200900854 九、發明說明： 【發明所屬之技術領域】 本發明係關於感光性樹脂組成物。更詳言之，係關於 可適用於耐焊劑（solder resist)、各種塗布漆、接著劑、印 刷油墨用黏著劑、彩色濾光片用黏著劑等，且可形成優異 的耐熱性、與基板之密接性、顯影特性之硬化塗膜之感光 性樹脂組成物。 【先前技術】 近年來，從節省資源、節省能源之觀點來看，在印刷、 塗料、接著劑之領域中已廣泛地使用可藉由紫外線或電子 線予以硬化之放射線硬化型樹脂。即使是印刷配線板等電 子機器領域，爲了能夠長時間保護搭載零件後之電路板， 亦已採用耐焊劑。作爲以光阻法使用於印刷配線板之材 料，通常爲酸懸吊型酚醛環氧樹脂，惟與銅電鍍之密接性 不夠充分，在作爲多層印刷配線板用來使用的情況下，除 了有導體電路間的密接強度不夠充分之問題外，尙有由於 可撓性亦爲惡劣，故容易碎裂之問題。 爲解決此等課題，已提議一種在使用（甲基）丙烯酸共 聚物之感光性樹脂組成物中混合無機塡料之方法（例如，專 利文獻1 )，但是仍有對酸懸吊型酚醛環氧樹脂之耐熱性差 之問題。 在彩色液晶顯示裝置、固體攝影元件中係使用彩色濾 光片，此等係由在基板上以指定圖案著色紅（R)、綠（G)、 藍（B)等色之著色塗膜、與該等之間之黑色的黑矩陣所構 200900854 成。通常’在玻璃等透明基板上形成黑矩陣，接著 成R、G、B等著色塗膜圖案來製成。 一般而言’彩色濾光片係以染色法、印刷法、 散法或電解沈積法等製造方法來製造。其中，特別 以鹼可溶性樹脂、反應性單體、光聚合啓發劑、顏 劑爲主體之光硬化性樹脂組成物，在透明基板上重 塗布、曝光、顯影、後硬化之微影術工法所製成之 散法，因耐光性·耐熱性等耐久性優異，且針孔等缺 而成爲現今的主流。 顏料分散法係具有上述優點，然而另一方面由 地形成矩陣、R、G、B等圖案，故要求成爲塗膜之 的鹼可溶性樹脂具有高耐熱性、與基板之密接性。 作爲提升鹼可溶性樹脂之耐熱性的方法，迄 議：將在側鏈上具有環狀構造之（甲基）丙烯酸酯當 合成分之樹脂組成物（例如，專利文獻2)、或將含馬 胺之單體作爲共聚合成分之樹脂組成物（例如，專利 等。 然而，前者之將在側鏈上具有環狀構造之（甲3 酸酯當作共聚合成分之樹脂組成物，爲提升耐熱性 其使用比率增加時，則有與基板之密接性下降之問 對於在顯影步驟使用之顯影液之樹脂溶解性下降’ 在顯影步驟中之時間變長，甚至變得無法顯影’而 指定圖案之問題、或是即使已經得到圖案，但爲了 膜，進行實施加熱處理後，在硬化時側鏈被熱分解 依序形 顏料分 是採用 料及溶 複進行 顏料分 陷少， 於重複 黏著劑 今已提 作共聚 來醯亞 文獻3) I )丙烯 ，而使 題、或 且不僅 得不到 固定塗 而成爲 200900854 揮發性成分，而污染了生產線之問題。 後者之將含馬來醯亞胺之單體作爲共聚合成分之樹脂 組成物，則有由於分子中含有氮原子，導致由黃色著色爲 黃褐色，使塗膜之透明性惡化。此外，進行加熱處理後， 在硬化時被更進一步地著色之問題。 專利文獻1 :特開2006- 1 90848號公報 專利文獻2:特開2004-240396號公報 專利文獻3 :特開2 0 0 3 - 2 9 0 1 8號公報 【發明內容】 發明所欲解決之問顆 本發明之目的係提供一種感光性樹脂組成物，除了具 有可用於微影術步驟之顯影特性，還可形成耐熱性、密接 性、透明性亦優異之硬化塗膜。 解決問顆之羊段 本發明人等爲了解決上述課題，進行了鑽硏探討。其 結果發現，包括含有以分子中具有2個以上的羥基之聚合 性單體（a-1)、與分子中具有亦可持有碳數6〜20之交聯構 造的脂環式骨架之聚合性單體（a-2)作爲必要成分之共聚物 的樹脂組成物係解決了上述課題，根據此發現而完成了本 發明。 也就是說，本發明之感光性樹脂組成物，其係含有聚 合物成分（A)與光聚合性單體（B)而成之感光性樹脂組成 物’其特徵爲聚合物成分（A)係含有以分子中具有2個以上 的羥基之聚合性單體（a_l)、與分子中具有亦可持有碳數6 200900854 〜20之交聯構造的脂環式骨架之聚合性單體（a — 2)作爲必要 單體成分而成之聚合物。 發明之効罢 若根據本發明，可以提供一種感光性樹脂組成物，其 係除了具有可用於微影術步驟之顯影特性外，尙可形成耐 熱性、密接性、透明性亦優異之硬化塗膜。 又’由本發明之感光性樹脂組成物所形成之硬化塗膜 係對玻璃基板或半導體基板之耐熱性·密接性優異，由於具 有鹼顯影性’因而在各種光阻領域之利用價値極高。 【實施方式】 复A發明之昜佳形態 以下詳細地說明本發明。 本發明之感光性樹脂組成物係藉由含有以分子中具有 2個以上的羥基之聚合性單體（a-1；)、與分子中具有亦可持有 碳數6〜20之交聯構造的脂環式骨架之聚合性單體（a_2)作 爲必要單體成分而成之共聚物作爲聚合物成分（A)，而除了 具有可用於微影術步驟之顯影特性以外，尙可形成耐熱 性、密接性、透明性亦優異之硬化塗膜。 以下，針對聚合物成分（A)加以説明。 分子中具有2個以上的羥基之聚合性單體（a-丨）係無特 別限定’作爲其具體例，可舉出丙三醇單（甲基）丙烯酸酯、 丁二醇單（甲基）丙烯酸酯、戊三醇單（甲基）丙烯酸酯等伸烷 基多醇單（甲基）丙烯酸酯類、咖啡因酸、莽草酸等。其中， 由密接性、顯影特性之點而言，特佳爲丙三醇單（甲基）丙 200900854 烯酸酯。 得到前述聚合物成分（A)之際，單體成分中之在分子中 具有2個以上的羥基之聚合性單體（a-1)的比例係無特別限 制，在全部單體成分中爲3〜30莫耳％，較佳爲5〜20莫耳 %，更佳爲5〜1 5莫耳％。該聚合性單體（a-1)係在該範圍内 時，除了密接性等塗膜性能亦爲足夠外，由於羥基之導入 量正好恰當地維持，故感光性樹脂組成物溶液之黏度不會 變高，由於亦不需使感光性樹脂組成物中的溶劑比率變 高，故摻合的自由度高。又，相對地，可藉由使其他單體 之摻合比率變高，而亦不使耐熱性降低，對於後述之鹼顯 影中必要的羧基、光硬化中必要的感光性基之導入量亦無 限制。 該聚合性單體（a -1)係由於用以賦予顯影性、密接性之 機能高，故最終摻合比例爲少，是以相對地賦予耐熱性之 聚合性單體、賦予顯影性之聚合性單體、或賦予感光性之 聚合性單體的摻合比例可以爲多，而可兼備作爲聚合物成 '」 分（A)之顯影性·感光性、以及耐熱性.密接性。 作爲分子中具有亦可持有碳數6〜20之交聯構造的脂 環式骨架之聚合性單體（a-2) ’其具體例可舉出（甲基）丙烯 酸環己酯、（甲基）丙烯酸甲基環己酯、（甲基）丙烯酸乙基環 己酯、（甲基）丙烯酸二環己酯、單（甲基）丙烯酸-1，4 -環己烷 二甲醇酯、（甲基）丙烯酸三環癸酯、（甲基）丙烯酸三環癸基 氧乙酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烯 基氧乙酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸金剛烷 200900854 酯、（甲基）丙烯酸松香酯、（甲基）丙烯酸降冰片烯酯 基）丙烯酸-5-甲基降冰片烯酯、（甲基）丙烯酸-5-乙基降 烯酯等（甲基）丙烯酸酯類；α-蒎烯、α-萜品醇（a_terpeni 在分子内持有C-C雙鍵之單萜烯類；降冰片烯、5-甲基 片烯、5-降冰片烯-2-羧酸、5-降冰片烯-2,3-二羧酸、 冰片烯-2,3-二羧酸酐等環烯類等。該等之中，尤其由 性之點而言，以（甲基）丙烯酸環己酯、（甲基）丙烯酸三 酯、（甲基）丙烯酸松香酯、降冰片烯爲較佳。 ^ 得到前述聚合物成分（A)之際，單體成分中之分子 有亦可持有碳數6〜20之交聯構造的脂環式骨架之聚 單體（a-2)的比例係無特別限制，宜爲全單體成分中2 莫耳％，較佳爲5〜20莫耳％，更佳爲5〜15莫耳％。 合物（a-2)在該範圍内，相對地其他單體之摻合比率亦 變低，與基板之密接性變得充分’後述之鹼顯影中必 羧基、光硬化中必需的感光性基之導入量亦無限制。 由於亦可持有交聯構造之脂環式骨架的導入量並沒 多，故樹脂對顯影液的溶解性不會降低，在顯影步驟 費的時間亦不會變長，不會無法顯影，而可得指定圖 又，耐熱性等塗膜性能亦充分。 前述聚合物成分（A)係酸價爲20〜180 mgKOH/g， 爲 30 〜150 mgK〇H/g，更佳爲 40 〜140 mgKOH/g。 若酸價在該範圍内，則可得充分之鹼顯影特性。 是說，如果酸價在該範圍内，對鹼顯影液的溶解性變 分，而沒有硬化部分時而溶解於鹼顯影液、時而膨潤 、（甲 冰片 〇1)等 降冰 5-降 耐熱 環癸 中具 合性 丨〜3 0 若化 可不 需的 又， 有變 中花 案。 較佳 也就 得充 之情 200900854 形。 前述聚合物成分（A)係重量平均分子量（GPC法之聚苯 乙烯換算數値）較佳爲5000〜80000。若重量平均分子量在 該範圍内的話，耐熱性、可撓性不會下降，對鹼顯影液的 溶解性亦變得充分。 關於在前述聚合物成分（A)導入酸價，已知將不飽和— 價酸U-3)作爲共聚合成分使用（共聚物（A-1)、共聚物 (A-2))、或使將具有環氧基之自由基聚合性化合物（a-5)作爲 f ；ι 共聚合成分使用之共聚物的環氧基與不飽和一價酸（a - 3)反 應後，使生成之羥基或共聚合成分（a-Ι)之羥基與多價酸酐 (a-6)反應（共聚物（A-3))之方法。 共聚物（A-1)係將（a-Ι)與（a-2)、（a-3)及（a-4)予以共聚合 而得，其共聚合比率係全單體成分中，（a-Ι)爲3〜30莫 耳％，較佳爲5〜20莫耳％，更佳爲5〜15莫耳％; (a-2)爲 3〜30莫耳％，較佳爲5〜20莫耳％，更佳爲5〜1 5莫耳％ ; (a-3)爲20〜70莫耳％，較佳爲20〜60莫耳％，更佳爲20 ^ 〜50莫耳％; (a-4)爲0〜75旲耳％，較佳爲20〜60吴耳％’ 更佳爲25〜50莫耳％，其合計爲100莫耳％。 使（a -1)爲3〜3 0莫耳％、（ a - 2)爲3〜3 0莫耳％係如前所 述。 (a-3)係用以使共聚物（A-1)之側鏈持有存在羧基之酸 價。作爲本發明之（a-3)的不飽和一價酸’並無特別限定’ 可舉出例如，（甲基）丙烯酸、巴豆酸、桂皮酸等。又’亦 可使用具有1個羥基與1個以上之（甲基）丙烯醯基之多官 200900854 能（甲基）丙烯酸酯（例如，（甲基）丙烯酸羥基乙酯、（甲基） 丙烯酸羥基丙酯、（甲基）丙烯酸羥基丁酯、二（甲基）丙烯酸 三羥甲基丙烷酯等）與多價酸酐之反應物等。該等之中，較 佳爲使用（甲基）丙稀酸。該等亦可併用1種或2種以上。 作爲（a -1 )、（ a - 2)及（a - 3)以外之自由基聚合性化合物 (a-4)，只要爲具有乙烯性不飽和基者，即無特別限定。作 爲其具體例，可舉出丁二烯、2,3 -二甲基丁二烯、異戊二烯、 氯丁二烯等二烯類；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙 酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙 烯酸正丁酯、（甲基）丙烯酸第二丁酯、（甲基）丙烯酸第三丁 酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸新戊酯、（甲基）丙烯 酸苄酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸己酯、（甲基） 丙烯酸2 -乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸十 二酯、（甲基）丙烯酸環戊酯、（甲基）丙烯酸烯丙酯、（甲基） 丙烯酸炔丙酯、（甲基）丙烯酸胡椒酯、（甲基）丙烯酸水楊 酯、（甲基）丙烯酸呋喃酯、（甲基）丙烯酸糠酯、（甲基）丙稀 酸四氫呋喃酯、（甲基）丙烯酸吡喃酯、（甲基）丙烯酸苯乙 酯、（甲基）丙烯酸甲苯酚酯、（甲基）丙烯酸三氟乙酷、 (甲基）丙烯酸全氟乙酯、（甲基）丙烯酸全氟正丙酯、（甲基） 丙烯酸全氟異丙酯、（甲基）丙烯酸三苯基甲酯、（甲基）丙稀 酸異丙苯酯、（甲基）丙烯酸3-(N，N-二甲基胺基）丙酯、（甲 基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基） 丙烯酸萘酯、（甲基）丙烯酸蒽酯等（甲基）丙烯酸酯類；（甲基） 丙烯酸醯胺、（甲基）丙烯酸N，N-二甲基醯胺、（甲基）丙烯酸 200900854 N，N-二乙基醯胺、（甲基）丙烯酸N，N-二丙基醯胺、（甲基） 丙烯酸N，N -二異丙基醯胺、（甲基）丙烯酸蒽基醯胺等（甲基） 丙烯酸醯胺；（甲基）丙烯酸醯苯胺、（甲基）丙烯醯基腈、丙 嫌酸、氯化乙烯、氯化亞乙烯、氟化乙烯、氟化亞乙烯、 N-乙烧基吡咯啶酮、乙烯基吡啶、乙酸乙烯酯等乙烯基化 合物；苯乙烯、苯乙烯之α-、〇_、m-、P-烷基、硝基、氰基、 醯胺衍生物；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙 醋、伊康酸二乙酯等不飽和二羧酸二酯；N -苯基馬來醯亞 月安' N-環己基馬來醯亞胺、&月桂基馬來醯亞胺、n_(4_羥 @$基）馬來醯亞胺等單馬來醯亞胺類；N-(甲基）丙烯醯基 苯二甲醯亞胺等。上述之中，由硬化塗膜之密接性、透明 性的觀點而言，較佳爲使用（甲基）丙烯酸苄酯、（甲基）丙烯 酸2-徑基乙酯、苯乙烯或乙烯基甲苯。該等係可倂用1種 或2種以上。 用以得到共聚物（A _ 1)之自由基共聚合反應係無特別 限·帝j 可適用迄今進行之_般自由基聚合法。例如，藉由 在丙一醇單甲基醚、丙二醇單甲基醚乙酸酯之類的二醇醚 系之溶劑、不具有甲苯或二甲苯之類的烴系或乙酸乙酯之 類的官能基之有機溶劑中’以所期望的比率溶解上述 (a·1)' (a-2)較佳爲（a_3)及（a-4)之共聚合成分，混合偶氮雙 異丁 ^、偶氮雙異戊腈、過氧化苯甲醯 '己酸過氧化第三 丁基-2'乙酯之類的聚合啓發劑，在迴流狀態、以5〇〜i 30 C左右，聚合1〜20小時左右，而得共聚物（Α_ι)之有機溶 劑溶液。聚合啓發劑之使用量係相對於（a_1：)、（a_2)、（a_3) 200900854 及（a-4)之合計量100質量份而言，通常爲0.5〜20質量份 左右，較佳爲1.0〜1 0質量份。 亦可不使用有機溶劑，僅以（a -1)、（ a - 2)、（ a - 3 )及（a - 4) 與聚合啓發劑進行塊狀聚合。 相對於（a-1)、（a-2)、（a-3)及（a-4)之合計量100質量份 而言，有機溶劑之使用量係通常爲30〜1 000質量份左右， 較佳爲50〜800質量份左右。藉由使有機溶劑之使用量爲 1 0 00質量份以下，防止因鏈轉移作用導致共聚物（A-1)之分 f ' 子量降低，且能夠將最終所得之共聚物（A-1)的固體成分濃 度控制在適切之範圍內。 藉由成爲30質量份以上，能夠防止異常的聚合反應， 而進行安定的聚合反應，可以防止樹脂著色、膠化。 本發明之共聚物（A -1)係當作混合後述反應性稀釋 劑、溶劑而成之感光性樹脂組成物，由於主要是作爲光阻 等電子材料使用，故以上述之類的自由基共聚合法製造共 聚物（A-1)之際，較佳係使用丙二醇單甲基醚乙酸酯之類的 r ； 八 i 二醇酯系溶劑。 共聚物（A-2)係將（a-1)、（a-2)、（a-3)及（a-4)予以共聚 合’使所得共聚物中之羧基與（a-5)成分反應而得。 (a-2)、（a-3)及（a-4)之共聚合比率係與共聚物（A-1)相同，惟 進一步使存在於側鏈之羧基與（a-5)之具有環氧基的自由基 聚合性化合物反應，將部分羧基轉換爲不飽和基。相胃M 存在於共聚物之側鏈的羧基100莫耳而言，（a-5)之具有·環 氧基的自由基聚合性化合物之使用量係5〜80莫耳。藉由 -14- 200900854 控制在5〜80莫耳內’羧基與不飽和基的平衡良好，且共 聚物（A - 2)之硬化性及鹼顯影性維持適當。 (a-1)、（a-2)、（a-3)及（a-4)之共聚合反應係可在與共聚 物（A-1)相同條件下反應。 作爲（a-5)之具有環氧基的自由基聚合性化合物，並無 特別限定，可舉出例如（甲基）丙烯酸縮水甘油酯、具有環 式環氧基之（甲基）丙烯酸3,4-環氧基環己基甲酯及其內酯 加成物[例如，Daicel化學工業（股）製 Cyclomer-A200、 ' M100]、3,4-環氧基環己基甲基-3’，4’-環氧基環己烷羧酸酯 之單（甲基）丙烯酸酯、（甲基）丙烯酸二環戊烯酯之環氧基化 物、（甲基）丙烯酸二環戊烯基氧乙酯之環氧基化物等，惟 從原料取得容易而言，較佳爲使用（甲基）丙烯酸縮水甘油 酯及（甲基）丙烯酸3,4-環氧基環己基甲酯。該等係可併用1 種或2種以上。 關於使共聚物中之羧基與U-5)之具有環氧基的自由基 聚合性化合物反應，係如下進行。也就是說’爲了防止不 飽和一價酸和含生成之不飽和基之共聚物的聚合所導致之 膠化。在氫醌、甲基氫醌、氫醌單甲基醚、氧等聚合防止 劑之存在下，並且在三乙基胺之類的三級胺、三乙基苄基 氯化銨之類的四級銨鹽 '三苯基膦之類的磷化合物、鉻之 螯合物化合物等觸媒之存在下，通常以50〜15〇°C左右 '較 佳爲8 0〜1 3 0 T：進行反應。在用以得到共聚物之自由基共聚 合反應使用有機溶劑的情形，可將共聚物有機溶劑之溶液 狀態原樣地用於以後之反應。 15- 200900854 共聚物（A-3)係使（a-l)、（a-2)、（a-5)及（a-4)進 f了共聚 合，並使所得之共聚物中的環氧基與（a-3)反應後，使生成 之羥基或（a _ 1)之羥基與多價酸酐之（a - 6)反應而得。（a -1)、 (a-2)、（a-5)及（a-4)之共聚合比率係全單體成分中’ U-1)爲 3〜30莫耳％、較佳爲5〜20莫耳％、更佳爲5〜15莫耳％’ (a-2)爲3〜30莫耳％、較佳爲5〜20莫耳％、更佳爲5〜15 莫耳％，（a-5)爲30〜85莫耳％、較佳爲30〜70莫耳％、更 佳爲30〜60莫耳％’（a_4)爲〇〜05莫耳％、較佳爲丨5〜55 莫耳％、更佳爲25〜50莫耳％ ’其合計爲100莫耳％。 使（a-Ι)爲3〜30吴耳％、（a-2)爲3〜.30莫耳％係如目υ所 述。 (a-5)係在共聚物的側鏈導入環氧基’用以與之後U-3) 之羧基反應，以導入不飽和基。再者’藉由使所生成之羥 基與多價酸酐之U-6)反應，亦用以導入酸價。因此’所謂 在共聚物（A-2)之側鏈所導入的（a-5)係機能相異、導入量亦 相異，但可使用相同之環氧基化合物。 藉由使（a-5)成爲30〜85莫耳％，可以控制環氧基之導 入量，亦即來自U-3)之不飽和一價酸的不飽和基之導入量， 而能夠控制共聚物（A-3)之硬化性。藉由使（a-1)、（a-2)及 (a-5)成爲如上述比率，U-4)係可在〇〜65莫耳％之範圍内 適當地選定。 該共聚物（A-3)爲藉由使上述（a-i)、（a-2)、較佳爲（a-5) 及（a-4)自由基共聚合形成共聚物後，使（a-3)之不飽和一價 酸反應，接著，使U-6)之多價酸酐反應而得。U-3)之不飽 200900854 和一價酸的羧基係與來自（a - 5 )之側鏈的環氧基反應，以將 環氧基開環’且在形成經基的同時於末端賦予不飽和基。 (a-6)之多價酸酐係與由（a-Ι)之羥基或（a-3)中的羧基及來自 (a - 5)之側鏈的環氧基反應所生成之羥基反應，酸酐基係開 環變換爲羧基。 相對於100莫耳之來自（a-5)之側鏈的環氧基而言， (a-3)之不飽和一價酸的使用量係1〇〜；[〇〇莫耳，較佳爲30 〜100莫耳，更佳爲50〜100莫耳。 藉由使不飽和一價酸之使用量爲1 〇莫耳以上，能夠導 入用以硬化樹脂所必需之不飽和基的最低量，藉由使不飽 和一價酸的使用量爲1 0 0莫耳以下，可以減少所得之本發 明共聚物（A-3)中未反應之不飽和—價酸的量。 相對於藉由（a-Ι)之經基及（a_3)中之竣基、與來自於 (a - 5 )之側鏈的環氧基反應所生成羥基合計丨〇 〇莫耳而言， 反應之（a - 6)的多價酸酐使用量係5〜1 〇 〇莫耳，較佳爲1 〇 〜90莫耳’更佳爲20〜90莫耳。藉由使相對於ι〇〇莫耳之 羥基而言’多價酸酐的莫耳數成爲5〜1〇〇莫耳之範圍，可 將所得共聚物（A-3)之酸價（〗IS κ69〇ι)控制於20〜 180mgKOH/g 之範圍。 上述共聚物之經基與多價酸酐（a_6)的反應係在將上述 共聚物中來自（a-5)側鏈之環氧基與（a_3)之不飽和一價酸反 應後’原樣地添加預疋量之該（a_6)，通常爲在50〜150 °C 左右’較佳爲80〜130 °C加熱進行。不需要重新添加觸媒。 