with all the patterns, apply 2 wt% sodium hydroxide aqueous solution at 40 ° C for 15 minutes (hereinafter referred to as NaOH treatment), 10 wt% hydrochloric acid Aqueous solution was immersed at 40 ° C for 30 minutes (hereinafter referred to as H C1 treatment), N-methylpyrrolidone was immersed at 40 ° C for 30 minutes (hereinafter referred to as NMP treatment), and 40 ° C in isopropanol After 30 minutes of dipping treatment (hereinafter referred to as 1 PA treatment), the heart rate of film thickness before and after each treatment, the rate of change of transmittance before and after each treatment, and the change of the surface of the coating film were observed. The case where the change rate of the transmittance before and after each treatment is less than 1% is 0, and the case where it is 1% or more is X. The case where the surface of the coating film is not changed is 0, and the case where the coating film is roughened is X. Example 2 In a separable 500 m 1 flask replaced with nitrogen with a stirring blade, N, N-dimethylacetamide 160 g, 2-butoxyethanol 40 g, as described above, were fed. 4 g of soluble resin obtained in Synthesis Example 2 was stirred and dissolved uniformly, and then Allonix M305 (trade name: manufactured by Toa Synthetic Chemical Industry Co., Ltd.) was added. 26. 4 g, Ingacure 907 (trade name: CIBA GEIGY) ) Manufactured) 8.8g, 2/3 / 3-naphthalenemethylene) -3-methylbenzothiazoline 0.22g ^ Paper size applies to Chinese National Standard (CNS > A4 specification (210 X 297 mm) ) -21-—: --------- ^ 3 Pack --------: Order --------- Lu :) '-(Please read the notes on the back first (Fill in this page again) 418347 Printed by the Consumer Sample Cooperative of the Central Sample Rate Bureau of the Ministry of Economic Affairs A7 B7 A. ______________ V. Description of the invention) After dissolving into a homogeneous solution, it is' invested in Byk — 3 44 (by Byk Chemie Co., Ltd.) 〇. 14 g, stirred for 1 hour at room temperature ', and filtered through a membrane filter with a pore size of 0.2 2 // m to obtain a solution of a photosensitive resin composition. Thereafter, a pattern was formed in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1. (Comparative Example 1) In a separable 500 m 1 flask substituted with nitrogen with a stirring blade, N, N-dimethylacetamide 1 600 g was fed and 2-butoxyethanol 4 0 g, alkali-soluble resin 4 obtained from Synthesis Example 3 above 4 g 'After stirring to dissolve uniformly, add Allonix M305 (trade name: Toa Synthetic Chemical Industry Co., Ltd.) 26.4 g, Irgacure 9 07 (product Name: manufactured by CIBA GEIGY) 8.8g, 2-(/ 5-naphthalenemethylene) -3-methylbenzothiazoline 0.22g, after dissolving to homogeneity, put Byk — 344 (Byk (Manufactured by Chemic Co., Ltd.) ◦. 14 g, stirred at room temperature for 1 hour, and filtered through a membrane filter with a pore size of 0.22 M m to obtain a solution of a photosensitive resin composition. Thereafter, in synchronism with Examples 1 and 2, a pattern was formed and evaluated. The evaluation results are shown in Table 1. (# .Please read the back of the note and fill in this page)
本紙張尺度適用中國國家標準(CNS ) Λ4規梠(210乂 297公_# > -22- 經濟部智慧財產局員工消費合作社印製 4 18 3 4 7 a? ' B7 五、發明說明(2〇 ) 耐藥品性 膜面 變化 〇 I PA處理 透過率 變化率 〇 〇 〇 膜厚變 化率 〇 〇 〇 ίΜΡ處理 膜面變 化 〇 〇 〇 透過率 變化率 〇 〇 〇 膜厚變 化率 〇 〇 〇 [C 1處璀 膜面變 化 〇 〇 〇 透過率 變化率 〇 〇 〇 膜厚變 化率 〇 〇 〇 N a ΟΗ處理 膜面 變化 〇 〇 〇 i透過率 :變化率 〇 〇 〇 膜厚變 化率 〇 〇 〇 耐熱性 透過率 〇 〇 〇 殘膜率 〇 〇 〇 透明性 〇 〇 〇 殘膜率 〇 〇 X 解像度 [/^m] 靈敏度 [mj/cm2] t-^ 嵐_1 麵丨J2 t麵1 (請先閱讀背面之注意事項再填寫本頁) ^裝--------;訂j----- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -23-This paper size applies Chinese National Standards (CNS) Λ4 Regulations (210 乂 297) _ # > -22- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 4 18 3 4 7 a? 'B7 V. Description of the invention (2 〇) Chemical resistance film surface change 〇 PA PA transmission rate change rate 〇OO film thickness change rate 〇〇ίΜΡ treatment film surface change 〇 Transmission rate change rate OO film thickness change rate OO [C 1 change in the film surface, the rate of change in the transmittance, the rate of change in the thickness of the film, and the change in the surface of the treated film. The transmittance of the change: the rate of change. The rate of change in the film thickness. Sexual transmittance: 00 residual film rate: 00 transparency: 00 residual film rate: 0 × Resolution [/ ^ m] Sensitivity [mj / cm2] t- ^ Lan_1 plane 丨 J2 t plane1 (please first Read the precautions on the reverse side and fill in this page) ^ ------------ Order j ----- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -23-