作爲本發明共聚物（A-3)中（a_6)之多價酸酐並無特別 200900854 限定，可舉出例如琥珀酸酐、馬來酸酐、檸康酸酐、伊康 酸酐、酞酸酐、四氫酞酸酐、內亞甲基四氫酞酸酐、甲基 四氫酞酸酐、六氫酞酸酐、偏苯三酸酐、均苯四酸酐等。 此等之中，較隹爲使用四氫酞酸酐、琥珀酸酐。該等係可 倂用1種或2種以上。 含有如上所得之共聚物（A-1)〜（A-3)之聚合物成分（A) 與光聚合性單體（B)而成的本發明之感光性樹脂組成物’係 可添加光聚合啓發劑（C)及溶劑（D)。 可使用之光聚合性單體（B)，只要爲可與聚合物成分 (A)反應者，即無特別限制。可舉出例如，苯乙烯、α-甲基 苯乙烯、α-氯甲基苯乙烯、乙烯基甲苯、二乙烯基苯、酞 酸二烯丙酯、二烯丙基苯膦酸酯等芳香族乙烯基系單體類； 乙酸乙烯酯、己二酸乙烯酯等聚羧酸單體類；（甲基）丙烯酸 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯 酸丁酯、（甲基）丙烯酸β-羥基乙酯、（甲基）丙烯酸羥基丙 酯、二（甲基）丙烯酸乙二醇酯、二（甲基）丙烯酸二乙二醇 酯、二（甲基）丙烯酸丙二醇酯、二（甲基）丙烯酸乙二醇酯、 二（甲基）丙烯酸三羥甲基丙烷酯、三（甲基）丙烯酸三羥甲基 丙烷酯、四（甲基）丙烯酸季戊四醇酯、六（甲基）丙烯酸二季 戊四醇酯、參（羥基乙基）三聚異氰酸酯之三（甲基）丙烯酸酯 等（甲基）丙烯酸系單體；三烯丙基氰脲酸酯等。亦可倂用此 等之1種或2種以上。 光聚合性單體（Β)之添加量相對於1〇〇質量份之聚合物 成分（Α)而言，通常爲10〜200質量份，較佳爲20〜150質 200900854 量份。 藉由在上述範圍内，可以將光硬化性保持於適當範圍 內，再者，亦能夠調整黏度。 作爲可添加於感光性樹脂組成物之溶劑（D) ’只要爲不 與聚合物成分（A)及光聚合性單體（B)反應之惰性溶劑，即 無限制而可以使用。 作爲可利用之溶劑（D )，可舉出丙二醇單甲基醚、丙二 醇單甲基醚乙酸酯、二丙二醇單甲基醚乙酸酯、乙酸乙酯、 5 乙酸丁酯、乙酸異丙酯、丙二醇單甲基醚、二丙二醇單甲 基醚、三丙二醇單甲基醚、乙二醇單甲基醚、二乙二醇單 甲基醚、甲基乙基酮、甲基異丁基酮、環己酮、乙二醇單 乙基醚乙酸酯、二乙二醇乙基醚乙酸酯等。此等之中，較 佳爲使用在前述自由基聚合反應中較佳使用之丙二醇單甲 基醚乙酸酯。 溶劑（D)之添加量係相對於1 00質量份之聚合物成分 (A)而言，通常爲30〜1000質量份，較佳爲50〜800質量份。 ' 藉由爲上述範圍，可將黏度保持適度。 本發明之感光性樹脂組成物係利用紫外線等活性光作 爲活性能量線進行光硬化的情況下’添加光聚合啓發劑 (C)。作爲可利用之光聚合啓發劑（C)並無特別限定，可舉出 例如，苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚等苯偶姻及 其垸基醚類；苯乙酮、2,2 -二甲氧基-2-苯基苯乙酮、ι，ΐ -二 氣苯乙酮、4-(1-第三丁基一氧基-1-甲基乙基）苯乙酮等苯乙 酮類；2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌、1 —氯蒽 -19- 200900854 醌等蒽醌類；2,4 -二甲基噻吨酮、2,4 -二異丙基噻吨酮、2-氯噻吨酮等噻吨酮類；苯乙酮二甲基縮酮、苄基二甲基縮酮 等縮酮類；二苯甲酮、4-(1-第三丁基二氧基-1-甲基乙基）二 苯甲酮、3,3’，4,4’·肆（第三丁基二氧基羰基）二苯甲酮等二 苯甲酮類；2-甲基-1-[4-(甲基硫）苯基]-2-嗎福啉基-丙烷-1-酮或2 -节基-2-二甲基胺基-1-(4 -嗎福啉基苯基）丁酮-1;戊 基氧化膦類及咕吨酮類等。該等係可倂用1種或2種以上。 光聚合啓發劑（C)之摻合量係相對於本發明之感光性樹脂 組成物中固體成分100質量份而言，通常宜爲0.1〜30質量 份’較佳爲0.5〜20質量份，更佳爲1〜1〇質量份。藉由爲 0. 1〜3 0質量份’能夠將光硬化性保持在適當範圍。 再者，本發明之感光性樹脂組成物係可視需要含有習 知之著色劑、消泡劑、偶合劑、整平劑等。 作爲該著色劑’可使用無機顏料或有機顏料、染料等 習知著色劑。 作爲可使用之顏料的具體例，可舉出例如，C. I .色素 黃 1、 3、 12、 13、 14、 15、 16、 17、 20、 24、 31、 53、 83、 86、93、94、109、110、117、125、128、137、138、139、 147、148、150、153、154、166、173、194、214 等黃色顏 料；C.I .色素橙 13、31、36、38、40、42、43、51、55、 59、61、64、65、71、73 等橙色顏料；C.I .色素紅 9、97、 105、 122、 123、 144、 149、 166、 168、 176、 177、 180、 192、 209、 215、 216、 224、 242、 254、 255、 264、 265 等紅色顏 料；C.I ·色素藍 15、15: 3、15: 4、15: 6、16、60 等藍色 -20- 200900854 顏料；C.I .色素紫1、19、23、29、32、36、38等紫色顔料；c. I ·色素綠7、36等綠色顏料；C I •色素棕23、25等茶色顏 料；C· I ·色素黑1、7、碳黑、鈦黑、氧化鐵等黑色顏料等。 此等著色劑係可因應目的畫素的顏色，分別單獨使用或組 合2種以上使用。 著色劑之摻合量係無特別限定，相對於本發明之感光 性樹脂組成物中固體成分1 〇〇質量份而言，通常宜爲2〇〜 70質量份’較佳爲25〜60質量份，更佳爲、30〜50質量 、份。 爲了提升顏料之分散性，亦可更添加習知之分散劑。 作爲分散劑，若採用高分子分散劑則經時分散安定性優 異’因而較佳。作爲高分子分散劑，可舉出例如，胺基甲 酸酯系分散劑、聚乙烯亞胺系分散劑、聚氧基伸乙基烷基 醚系分散劑、聚氧基乙二醇二酯系分散劑、脫水山梨糖醇 脂肪族酯系分散劑、脂肪族變性酯系分散劑等。作爲該分 散劑之具體例，以商品名表示可舉出EFK A (EFK A Chemicals B.V.(EFKA)社製）、D1Sperbyk(BYK 化學公司製）、 Disperlon(楠本化成股份有限公司製）、S〇LSPERSE(ZENECA 公司製）等。 分散劑之摻合量係無特別限定，相對於1 00質量份的 所用之顏料而言，通常宜爲1 00質量份以下，較佳爲1〜90 質量份，更佳爲10〜70質量份。 如上所述，本發明之聚合物成分（A)係酸價爲20〜 1 8 0mgKOH/g，因此使用含該等之感光性樹脂組成物的光阻 -21- 200900854 類係可用鹼水溶液進行顯影。 本發明之感光性樹脂組成物係能夠在例如，印刷配線 基板、玻璃基板、陣列基板上，以篩網印刷法、輥塗布法、 簾幕塗布法、噴灑塗布法、旋塗法等予以塗布，使必要部 分光硬化後，將其未硬化（未曝光）部分以鹼水溶液洗去’ 以進行顯影。作爲在顯影所使用之鹼水溶液，可舉出碳酸 鈉、碳酸鉀、碳酸鈣、氫氧化鈉等水溶液，胺系亦有使用 胺基苯酚系化合物，惟較佳係使用P-伸苯二胺系化合物， " 其代表例可舉出3-甲基-4-胺基-N，N-二乙基苯胺、3-甲基- 4-胺基-N-乙基-Ν-β-羥基乙基苯胺、3-甲基-4-胺基-N-乙基 -Ν-β-甲磺醯胺乙基苯胺、3-甲基-4-胺基乙基-Ν-β-甲氧 基乙基苯胺及此等之硫酸鹽、鹽酸鹽、或ρ-甲苯磺酸鹽之 水溶液。 在光照射以使塗布面硬化之際所採用之光源，係使用 低壓水銀燈、中壓水銀燈、高壓水銀燈、氙燈、金屬鹵素 燈等。 ^ 實施例 以下顯示實施例及比較例，以具體地說明本發明，惟 本發明係不因此等例而有任何限定。 又’份及百分比若無特別說明，則全部係以質量爲基 準。共聚物之分子量係以GPC(凝膠滲透層析法）所測定之 聚本乙嫌換算的重量平均分子量（Mw)。 合成例1 在配備攪拌裝置、滴液漏斗、冷凝器、溫度計、氣體 -22 - 200900854 導入管之燒瓶中’置入作爲溶劑之丙二醇單甲基醚乙酸酯 700g，邊進行氮置換邊進行攪拌，昇溫至12〇 r。接著，在 甲基丙烯酸三環癸酯（a_2)53.2g、丙三醇單丙烯酸酯 (a-l)19.3g、乙烧基甲苯（a_4)165.4g及甲基丙烯酸（a_3)56.lg 所構成之單體混合物中’添加己酸第三丁基過氧基-2_乙酯 6.0g。將其從滴液漏斗費2小時滴下至燒瓶，然後，以12〇 °C攪拌2小時，得到固體成分酸價i22.0mgKOH/g、重量平 均分子量29 8 00之共聚物（A-l)-l(感光性樹脂1)的溶液。 合成例2 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g ’邊進行氮置換邊進行攪拌，昇溫至120 °C。接著，在甲基丙烯酸環己酯（a-2)73.4g、丙三醇單丙烯 酸酯（a-l)69.9g、乙烯基甲苯（a-4)171.9g、甲基丙烯酸 (a-3)50.U所構成之單體混合物中，添加己酸第三丁基過氧 基-2-乙酯34.7g。將其從滴液漏斗費2小時滴下至燒瓶， 然後，以 120 °C攪拌 2小時，得到固體成分酸價 ^ 81 .7mgKOH/g、重量平均分子量9500的共聚物（A-l)-2(感光 性樹脂2)之溶液。 合成例3 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯700g，邊進行氮置換邊進行攪拌，昇溫至120 。(：。接著，在甲基丙烯酸三環癸酯（a-2)45.9g、丙三醇單丙 烯酸酯（a-l)33.4g、乙烯基甲苯（a-4)96.0g及甲基丙烯酸 (a-3)73.6g所構成之單體混合物中，添加己酸第三丁基過氧 -23 - 200900854 基-2 -乙酯5 · 0 g。將其從滴液漏斗費2小時滴下至燒瓶，然 後，以120 °C攪拌2小時，得到共聚物之溶液。接著，將燒 瓶内置換爲空氣，把甲基丙烯酸縮水甘油酯（a-5)4 4.4g、三 苯基膦0.8g、及甲基氫醌0.8g投入上述共聚物溶液中，以 120°C持續反應，得到固體成分酸價i〇i.4mgKOH/g、重量 平均分子量30500的共聚物（A-2)-l(感光性樹脂3)之溶液。 合成例4 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g，邊進行氮置換邊進行攪拌，昇溫至120 °C。接著’在環己基甲基丙烯酸酯（a-2)40.5g、丙三醇單丙 烯酸酯（a-l)38.6g、甲基丙烯酸（a_3)93.3g、甲基丙烯酸苄酯 (a-4)l 48.5g所構成之單體混合物中，添加己酸第三丁基過 氧基-2-乙酯25.3g。將其從滴液漏斗費2小時滴下至燒瓶， 然後，以120 °C攪拌2小時，得到共聚物之溶液。接著，將 燒瓶内置換爲空氣’把甲基丙烯酸縮水甘油酯（a_5)51.4g、 三苯基膦1.2g及甲基氫醌i.2g投入上述共聚物溶液中，以 120°C持續反應，得到固體成分酸價ι〇14ιη§κ〇Η^、重量 平均分子量1 0500的共聚物（A_2)_ 2 (感光性樹脂4)之溶液。 合成例5 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基酸乙酸酯700g’邊進行氮置換邊進行攪拌，昇溫至120 °c。接著’投入甲基丙烯酸三環癸酯（a_2)27.9g、丙三醇單 丙嫌酸醋（a-l)20.3g、甲基丙烯酸縮水甘油酯（a_5)99.2g及 苯乙燦單體（a_4)33.0g，並添加己酸第三丁基過氧基-2_乙酯 -24 - 200900854 3.7g。將其從滴液漏斗費2小時滴下至燒瓶，然後，以i20 °C攪拌2小時，得到共聚物1之溶液。接著，將燒瓶内置 換爲空氣’把丙烯酸（a-3)48.8g、三苯基膦o.gg及甲基氫醌 0.8g投入上述共聚物1之溶液中以120 °C持續反應，在固體 成分之酸價成爲〇 . 8 m g Κ Ο H / g時反應結束，而得到共聚物 la之溶液。接著’藉由加入四氫酞酸酐（a_6)65.6g，以n5 °C反應2小時’而得固體成分酸價80.7mgKOH/g、重量平 均分子量30800的共聚物（A-3)-l(感光性樹脂5)之溶液。 合成例6 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g，邊進行氮置換邊進行攪拌，昇溫至1 20 °C。接著，在甲基丙烯酸三環癸酯（a-2)36.3g、環己基甲基 丙烯酸酯（a-2)55.4g、丙三醇單丙烯酸酯（a-i)26.4g、甲基丙 烯酸縮水甘油酯（a-5)117,lg及乙烯基甲苯（a-4)19.5g所構 成之單體混合物中，添加t- 丁基過氧基-2-乙基己酸酯 20.5g。將其從滴液漏斗費2小時滴下至燒瓶，然後，以120 °C攪拌2小時，得到共聚物2之溶液。接著，將燒瓶内置 換爲空氣，投入丙烯酸（a-3)57.6g、三苯基縢l.Og及甲基氫 醌l.Og，以 120 °C持續反應，在固體成分之酸價成爲 0.8mgKOH/g時反應結束，得到共聚物2a之溶液。接著， 藉由加入四氫酞酸酐U-6)65.2g，以115°C反應2小時，而 得固體成分酸價60.2mgK〇H/g、重量平均分子量9400的共 聚物（A-3)-2(感光性樹脂6)之溶液。 比較合成例1 -25 - 200900854 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g，邊進行氮置換邊進行攪拌，昇溫至120 °C。接著，在丙三醇單丙烯酸酯（a-1)74.4g、乙烯基甲苯 (a-4)241.8g、甲基丙烯酸（a-3)50.7g所構成之單體混合物 中，添加己酸第三丁基過氧基-2-乙酯32.9g。將其從滴液 漏斗費2小時滴下至燒瓶，然後，以1 2 0 °C攪拌2小時，得 到固體成分酸價82.7mgKOH/g、重量平均分子量1 0200之 比較感光性樹脂1之溶液。 比較合成例2 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g，邊進行氮置換邊進行攪拌，昇溫至120 °C。接著’在環己基甲基丙烯酸酯（a-2)190.7g、乙烯基甲 苯（a-4)130.6g、甲基丙烯酸（a-3)51.2g所構成之單體混合物 中’添加己酸第三丁基過氧基-2 -乙酯27.5g。將其從滴液 漏斗費2小時滴下至燒瓶，然後，以1 2 0。(：攪拌2小時，得 到固體成分酸價83.6mgKOH/g、重量平均分子量92〇〇之比 'j 較感光性樹脂2之溶液。 比較合成例3 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯700g’邊進行氮置換邊進行攪拌，昇溫至12〇 。(：。接著’在甲基丙烯酸三環癸酷（a-2)46.9g、甲基丙稀酸 2 -經基乙酯（a-4)27.7g、乙燒基甲苯（a_4)98.1g、甲基丙稀酸 (a-3)75.1g所構成之單體混合物中，添加己酸第三丁基過氧 基-2-乙酯5 . 1 g。將其從滴液漏斗費2小時滴下至燒瓶，然 -26 - 200900854 後’以1 20°C攪拌2小時，得到共聚物之溶液。接著，將燒 瓶内置換爲空氣，將甲基丙烯酸縮水甘油酯（a-5)45.4g、三 苯基膦0.9g及甲基氫醌0.9g投入上述共聚物溶液中，以 120°C持續反應，得到固體成分酸價l〇3.6mgKOH/g、重量 平均分子量29 800之比較感光性樹脂3之溶液。 比較合成例4 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯650g，邊進行氮置換邊進行攪拌，昇溫至120 J °C。接著，在甲基丙烯酸三環癸酯（a-2)128.5g、甲基丙烯 酸U-3)6 8.6g及甲基丙烯酸苄酯（a-4)99.4g所構成之單體混 合物中，添加己酸第三丁基過氧基-2-乙酯10.lg。將其從 滴液漏斗費2小時滴下至燒瓶，然後，以1 20°C攪拌2小時、 進行反應，而得共聚物之溶液。接著，將燒瓶内置換爲空 氣，將甲基丙烯酸縮水甘油酯（a-5)41.5g、三苯基膦l.〇g及 甲基氫醌l.Og投入上述共聚物溶液中，以120°C持續反應， 得到固體成分酸價81.1mgKOH/g、重量平均分子量20800 / 之比較感光性樹脂4之溶液。 比較合成例5 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯600g，邊進行氮置換邊進行攪拌，昇溫至120 °C。接著，在丙三醇單丙烯酸酯（a-l)27.1g、甲基丙烯酸縮 水甘油酯（a-5)144.2g、甲基丙烯酸正丁酯U-4)72.1g所構成 之單體混合物中，添加己酸第三丁基過氧基-2-乙酯19.5g。 將其從滴液漏斗費2小時滴下至燒瓶，然後，以120°C攪拌 -27 - 200900854 2小時、進行反應，而得共聚物之溶液。接著，將燒瓶内 置換爲空氣，把丙烯酸（a-3)70.9g、三苯基膦l.Og及甲基氫 醌1.0 g投入上述共聚物之溶液中，以1 2 0 °C持續反應，在 固體成分之酸價成爲0.8mgK〇H/g時反應結束，得到共聚物 之溶液。接著，藉由加入四氫酞酸酐（a-6)64.3g，以115°C 反應2小時，得到固體成分酸價59.3mgKOH/g、重量平均 分子量9800之比較感光性樹脂5之溶液。 比較合成例6 在與合成例1相同之燒瓶中置入作爲溶劑的丙二醇單 甲基醚乙酸酯700g，邊進行氮置換邊進行攪泮，昇溫至120 °C。接著，在環己基甲基丙烯酸酯（a-2)56.9g、甲基丙烯酸 縮水甘油酯（a-5)96.2g、甲基丙烯酸正丁酯（a-4)16.0g所構 成之單體混合物中，添加己酸第三丁基過氧基-2-乙酯 5. lg。將其從滴液漏斗費2小時滴下至燒瓶然後，以120 °C 攪拌2小時、進行反應，而得共聚物之溶液。接著，將燒 瓶内置換爲空氣，把丙烯酸（a-3)47.3g、三苯基膦0.7g及甲 基氫醌0.7g投入上述共聚物溶液，以120°C持續反應’在 固體成分之酸價成爲0.8 m gKOH/g時反應結束’得到共聚物 之溶液。接著，藉由加入四氫酞酸酐（a-6)77.2g ’以115°C 反應2小時，得到固體成分酸價95.0mgKOH/g、重量平均 分子量3 1 000之比較感光性樹脂6之溶液。 實施例1〜6、比較例1〜6 分別使用合成例1〜6所得之感光性樹脂1〜6的各溶 液作爲實施例1〜6，比較合成例1〜6所得之比較感光性樹 -28 - 200900854 脂1〜6之各溶液作爲比較例1〜6。將在各感光性樹脂之溶 液的固體成分100份中，添加季戊四醇四丙烯酸酯30份作 爲光聚合啓發劑、2,2 -二甲氧基-2-苯基苯乙酮4份所調製 而成之感光性樹脂組成物’以塗抹器（applicator)在玻璃基 板上塗布爲濕潤時之厚度係ΙΟμιη，在100 °C之熱風乾燥器 中使低沸點物揮發後，用 ORC MANUFACTURING C〇.，LTD.(股）製超高壓水銀燈，視需要通過遮罩以 150m〗/cm2進行曝光，得到厚度2/zm之硬化塗膜，接著進 r\ • 行鹼顯影。 <綠色顏料分散液1之·調製> 在經塡充直徑0.5 m m之锆珠粒1 8 0質量份的S U S容器 中，投入7.58質量份之C.I色素綠36、7.58質量份之合成 例2所得之感光性樹脂2、2 8.5 4質量份之丙二醇單甲基醚 乙酸酯及 6.31質量份之分散劑（BYK化學公司製 Disperbyk-161)，以塗料攪拌器（paint shaker)進行分散6小 時，而得綠色顏料分散液1。 ^ <綠色顏料分散液2之調製> 在經塡充直徑0.5mm之锆珠粒180質量份的SUS容器 中’投入7.58質量份之C.I色素綠36、7.58質量份之比較 合成例2所得之比較感光性樹脂2、2 8.5 4質量份之丙二醇 單甲基醚乙酸酯及6.31質量份之分散劑（BYK化學公司製 Disperbyk-16 1)，以塗料攪拌器進行分散6小時，而得綠色 顏料分散液2。 <綠色感光性樹脂組成物1之調製> -29 - 200900854 混合50質量份之上述所得之綠色顏料分散液1、20.8 質量份之合成例3所得之感光性樹脂3、6.25質量份之六 丙嫌酸二季戊四醇酯、2.5質量份之 Irgacure 907(Ciba Specially Chemicals股份有限公司製）、31.1質量份之丙二 醇單甲基醚乙酸酯Μ得到綠色感光性樹脂組成物1。 <綠色感光性樹脂組成物2之調製> 混合50質量份之上述所得之綠色顏料分散液2、20.8 質量份之比較合成例4所得之比較感光性樹脂4、6.25質 量份之六丙烯酸二季戊四醇酯、2.5質量份之Irgacure 907(Ciba Specially Chemicals 股份有限公司製）、31.1 質量 份之丙二醇單甲基醚乙酸酯，得到綠色感光性樹脂組成物 2 ° 實施例7、比較例7 分別使用綠色感光性樹脂組成物1作爲實施例7、綠 色感光性樹脂組成物2作爲比較例7，以塗抹器在玻璃基 板上塗布成乾燥時之厚度爲2；am，在100 °C之熱風乾燥器 ' 中使低沸點物揮發後，用 0 r c M a n u f a c t u r i n g C 〇 .，L t d .(股） 製超高壓水銀燈，視需要通過遮罩以150m】/cm2進行曝光， 得到厚度2/im之硬化塗膜，接著進行鹼顯影。 (1) 耐熱性試驗 切出實施例1〜7及比較例1〜7所得之各硬化塗膜， 進行熱重量分析（TGA)。將切出之試料加熱至220 °C爲止， 測定保持2小時時之重量變化率。 (2) 耐熱變色性試驗 -30 - 200900854 將製膜於玻璃基板上之塗膜在23 0°C之乾燥機中放置1 小時，以色差計比較加熱處理前後塗膜之著色’根據以下 基準進行評價。 〇：AE*ab爲0.3以下 X : △Ehb 超過 〇.3 (3) 透明性 將製膜於玻璃基板上之塗膜在2 3 0 °C之乾燥機中放置1 小時，以分光光度計測定加熱處理前後塗膜在400nm之透 過率，根據以下基準進行評價。 〇：透過率之變化率爲1 %以下 x :透過率之變化率超過1 % (4) 密接性 用硬化塗膜、依據HS K5 400進行矩形試驗，以目視觀 察1 00個矩形之剝離狀態，根據以下基準進行評價。 〇 :判斷完全無剝離者。 x :判斷整體的1 0%以上剝離者。 (5) 驗顯影性 將將通過遮罩曝光之硬化塗膜在2 3 °C用0.1 %之碳酸鈉 水溶液噴灑顯影，觀察水洗後塗膜之有無’跟據以下基準 進行評價。 〇 :顯影時間7 0秒後，目視無塗膜 X :顯影時間70秒後，目視有塗膜 200900854 [表1]200900854 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. More specifically, it is applicable to solder resists, various coating lacquers, adhesives, adhesives for printing inks, adhesives for color filters, etc., and can form excellent heat resistance and substrates. A photosensitive resin composition of a cured coating film having adhesive properties and development characteristics. [Prior Art] In recent years, from the viewpoint of saving resources and saving energy, radiation curable resins which can be cured by ultraviolet rays or electron wires have been widely used in the fields of printing, coatings, and adhesives. Even in the field of electronic equipment such as printed wiring boards, solder resists have been used in order to protect the board after mounting the components for a long time. As a material used for the printed wiring board by the photoresist method, it is usually an acid suspension type novolac epoxy resin, but the adhesion to copper plating is insufficient, and in the case of being used as a multilayer printed wiring board, there is a conductor. In addition to the problem that the bonding strength between the circuits is insufficient, the problem is that it is easily broken due to the fact that the flexibility is also poor. In order to solve such problems, a method of mixing an inorganic tantalum material in a photosensitive resin composition using a (meth)acrylic copolymer has been proposed (for example, Patent Document 1), but there is still an acid suspension type phenolic epoxy resin. The problem of poor heat resistance of the resin. In a color liquid crystal display device or a solid-state imaging device, a color filter is used, which is a color coating film that colors red (R), green (G), and blue (B) colors on a substrate in a predetermined pattern, and The black black matrix between these is constructed as 200900854. Usually, a black matrix is formed on a transparent substrate such as glass, and then formed into a colored coating film pattern such as R, G or B. In general, a color filter is produced by a production method such as a dyeing method, a printing method, a bulk method, or an electrolytic deposition method. Among them, a photocurable resin composition mainly composed of an alkali-soluble resin, a reactive monomer, a photopolymerization initiator, and a pigment is prepared by a lithography method of recoating, exposing, developing, and post-curing on a transparent substrate. The method of forming a powder is excellent in durability such as light resistance and heat resistance, and pinholes and the like are becoming mainstream. The pigment dispersion method has the above-described advantages. On the other hand, a matrix, a pattern of R, G, and B is formed, and the alkali-soluble resin which is required to be a coating film has high heat resistance and adhesion to a substrate. As a method of improving the heat resistance of the alkali-soluble resin, a resin composition having a cyclic structure of a (meth) acrylate having a cyclic structure as a synthetic component (for example, Patent Document 2), or containing a male amine The monomer is a resin composition of a copolymerization component (for example, a patent, etc. However, the former has a cyclic structure in a side chain (a resin composition of a methyl ester as a copolymer component) for improving heat resistance When the use ratio is increased, there is a problem that the adhesion to the substrate is lowered, and the solubility of the resin in the developer used in the development step is decreased, and the time in the development step becomes long, and even becomes impossible to develop, and the pattern is specified. Or, even if a pattern has been obtained, after the heat treatment is performed for the film, the side chain is thermally decomposed during the hardening, and the pigment is divided into small portions by using the material and the solution, and the repeating adhesive has been proposed. Copolymerization of the literature 3) I) propylene, and the problem, or not only the fixed coating, became the 200900854 volatile component, which pollutes the production line. In the latter, a resin composition containing a monomer of a maleimide as a copolymerization component may be colored yellowish brown due to a nitrogen atom contained in the molecule, thereby deteriorating the transparency of the coating film. Further, after the heat treatment, there is a problem that it is further colored during hardening. [Patent Document 1] JP-A-2006-240396, JP-A-2004-240396, JP-A-2004-240396 The object of the present invention is to provide a photosensitive resin composition which can form a cured coating film which is excellent in heat resistance, adhesion, and transparency, in addition to the development characteristics which can be used in the lithography step. In order to solve the above problems, the inventors of the present invention have conducted a drill collar discussion. As a result, it has been found that the polymerization includes a polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule, and an alicyclic skeleton having a crosslinked structure having a carbon number of 6 to 20 in the molecule. The resin composition of the copolymer (a-2) as an essential component solves the above problems, and the present invention has been completed based on the findings. In other words, the photosensitive resin composition of the present invention contains a polymer component (A) and a photopolymerizable monomer (B), and is characterized in that the polymer component (A) is a polymer component (A). a polymerizable monomer (a-1) having two or more hydroxyl groups in a molecule, and a polymerizable monomer having an alicyclic skeleton having a crosslinked structure of carbon number 6 200900854 to 20 in the molecule (a — 2) A polymer obtained as an essential monomer component. According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in heat resistance, adhesion, and transparency, in addition to the development characteristics which can be used in the lithography step. . Further, the cured coating film formed of the photosensitive resin composition of the present invention is excellent in heat resistance and adhesion to a glass substrate or a semiconductor substrate, and has an extremely high utilization rate in various photoresist fields due to alkali developability. [Embodiment] The present invention is described in detail below. The photosensitive resin composition of the present invention contains a polymerizable monomer (a-1;) having two or more hydroxyl groups in the molecule, and a crosslinked structure having a carbon number of 6 to 20 in the molecule. The copolymer of the alicyclic skeleton polymerizable monomer (a_2) as an essential monomer component as the polymer component (A), and in addition to having development characteristics usable for the lithography step, yttrium can form heat resistance A hardened coating film which is excellent in adhesion and transparency. Hereinafter, the polymer component (A) will be described. The polymerizable monomer (a-fluorene) having two or more hydroxyl groups in the molecule is not particularly limited. Specific examples thereof include glycerin mono(meth)acrylate and butanediol mono(methyl). An alkyl alcohol polyol mono(meth)acrylate such as acrylate or glutitol mono(meth)acrylate, caffeic acid, shikimic acid, or the like. Among them, in terms of adhesion and development characteristics, glycerin mono(methyl)propyl 200900854 enoate is particularly preferred. When the polymer component (A) is obtained, the ratio of the polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule in the monomer component is not particularly limited, and is 3 in all the monomer components. ~30% by mole, preferably 5 to 20% by mole, more preferably 5 to 15% by mole. When the polymerizable