A t83 4T A7 El 五、發明説明W ) 如表1所示般,屬於本發明之範圍的實施例1及2之 含有由含以一般式(1 )表示的自由基聚合性化合物(a 一 2 )成分之鹼可溶性樹脂〔A〕與具有至少一個以上的 乙烯性不飽和和雙鍵鍵結之化合物〔B〕,及光聚合引發 劑〔C〕之感光性樹脂組成物,由於紫外線及熱,鹼可溶 性樹脂〔A〕及具有至少一個以上乙烯性不飽和雙鍵鍵結 之化合物〔B〕會引起化學鍵結(交聯),故與採用比較 例1之未含有以一般式(1 )表示的自由基聚合性化合物 (a - 2 )之鹼可溶性樹脂〔A〕的情形相比,曝光部及 未曝光部之對鹼顯影液之溶解速度差變大’得知可得顯影 後之殘膜率,靈敏度及解析度優越的圖型被膜。 又,在透明性,耐熱性及耐藥品性方面亦優越’實用 上不僅無任何問題,或由上述的優越特性亦顯而可知用作 於有源矩陣型之L C D的T F T與透明電極之間配設的透 明絕緣膜,於定向膜及透明電極之間配設的透明絕緣膜或 配設於濾色鏡之保護膜係尤其有用的。 經濟部中央標率局貝工消费合作社印製 再者,由相關的特性,可顯而得知本發明之感光性樹 脂組成物,係較合適使用作P D P之透明絕緣膜或保護膜 ,或L E D發光體之保護膜。 發明之功效 如上述般,依本發明,由於係予作成配合指定的鹼可 溶性樹脂,具有至少一種乙烯性不飽和雙鍵鍵結之化合物 及光聚合引發劑,可提供在靈敏度’解析度,透明性’耐 本紙張尺度適用中國國家標率(CNS ) Λ4規私(210 X 297公垃) -24 - t 418341 五、發明説明如) 熱性及耐藥品性均衡的負片型感光性樹脂組成物,及使用 此組成物之各種顯示元件。 亦即,利用本發明之感光性樹脂組成物,可形成在靈 敏度,解析度,透明性,耐熱性及耐藥品性等全部優越的 被膜圖型,相關的被膜圖型,可較合適的使用作於構成液 晶顯示元件之T F T及透明電極間形成的透明絕緣膜,定 向膜及透明電極間形成的透明絕緣膜及濾色鏡上形成的保 護膜,亦可適用於PDP或LED發光體。 圖式之簡單說明 第1圖爲表示採用於感光性樹脂組成物之特性評估的 掩膜圖型之平面圖。 ; - 裝 Γ* 訂"ϊ 遢 _ (¾^閱讀背面之注意寧項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 本紙張尺度適用中國國家摞準(CNS ),\4规#, ( 2〗ΟΧ29·7*^ ) -25A t83 4T A7 El V. Description of the invention W) As shown in Table 1, Examples 1 and 2 which belong to the scope of the present invention contain a radical polymerizable compound (a-2) represented by the general formula (1). ) The alkali-soluble resin [A] and the photosensitive resin composition having at least one ethylenically unsaturated and double-bonded compound [B] and the photopolymerization initiator [C], due to ultraviolet rays and heat, The alkali-soluble resin [A] and the compound [B] having at least one ethylenically unsaturated double bond bond cause chemical bonding (crosslinking). Therefore, it is the same as that in Comparative Example 1 which does not contain Compared with the case of the alkali-soluble resin [A] of the radically polymerizable compound (a-2), the difference between the dissolution rate of the alkali developer in the exposed portion and the unexposed portion becomes larger. , Graphic coating with superior sensitivity and resolution. In addition, it is superior in transparency, heat resistance, and chemical resistance. Not only is there no problem in practical use, or it can be seen from the above-mentioned superior characteristics that the TFT used in the active matrix LCD and the transparent electrode are compatible. The transparent insulating film provided is particularly useful as a transparent insulating film provided between the alignment film and the transparent electrode or a protective film provided in a color filter. Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. From the relevant characteristics, it can be clearly known that the photosensitive resin composition of the present invention is a transparent insulating film or protective film suitable for PDP, or LED. Protective film for luminous body. The effect of the invention is as described above. According to the present invention, a compound having a specified alkali-soluble resin, at least one ethylenically unsaturated double bond bond, and a photopolymerization initiator can be provided. The properties of this paper are applicable to China National Standards (CNS) Λ4 Regulations (210 X 297 public waste) -24-t 418341 5. Invention description such as) Negative-type photosensitive resin composition with balanced heat resistance and chemical resistance, And various display elements using this composition. That is, by using the photosensitive resin composition of the present invention, it is possible to form a coating pattern that is superior in sensitivity, resolution, transparency, heat resistance, and chemical resistance, etc., and the relevant coating pattern can be suitably used as The transparent insulating film formed between the TFT and the transparent electrode constituting the liquid crystal display element, the transparent insulating film formed between the alignment film and the transparent electrode, and the protective film formed on the color filter can also be applied to PDP or LED light emitters. Brief Description of the Drawings Fig. 1 is a plan view showing a mask pattern used for evaluating the characteristics of a photosensitive resin composition. ;-Install Γ * Order " ϊ 遢 _ (¾ ^ Please read the note on the back, and then fill out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, this paper is printed in accordance with China National Standards (CNS), \ 4 Rule #, (2 〖〇Χ29 · 7 * ^) -25