monomer (a-1) is in this range, in addition to the coating film properties such as adhesion, the amount of the hydroxyl group introduced is appropriately maintained, so that the viscosity of the photosensitive resin composition solution is not When the ratio of the solvent in the photosensitive resin composition is increased, the degree of freedom of blending is high. In addition, by the fact that the blending ratio of the other monomers is increased, the heat resistance is not lowered, and the amount of the photosensitive group necessary for alkali development and the photosensitive group necessary for photocuring, which will be described later, is not limit. Since the polymerizable monomer (a-1) has a high function for imparting developability and adhesion, the final blending ratio is small, and a polymerizable monomer which imparts heat resistance to each other and a polymerizable property are provided. The blending ratio of the monomer or the polymerizable monomer which imparts photosensitivity may be large, and it may have both developability, photosensitivity, and heat resistance as a polymer (A). Adhesion. The polymerizable monomer (a-2) having an alicyclic skeleton which may have a crosslinked structure of 6 to 20 carbon atoms in the molecule, and specific examples thereof include cyclohexyl (meth)acrylate, (A) Methylcyclohexyl acrylate, ethylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (A) Tricyclodecyl acrylate, tricyclodecyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (methyl) Isobornyl acrylate, adamantane (meth)acrylate 200900854 ester, rosin (meth)acrylate, norbornene (meth)acrylate)-5-methylnorbornene, (meth)acrylic acid -5-ethyl pentene ester and other (meth) acrylates; α-pinene, α-terpineol (a-terpeni monoterpene having CC double bond in the molecule; norbornene, 5-A a olefin such as a substrate olefin, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid or bornene-2,3-dicarboxylic anhydride; Particularly, in terms of properties, cyclohexyl (meth)acrylate, (meth)acrylic acid triester, (meth)acrylic acid rosin ester, norbornene are preferred. ^ The aforementioned polymer component is obtained (A) The ratio of the monomer in the monomer component to the polycyclic monomer (a-2) which may also have an alicyclic skeleton having a crosslinked structure of 6 to 20 carbon atoms is not particularly limited, and is preferably a wholly monomer. 2 mol%, preferably 5 to 20 mol%, more preferably 5 to 15 mol%, of the composition. In the range, the blend ratio of the other monomers is also changed. In addition, the adhesion to the substrate is sufficient. The amount of introduction of the photosensitive group necessary for photo-hardening in the alkali development to be described later is not limited. The amount of introduction of the alicyclic skeleton having a crosslinked structure can also be exhibited. There is not much, so the solubility of the resin in the developing solution is not lowered, and the time required for the development step does not become long, and development is not impossible, and the specified pattern can be obtained, and the film properties such as heat resistance are also sufficient. The polymer component (A) has an acid value of 20 to 180 mgKOH/g, and is 30 to 150 mgK〇H/g, more preferably 40 to 140 mgKOH/ g. If the acid value is within this range, sufficient alkali development characteristics can be obtained. That is, if the acid value is within the range, the solubility of the alkali developing solution is changed, and when there is no hardened portion, it is dissolved in the alkali developing. Liquid, sometimes swell, (A borneol 〇 1) and other ice-reducing 5-reducing heat ring 具 具 丨 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 The weight average molecular weight (the polystyrene equivalent number of the GPC method) of the polymer component (A) is preferably 5,000 to 80,000. If the weight average molecular weight is within this range, heat resistance and flexibility are not lowered. The solubility in the alkali developer is also sufficient. Regarding the introduction of an acid value in the polymer component (A), it is known to use an unsaturated-valence acid U-3 as a copolymerization component (copolymer (A-1), copolymer (A-2)), or The epoxy group-forming radical polymerizable compound (a-5) is reacted with an unsaturated monovalent acid (a-3) as an epoxy group of the copolymer used in the copolymerization component, and the resulting hydroxyl group or A method of reacting a hydroxyl group of a copolymerization component (a-fluorene) with a polyvalent acid anhydride (a-6) (copolymer (A-3)). The copolymer (A-1) is obtained by copolymerizing (a-Ι) with (a-2), (a-3) and (a-4), and the copolymerization ratio is in the all monomer component, ( A-Ι) is 3 to 30 mol%, preferably 5 to 20 mol%, more preferably 5 to 15 mol%; (a-2) is 3 to 30 mol%, preferably 5~ 20% by mole, more preferably 5 to 15% by mole; (a-3) is 20 to 70% by mole, preferably 20 to 60% by mole, more preferably 20^ to 50% by mole; (a-4) is 0 to 75 旲%, preferably 20 to 60 AU%, more preferably 25 to 50 mol%, and the total is 100 mol%. Let (a -1) be 3 to 30 mol%, and (a - 2) be 3 to 30 mol% as described above. (a-3) is for allowing the side chain of the copolymer (A-1) to have an acid value at which a carboxyl group is present. The unsaturated monovalent acid (a-3) of the present invention is not particularly limited, and examples thereof include (meth)acrylic acid, crotonic acid, and cinnamic acid. Further, it is also possible to use a multi-industry 200900854 (meth) acrylate having one hydroxyl group and one or more (meth) acryloyl fluorenyl groups (for example, hydroxyethyl (meth) acrylate, hydroxy (meth) acrylate) A reaction product of a propyl ester, hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, or the like, and a polyvalent acid anhydride. Among these, it is preferred to use (meth)acrylic acid. These may be used alone or in combination of two or more. The radically polymerizable compound (a-4) other than (a-1), (a-2), and (a-3) is not particularly limited as long as it has an ethylenically unsaturated group. Specific examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate and (meth)acrylic acid. Ethyl ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, Amyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-(ethyl)acrylate Hexyl hexyl ester, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, (a) Phenyl acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, decyl (meth) acrylate, tetrahydrofuran (meth) acrylate, pyrrolyl (meth) acrylate, Phenylethyl (meth)acrylate, cresyl (meth)acrylate, (methyl) propyl Acid trifluoroethane, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, ( Methyl) cumene propionate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate (meth) acrylates such as hydroxypropyl ester, naphthyl (meth) acrylate, decyl (meth) acrylate; decyl (meth) acrylate, N, N-dimethyl decyl (meth) acrylate , (meth)acrylic acid 200900854 N,N-diethylguanamine, N,N-dipropyl decylamine (meth)acrylate, N,N-diisopropyldecylamine (meth)acrylate, (A) (meth)acrylic acid decylamine or the like (meth)acrylic acid decylamine; (meth)acrylic acid aniline, (meth) acrylonitrile nitrile, acrylic acid, ethylene chloride, vinylidene chloride, vinyl fluoride, a vinyl compound such as vinylidene fluoride, N-ethylpyrrolidone, vinylpyridine or vinyl acetate; α-, 〇_, m-, P- of styrene and styrene Base, nitro, cyano, decylamine derivatives; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, diethyl itaconate; -Phenyl-Malay 醯亚月安' N-cyclohexylmaleimide, & lauryl maleate, n_(4_hydroxy@$ base) maleic imine, etc. Amines; N-(methyl) propylene phthalic acid imine. Among the above, from the viewpoint of adhesion between the cured coating film and transparency, benzyl (meth)acrylate, 2-diethylethyl (meth)acrylate, styrene or vinyltoluene is preferably used. These systems may be used alone or in combination of two or more. The radical copolymerization reaction for obtaining the copolymer (A _ 1) is not particularly limited. The radical polymerization method which has been carried out so far can be applied. For example, a solvent such as a glycol ether type such as propanol monomethyl ether or propylene glycol monomethyl ether acetate, or a hydrocarbon type such as toluene or xylene or ethyl acetate In the organic solvent, the above (a·1)' (a-2) is preferably dissolved in a desired ratio, and the copolymerized components of (a-3) and (a-4) are preferably mixed with azobisisobutene and A polymerization heuristic agent such as nitrogen bisisovaleronitrile or benzamidine peroxide, butyl hexanoate-2' ethyl acrylate, which is polymerized in a reflux state at a temperature of about 5 〇 to 30 ° C for 1 to 20 hours. Left and right, the organic solvent solution of the copolymer (Α_ι) is obtained. The amount of the polymerization heuristic agent used is usually 0% with respect to 100 parts by mass of the total of (a_1:), (a_2), (a_3) 200900854 and (a-4). 5 to 20 parts by mass or so, preferably 1. 0 to 1 0 parts by mass. It is also possible to carry out bulk polymerization with a polymerization heuristic agent only with (a-1), (a-2), (a-3) and (a-4) without using an organic solvent. The amount of the organic solvent used is usually about 30 to 1,000 parts by mass, based on 100 parts by mass of the total of (a-1), (a-2), (a-3), and (a-4). It is preferably about 50 to 800 parts by mass. By using the organic solvent in an amount of 100 parts by mass or less, the amount of the copolymer (A-1) is prevented from decreasing due to chain transfer, and the finally obtained copolymer (A-1) can be obtained. The solid content concentration is controlled within a suitable range. When it is 30 parts by mass or more, it is possible to prevent an abnormal polymerization reaction and to carry out a stable polymerization reaction, thereby preventing coloring and gelation of the resin. The copolymer (A-1) of the present invention is a photosensitive resin composition obtained by mixing a reactive diluent and a solvent described later, and is mainly used as an electronic material such as a photoresist, so that radical copolymerization as described above is used. When the copolymer (A-1) is legally produced, it is preferred to use r or an octadiol ester solvent such as propylene glycol monomethyl ether acetate. The copolymer (A-2) is obtained by copolymerizing (a-1), (a-2), (a-3) and (a-4) to form a carboxyl group and a component (a-5) in the obtained copolymer. The reaction comes. The copolymerization ratios of (a-2), (a-3) and (a-4) are the same as those of the copolymer (A-1), but further have a ring existing in the carboxyl group of the side chain and (a-5) The radically polymerizable compound of the oxy group reacts to convert a part of the carboxyl group to an unsaturated group. The phase stomach M is present in the carboxyl group of the side chain of the copolymer, and the amount of the radically polymerizable compound having an epoxy group of (a-5) is 5 to 80 moles. The balance between the carboxyl group and the unsaturated group was controlled by -14-200900854 in 5 to 80 mol, and the hardenability and alkali developability of the copolymer (A-2) were maintained appropriately. The copolymerization reaction of (a-1), (a-2), (a-3) and (a-4) can be carried out under the same conditions as in the case of the copolymer (A-1). The radically polymerizable compound having an epoxy group (a-5) is not particularly limited, and examples thereof include glycidyl (meth)acrylate and (meth)acrylic acid 3 having a cyclic epoxy group. 4-epoxycyclohexylmethyl ester and its lactone adducts [for example, Cyclomer-A200, 'M100] manufactured by Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl-3',4 '-Ethyl (meth) acrylate of epoxy-cyclohexane carboxylate, epoxy group of dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate An epoxy group or the like is preferably a glycidyl (meth)acrylate or a 3,4-epoxycyclohexylmethyl (meth)acrylate, since it is easy to obtain from a raw material. These systems may be used alone or in combination of two or more. The reaction of the carboxyl group in the copolymer with the radically polymerizable compound having an epoxy group of U-5) is carried out as follows. That is to say, 'in order to prevent gelation caused by polymerization of an unsaturated monovalent acid and a copolymer containing a resulting unsaturated group. In the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether or oxygen, and a tertiary amine such as triethylamine or a triethylbenzylammonium chloride or the like In the presence of a catalyst such as a phosphorus compound such as triphenylphosphine or a chelate compound such as chromium, the reaction is usually carried out at about 50 to 15 ° C, preferably 80 to 130 T: . In the case where an organic solvent is used for the radical copolymerization reaction for obtaining a copolymer, the solution state of the copolymer organic solvent can be used as it is for the subsequent reaction. 15-200900854 Copolymer (A-3) is obtained by copolymerizing (al), (a-2), (a-5) and (a-4) with an epoxy group in the obtained copolymer. After the reaction with (a-3), the resulting hydroxyl group or the hydroxyl group of (a-1) is reacted with (a-6) of the polyvalent acid anhydride. The copolymerization ratio of (a-1), (a-2), (a-5), and (a-4) is 3 to 30 mol%, preferably 5, in the all monomer component. 〜20摩尔%, more preferably 5~15mol%' (a-2) is 3 to 30% by mole, preferably 5 to 20% by mole, more preferably 5 to 15% by mole, ( A-5) is 30 to 85 mol%, preferably 30 to 70 mol%, more preferably 30 to 60 mol% '(a_4) is 〇~05 mol%, preferably 丨5 to 55 The % of moles, more preferably 25 to 50 mole%, is a total of 100% by mole. Let (a-Ι) be 3~30 耳%, and (a-2) be 3~. 30% of the moles are as described. (a-5) is carried out by introducing an epoxy group at the side chain of the copolymer to react with a carboxyl group of U-3 afterwards to introduce an unsaturated group. Further, by reacting the generated hydroxyl group with U-6 of a polyvalent acid anhydride, it is also used to introduce an acid value. Therefore, the (a-5) system introduced into the side chain of the copolymer (A-2) is different in function and the amount of introduction is also different, but the same epoxy compound can be used. By making (a-5) 30% to 85 mol%, it is possible to control the introduction amount of the epoxy group, that is, the introduction amount of the unsaturated group derived from the unsaturated monovalent acid of U-3), and to control the copolymerization. The hardenability of the substance (A-3). By making (a-1), (a-2), and (a-5) the above ratio, U-4) can be appropriately selected within the range of 〇 to 65 mol%. The copolymer (A-3) is formed by copolymerizing the above (ai), (a-2), preferably (a-5) and (a-4) radicals to form a copolymer (a- 3) an unsaturated monovalent acid reaction, followed by reacting a polyvalent anhydride of U-6). U-3) is not rich in 200900854 and the carboxyl group of the monovalent acid reacts with the epoxy group from the side chain of (a - 5 ) to ring-open the epoxy group' and imparts a Saturated base. The polyvalent acid anhydride of (a-6) reacts with a hydroxyl group formed by reacting a hydroxyl group of (a-Ι) or a carboxyl group of (a-3) and an epoxy group of a side chain of (a-5), an acid anhydride The base system is converted into a carboxyl group by ring opening. The amount of the unsaturated monovalent acid of (a-3) is 1 〇~; relative to 100 moles of the epoxy group derived from the side chain of (a-5); [〇〇莫耳, preferably 30 to 100 moles, more preferably 50 to 100 moles. By using the amount of the unsaturated monovalent acid to be 1 Torr or more, the minimum amount of the unsaturated group necessary for hardening the resin can be introduced by using the amount of the unsaturated monovalent acid to be 1 0 0 Below the ear, the amount of unreacted unsaturated-valence acid in the obtained copolymer (A-3) of the present invention can be reduced. The reaction is carried out with respect to the hydroxyl group formed by the reaction of the (a-Ι) thiol group and the fluorenyl group in (a-3) with the epoxy group derived from the side chain of (a - 5 ). The amount of the polyvalent acid anhydride of (a-6) is 5 to 1 mole, preferably 1 to 90 moles, more preferably 20 to 90 moles. The acid value of the obtained copolymer (A-3) can be obtained by making the number of moles of the polyvalent acid anhydride into the range of 5 to 1 mole relative to the hydroxyl group of the oxime. 〇ι) is controlled in the range of 20 to 180 mgKOH/g. The reaction of the permeation group of the above copolymer with the polyvalent acid anhydride (a-6) is carried out as it is after reacting the epoxy group derived from the (a-5) side chain of the above copolymer with the unsaturated monovalent acid of (a-3). The pre-measurement amount (a_6) is usually carried out at a temperature of about 50 to 150 ° C, preferably 80 to 130 ° C. There is no need to re-add the catalyst. The polyvalent acid anhydride of (a-6) in the copolymer (A-3) of the present invention is not particularly limited to 200900854, and examples thereof include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. And methylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among these, tetrahydrophthalic anhydride and succinic anhydride are used. These systems may be used alone or in combination of two or more. The photosensitive resin composition of the present invention comprising the polymer component (A) of the copolymers (A-1) to (A-3) obtained as described above and the photopolymerizable monomer (B) can be added with photopolymerization. Heuristic (C) and solvent (D). The photopolymerizable monomer (B) which can be used is not particularly limited as long as it can react with the polymer component (A). For example, aromatics such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, diallyl phenylphosphonate, etc. Vinyl monomer; polycarboxylic acid monomer such as vinyl acetate or vinyl adipate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (a) Butyl acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Propylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetra(methyl) (meth)acrylic monomers such as pentaerythritol acrylate, dipentaerythritol hexa(meth)acrylate, tris(meth)acrylate of hydroxy(hydroxyethyl)trimeric isocyanate; triallyl cyanurate, etc. . One or two or more of these may be used. The amount of the photopolymerizable monomer (Β) to be added is usually 10 to 200 parts by mass, preferably 20 to 150 parts by mass of the polymer component (Α). By being within the above range, the photocurability can be maintained within an appropriate range, and further, the viscosity can be adjusted. The solvent (D)' which can be added to the photosensitive resin composition is an inert solvent which does not react with the polymer component (A) and the photopolymerizable monomer (B), and can be used without limitation. Examples of the solvent (D) that can be used include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, 5 butyl acetate, and isopropyl acetate. , propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone , cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, and the like. Among these, it is preferred to use propylene glycol monomethyl ether acetate which is preferably used in the above-mentioned radical polymerization reaction. The amount of the solvent (D) to be added is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the polymer component (A). By maintaining the above range, the viscosity can be kept moderate. When the photosensitive resin composition of the present invention is photocured by using active light such as ultraviolet rays as an active energy ray, a photopolymerization initiator (C) is added. The photopolymerization initiator (C) which can be used is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether, and decyl ethers thereof; Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, ι, ΐ-diacetophenone, 4-(1-tert-butyloxy-1-methylethyl) Acetophenones such as acetophenone; 2-methylindole, 2-pentylindole, 2-tert-butylindole, 1-chloropurine-19-200900854, etc.; 2,4 - Thioxanone such as dimethylthioxanthone, 2,4-diisopropylthioxanthone or 2-chlorothioxanthone; ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal Class; benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'·肆 (t-butyldioxy Benzophenones such as benzoyl benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propan-1-one or 2-phenylene -2-Dimethylamino-1-(4-norpolinylphenyl)butanone-1; pentyl phosphine oxides and xanthones. These systems may be used alone or in combination of two or more. The blending amount of the photopolymerization-inducing agent (C) is usually preferably 0% by weight based on 100 parts by mass of the solid content of the photosensitive resin composition of the present invention. 1 to 30 parts by mass is preferably 0. 5 to 20 parts by mass, more preferably 1 to 1 part by mass. By 0. 1 to 30 parts by mass ' can maintain photocurability in an appropriate range. Further, the photosensitive resin composition of the present invention may optionally contain a conventional coloring agent, an antifoaming agent, a coupling agent, a leveling agent and the like. As the coloring agent, a conventional coloring agent such as an inorganic pigment, an organic pigment, or a dye can be used. Specific examples of the pigment that can be used include, for example, C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Orange pigments such as 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; . I · Pigment Blue 15、15: 3, 15: 4, 15: 6, 16, 60, etc. Blue -20- 200900854 Pigment; C. I. Purple pigments such as pigment purple 1, 19, 23, 29, 32, 36, 38; c. I · Pigment green 7, 36 and other green pigments; C I • Pigment brown 23, 25 and other brown pigments; C · I · Pigment black 1, 7, carbon black, titanium black, iron oxide and other black pigments. These coloring agents can be used singly or in combination of two or more kinds depending on the color of the pixel of interest. The blending amount of the coloring agent is not particularly limited, and is usually 2 to 70 parts by mass, preferably 25 to 60 parts by mass, based on 1 part by mass of the solid content of the photosensitive resin composition of the present invention. More preferably, 30~50 quality, part. In order to enhance the dispersibility of the pigment, a conventional dispersant may be further added. As the dispersing agent, if a polymer dispersing agent is used, the dispersion stability is excellent over time, which is preferable. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylidene ether dispersant, and a polyoxyethylene glycol diester dispersion. Agent, sorbitan fatty ester dispersant, aliphatic denaturing ester dispersant, and the like. Specific examples of the dispersing agent are EFK A (EFK A Chemicals B.) V. (EFKA), D1Sperbyk (manufactured by BYK Chemical Co., Ltd.), Disperlon (manufactured by Nanmoto Chemical Co., Ltd.), S〇LSPERSE (manufactured by ZENECA Co., Ltd.), and the like. The blending amount of the dispersing agent is not particularly limited, and is usually preferably 100 parts by mass or less, preferably 1 to 90 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the pigment to be used. . As described above, the polymer component (A) of the present invention has an acid value of from 20 to 180 mgKOH/g, and therefore, a photoresist using the photosensitive resin composition containing the photosensitive resin composition can be developed with an aqueous alkali solution. . The photosensitive resin composition of the present invention can be applied, for example, to a printed wiring board, a glass substrate, or an array substrate by a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like. After the necessary portion is photohardened, its uncured (unexposed) portion is washed away with an aqueous alkali solution for development. Examples of the aqueous alkali solution used for development include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, and sodium hydroxide, and amine-based compounds are also used, but P-phenylenediamine is preferred. The compound, " representative examples thereof are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-oxime-β-hydroxyl Aniline, 3-methyl-4-amino-N-ethyl-Ν-β-methanesulfonamide ethyl aniline, 3-methyl-4-aminoethyl-Ν-β-methoxy Alkyl aniline and an aqueous solution of such a sulfate, hydrochloride, or p-toluenesulfonate. A light source used for light irradiation to harden the coated surface is a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp or the like. EXAMPLES The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited thereto. In addition, the percentages and percentages are based on quality unless otherwise stated. The molecular weight of the copolymer is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). Synthesis Example 1 700 g of propylene glycol monomethyl ether acetate as a solvent was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas-22 - 200900854 introduction tube, and stirred while performing nitrogen substitution. , heat up to 12〇r. Next, in tricyclodecyl methacrylate (a_2) 53. 2g, glycerol monoacrylate (a-l) 19. 3g, ethene toluene (a_4) 165. 4g and methacrylic acid (a_3) 56. Adding butyl hexanoperoxy-2_ethyl hexanoate to the monomer mixture consisting of lg 0g. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 12 ° C for 2 hours to obtain a solid component acid value i22. A solution of a copolymer (A-1)-1 (photosensitive resin 1) having a weight average molecular weight of 29 8 00 at 0 mg KOH/g. Synthesis Example 2 Into a flask similar to that of Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate as a solvent was placed while stirring, and the mixture was stirred and heated to 120 °C. Next, in cyclohexyl methacrylate (a-2) 73. 4g, glycerol monoacrylate (a-l) 69. 9g, vinyl toluene (a-4) 171. 9g, methacrylic acid (a-3) 50. In the monomer mixture composed of U, tributylperoxy-2-ethyl hexanoate was added. 7g. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to obtain a solid content acid value of ^ 81 . A solution of 7 mg KOH/g of a copolymer (A-1)-2 (photosensitive resin 2) having a weight average molecular weight of 9,500. Synthesis Example 3 700 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being nitrogen-substituted, and the temperature was raised to 120. (:. Next, in tricyclodecyl methacrylate (a-2) 45. 9g, glycerol monoacrylate (a-l) 33. 4g, vinyl toluene (a-4) 96. 0g and methacrylic acid (a-3) 73. To the monomer mixture composed of 6 g, t-butyl peroxyperoxy phthalate - 200900854 - 2 - ethyl ester 5 · 0 g of hexanoic acid was added. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to obtain a solution of the copolymer. Next, the inside of the flask was replaced with air to give glycidyl methacrylate (a-5) 4 4. 4g, triphenylphosphine 0. 8g, and methylhydroquinone 0. 8 g was charged into the above copolymer solution, and the reaction was continued at 120 ° C to obtain a solid component acid value i〇i. A solution of 4 mg KOH/g of a copolymer (A-2)-1 (photosensitive resin 3) having a weight average molecular weight of 30,500. Synthesis Example 4 600 g of propylene glycol monomethyl ether acetate as a solvent was placed in a flask similar to that of Synthesis Example 1, and the mixture was stirred while being nitrogen-substituted, and the temperature was raised to 120 °C. Then 'in cyclohexyl methacrylate (a-2) 40. 5g, glycerol monoacrylate (a-l) 38. 6g, methacrylic acid (a_3) 93. 3g, benzyl methacrylate (a-4) l 48. 5 g of the monomer mixture is composed of t-butyl peroxy-2-ethyl hexanoate. 3g. This was dropped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to obtain a solution of the copolymer. Next, the inside of the flask was replaced with air 'glycidyl methacrylate (a_5) 51. 4g, triphenylphosphine 1. 2g and methylhydroquinone i. 2 g was charged into the above copolymer solution, and the reaction was continued at 120 ° C to obtain a solution of a copolymer (A_2)_ 2 (photosensitive resin 4) having a solid content of an acid value of ι〇14ιη§κ〇Η^ and a weight average molecular weight of 1,0500. . Synthesis Example 5 Into a flask similar to that of Synthesis Example 1, 700 g of propylene glycol monomethyl acetate as a solvent was placed while stirring, and the mixture was stirred and heated to 120 °C. Then 'input tricyclodecyl methacrylate (a_2) 27. 9g, glycerol, single-acrylic acid vinegar (a-l) 20. 3g, glycidyl methacrylate (a_5) 99. 2g and styrene monomer (a_4) 33. 0g, and added t-butylperoxy-2-ethyl hexanoate -24 - 200900854 3. 7g. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at i20 ° C for 2 hours to obtain a solution of the copolymer 1. Next, change the flask to air. 'Acrylic acid (a-3) 48. 8g, triphenylphosphine o. Gg and methylhydroquinone 0. 8 g of the solution of the above copolymer 1 was continuously reacted at 120 ° C, and the acid value of the solid component became 〇. When 8 m g Κ Ο H / g, the reaction is completed, and a solution of the copolymer la is obtained. Then 'by adding tetrahydrophthalic anhydride (a_6) 65. 6g, reacted at n5 °C for 2 hours' to obtain a solid content acid value of 80. A solution of 7 mg KOH/g of a copolymer (A-3)-1 (photosensitive resin 5) having a weight average molecular weight of 30,800. Synthesis Example 6 600 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 1,200 °C. Next, in tricyclodecyl methacrylate (a-2) 36. 3g, cyclohexyl methacrylate (a-2) 55. 4g, glycerol monoacrylate (a-i) 26. 4g, glycidyl methacrylate (a-5) 117, lg and vinyl toluene (a-4) 19. To 5 g of the monomer mixture formed, t-butylperoxy-2-ethylhexanoate was added. 5g. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to obtain a solution of the copolymer 2. Next, the flask was replaced with air and charged with acrylic acid (a-3) 57. 6g, triphenyl sulfonium l. Og and methyl hydrogen 醌l. Og, the reaction is continued at 120 °C, and the acid value of the solid component becomes 0. At 8 mg KOH/g, the reaction was completed, and a solution of the copolymer 2a was obtained. Next, by adding tetrahydrophthalic anhydride U-6) 65. 2 g, reacted at 115 ° C for 2 hours to obtain a solid component acid value of 60. A solution of 2 mg K 〇 H / g of a copolymer (A-3)-2 (photosensitive resin 6) having a weight average molecular weight of 9,400. Comparative Synthesis Example 1 - 25 - 200900854 Into a flask similar to the synthesis example 1, 600 g of propylene glycol monomethyl ether acetate as a solvent was placed, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 °C. Next, in glycerol monoacrylate (a-1) 74. 4g, vinyl toluene (a-4) 241. 8g, methacrylic acid (a-3) 50. 7 g of the monomer mixture is composed of tributyl butyl peroxy-2-ethyl hexanoate. 9g. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to obtain a solid content acid value of 82. A solution of photosensitive resin 1 was compared with 7 mg KOH/g and a weight average molecular weight of 1,200. Comparative Synthesis Example 2 600 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being nitrogen-substituted, and the temperature was raised to 120 °C. Then 'in cyclohexyl methacrylate (a-2) 190. 7g, vinyl toluene (a-4) 130. 6g, methacrylic acid (a-3) 51. 2g of the monomer mixture formed by adding 't-butylperoxy-peroxy-2-ethyl hexanoate. 5g. This was dripped from the dropping funnel for 2 hours to the flask, and then, 1 2 0. (: Stirring for 2 hours, obtaining a solid content acid price of 83. 6 mg KOH / g, a weight average molecular weight of 92 比 'j is a solution of the photosensitive resin 2 . Comparative Synthesis Example 3 In the same flask as in Synthesis Example 1, 700 g of propylene glycol monomethyl ether acetate as a solvent was placed while stirring, and the mixture was stirred and heated to 12 Torr. (:. Then 'in the methacrylic acid tricyclic 癸 cool (a-2) 46. 9g, methyl acrylate 2 - thioethyl (a-4) 27. 7g, ethene toluene (a_4) 98. 1g, methyl acrylate (a-3) 75. To the monomer mixture composed of 1 g, tert-butylperoxy-2-ethyl hexanoate was added. 1 g. This was dropped from the dropping funnel for 2 hours to the flask, and then -26 - 200900854 was stirred at 1200 ° C for 2 hours to obtain a solution of the copolymer. Next, the inside of the flask was replaced with air, and glycidyl methacrylate (a-5) was used. 4g, triphenylphosphine 0. 9g and methylhydroquinone 0. 9 g was charged into the above copolymer solution, and the reaction was continued at 120 ° C to obtain a solid content acid value l〇3. A solution of a photosensitive resin 3 of 6 mg KOH/g and a weight average molecular weight of 29,800. Comparative Synthesis Example 4 650 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 J °C. Next, in tricyclodecyl methacrylate (a-2) 128. 5g, methacrylic acid U-3)6 8. 6g and benzyl methacrylate (a-4) 99. To 4 g of the monomer mixture, tributyl butylperoxy-2-ethyl hexanoate was added. Lg. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 1,200 ° C for 2 hours to carry out a reaction to obtain a solution of the copolymer. Next, the inside of the flask was replaced with air, and glycidyl methacrylate (a-5) was 41. 5g, triphenylphosphine l. 〇g and methylhydroquinone l. Og was put into the above copolymer solution, and the reaction was continued at 120 ° C to obtain a solid component acid value of 81. A solution of 1 mg KOH/g and a weight average molecular weight of 20,800 / of the comparative photosensitive resin 4. Comparative Synthesis Example 5 600 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 °C. Next, in glycerol monoacrylate (a-l) 27. 1g, glycidyl methacrylate (a-5) 144. 2g, n-butyl methacrylate U-4) 72. To the monomer mixture composed of 1 g, t-butylperoxy-2-ethyl hexanoate was added. 5g. This was dropped from the dropping funnel for 2 hours to the flask, and then the mixture was stirred at 120 ° C for -27 - 200900854 for 2 hours to carry out a reaction to obtain a solution of the copolymer. Next, the flask was replaced with air to give acrylic acid (a-3) 70. 9g, triphenylphosphine l. Og and methyl hydrogen 醌1. 0 g was charged into the solution of the above copolymer, and the reaction was continued at 120 ° C, and the acid value of the solid component became 0. The reaction was completed at 8 mg K 〇 H / g to obtain a solution of the copolymer. Next, by adding tetrahydrophthalic anhydride (a-6) 64. 3g, reacted at 115 ° C for 2 hours to obtain a solid content acid value of 59. A solution of the photosensitive resin 5 of 3 mg KOH/g and a weight average molecular weight of 9,800. Comparative Synthesis Example 6 700 g of propylene glycol monomethyl ether acetate as a solvent was placed in the same flask as in Synthesis Example 1, and the mixture was stirred while being nitrogen-substituted, and the temperature was raised to 120 °C. Next, in cyclohexyl methacrylate (a-2) 56. 9g, glycidyl methacrylate (a-5) 96. 2g, n-butyl methacrylate (a-4) 16. To the monomer mixture of 0 g, tert-butylperoxy-2-ethyl hexanoate was added. Lg. This was dripped from the dropping funnel for 2 hours to the flask, and then stirred at 120 ° C for 2 hours to carry out a reaction to obtain a solution of the copolymer. Next, the inside of the flask was replaced with air, and acrylic acid (a-3) was used. 3g, triphenylphosphine 0. 7g and methylhydroquinone 0. 7 g of the above copolymer solution was charged, and the reaction was continued at 120 ° C. The acid value of the solid component became 0. At the end of the reaction at 8 m gKOH/g, a solution of the copolymer was obtained. Next, by adding tetrahydrophthalic anhydride (a-6) 77. 2g 'reacted at 115 ° C for 2 hours to obtain a solid content acid value of 95. A solution of the photosensitive resin 6 of 0 mg KOH/g and a weight average molecular weight of 31,000. In each of Examples 1 to 6 and Comparative Examples 1 to 6, the respective photosensitive resins 1 to 6 obtained in Synthesis Examples 1 to 6 were used as Examples 1 to 6, and the comparative photosensitive trees 28 obtained in Comparative Synthesis Examples 1 to 6 were compared. - 200900854 Each of the solutions of the lipids 1 to 6 was used as Comparative Examples 1 to 6. 30 parts of pentaerythritol tetraacrylate was added to 100 parts of the solid content of each photosensitive resin solution as a photopolymerization initiator and 4 parts of 2,2-dimethoxy-2-phenylacetophenone. The photosensitive resin composition 'applicator is coated on a glass substrate to have a thickness of ΙΟμιη when wet, and the low-boiling substance is volatilized in a hot air dryer at 100 ° C, and then ORC MANUFACTURING C〇. ,LTD. The ultra-high pressure mercury lamp made of (strand) is exposed to a mask of 150 m/cm2 as needed to obtain a hardened coating film having a thickness of 2/zm, and then subjected to alkali development. <Preparation of Green Pigment Dispersion 1> In a SUS container having 180 parts by mass of zirconium beads having a diameter of 0.5 mm, 7.58 parts by mass of CI Pigment Green 36 and 7.58 parts by mass of Synthesis Example 2 were charged. The obtained photosensitive resin 2, 2 8.5 4 parts by mass of propylene glycol monomethyl ether acetate, and 6.31 parts by mass of a dispersing agent (Disperbyk-161 manufactured by BYK Chemical Co., Ltd.) were dispersed by a paint shaker for 6 hours. , and obtained a green pigment dispersion 1. ^ <Preparation of Green Pigment Dispersion Liquid 2> In a SUS container filled with 180 parts by mass of zirconium beads having a diameter of 0.5 mm, 7.58 parts by mass of CI dye green 36 and 7.58 parts by mass of Comparative Synthesis Example 2 were obtained. Comparative photosensitive resin 2, 2 8.5 4 parts by mass of propylene glycol monomethyl ether acetate and 6.31 parts by mass of dispersant (Disperbyk-16 1 manufactured by BYK Chemical Co., Ltd.), dispersed by a paint shaker for 6 hours, and obtained green Pigment dispersion 2 . <Preparation of Green Photosensitive Resin Composition 1> -29 - 200900854 50 parts by mass of the above-obtained green pigment dispersion liquid 1 and 20.8 parts by mass of the photosensitive resin 3 obtained in Synthesis Example 3, 6.25 parts by mass A green photosensitive resin composition 1 was obtained by dissolving dipentaerythritol acrylate, 2.5 parts by mass of Irgacure 907 (manufactured by Ciba Specially Chemicals Co., Ltd.), and 31.1 parts by mass of propylene glycol monomethyl ether acetate oxime. <Preparation of Green Photosensitive Resin Composition 2> 50 parts by mass of the above-obtained green pigment dispersion liquid 2, 20.8 parts by mass of Comparative Comparative Synthesis Example 4, Comparative Photosensitive Resin 4, and 6.25 parts by mass of hexaacrylic acid Pentaerythritol ester, 2.5 parts by mass of Irgacure 907 (manufactured by Ciba Specially Chemicals Co., Ltd.), and 31.1 parts by mass of propylene glycol monomethyl ether acetate, and obtained green photosensitive resin composition 2 ° Example 7 and Comparative Example 7 were used, respectively. Green photosensitive resin composition 1 was used as Comparative Example 7 as Example 7 and green photosensitive resin composition 2, and the thickness was 2 when the applicator was applied to the glass substrate to have a thickness of 2; am, a hot air dryer at 100 ° C After the low-boiling substance is volatilized, the ultra-high pressure mercury lamp is made by 0 rc M anufacturing C 〇., L td. (share), and exposed by a mask at 150 m]/cm 2 to obtain a hardened coating having a thickness of 2/im. The film is then subjected to alkali development. (1) Heat resistance test Each of the cured coating films obtained in Examples 1 to 7 and Comparative Examples 1 to 7 was cut out and subjected to thermogravimetric analysis (TGA). The cut sample was heated to 220 ° C, and the weight change rate at the time of holding for 2 hours was measured. (2) Heat-resistant discoloration test -30 - 200900854 The film formed on the glass substrate was placed in a dryer at 23 °C for 1 hour, and the color of the coating film before and after the heat treatment was compared with a color difference meter. Evaluation. 〇: AE*ab is 0.3 or less X: △Ehb exceeds 〇.3 (3) Transparency The film formed on the glass substrate is placed in a dryer at 230 °C for 1 hour, and measured by a spectrophotometer. The transmittance of the coating film at 400 nm before and after the heat treatment was evaluated based on the following criteria. 〇: The rate of change of transmittance is less than 1%. x: The rate of change of transmittance is more than 1%. (4) The hardened coating film for adhesion is subjected to a rectangular test according to HS K5 400, and the peeling state of 100 rectangles is visually observed. Evaluation was performed based on the following criteria. 〇 : Judging that there is no peeling at all. x : Determines the overall 10% or more peeling. (5) Developability The cured coating film exposed by the mask was sprayed and developed with a 0.1% aqueous solution of sodium carbonate at 23 ° C, and the presence or absence of the coating film after washing was observed, and evaluated according to the following criteria. 〇 : After the development time of 70 seconds, the film is visually unapplied X: After 70 seconds of development time, the film is visually observed. 200900854 [Table 1]
實施例1 實施例2 比較例1 比較例2 耐熱性(％) -0.6 -0.8 -0.9 -2.8 耐熱變色(AE*ab) 〇 〇 X 〇 透明性(400nm · %) 〇 〇 〇 〇 密接性 〇 〇 〇 X 鹼顯影性 〇 〇 X XExample 1 Example 2 Comparative Example 1 Comparative Example 2 Heat resistance (%) -0.6 -0.8 -0.9 -2.8 Heat-resistant discoloration (AE*ab) 〇〇X 〇 transparency (400 nm · %) 〇〇〇〇 adhesion 〇 〇〇X alkali developability 〇〇XX
[表2][Table 2]
實施例3 實施例4 比較例3 比較例4 耐熱性(％) -0.9 -1.2 -1.0 -2.1 耐熱變色（AE*ab) 〇 〇 〇 〇 透明性(400nm · %) 〇 〇 〇 〇 密接性 〇 〇 X X 鹼顯影性 〇 〇 X XExample 3 Example 4 Comparative Example 3 Comparative Example 4 Heat resistance (%) -0.9 -1.2 -1.0 -2.1 Heat-resistant discoloration (AE*ab) 〇〇〇〇Transparency (400 nm · %) 〇〇〇〇Adhesiveness〇 〇XX alkali developability 〇〇XX
[表3][table 3]
實施例5 實施例6 比較例5 比較例6 耐熱性(％) -0.4 -0.8 -3.8 -2.9 耐熱變色(AEbb) 〇 〇 X 〇 透明性(400nm · %) 〇 〇 X 〇 密接性 〇 〇 〇 X 鹼顯影性 〇 〇 〇 X 200900854 [表4]Example 5 Example 6 Comparative Example 5 Comparative Example 6 Heat resistance (%) -0.4 -0.8 -3.8 -2.9 Heat-resistant discoloration (AEbb) 〇〇X 〇Transparency (400 nm · %) 〇〇X 〇Adhesion 〇〇〇 X alkali developability 〇〇〇X 200900854 [Table 4]
實施例7 比較例7 耐熱性(％) -1.0 -2.3 耐熱變色(△Ehb) 〇 〇 透明性(400nm . %) 〇 〇 密接性 〇 X 驗顯影性 〇 X 由表1〜4，實施例中加熱時的重量減少或耐熱變色、 透明性之惡化少，並且判斷無硬化塗膜之剝離，更且亦無 損鹼顯影性。 產業上之可利用件 由本發明之感光性樹脂組成物所形成之硬化塗膜係對 玻璃基板或半導體基板之耐熱性·密接性優異，由於具有鹼 顯影性，因此在各種光阻領域之利用價値極高。 【圖式簡單說明】 4FR1 〇 j \ w 【元件符號說明】 姐〇Example 7 Comparative Example 7 Heat resistance (%) -1.0 -2.3 Heat-resistant discoloration (?Ehb) 〇〇Transparency (400 nm.%) 〇〇Adhesion 〇X Testability 〇X From Tables 1 to 4, in Examples The weight loss during heating or heat discoloration and the deterioration of transparency are small, and the peeling of the hardened coating film is judged, and the alkali developability is also not impaired. INDUSTRIAL APPLICABILITY The cured coating film formed of the photosensitive resin composition of the present invention is excellent in heat resistance and adhesion to a glass substrate or a semiconductor substrate, and has an alkali developability, so that it is used in various photoresist fields. Extremely high. [Simple description of the diagram] 4FR1 〇 j \ w [Component symbol description] Sister
/X NN/X NN