200921272 九、發明說明 【發明所屬之技術領域】 本發明係關於一種不含鹵素之酞菁綠的著色光硬化性 樹脂組成物。更詳細而言’本發明關於不含鹵素之酞菁綠 的著色光硬化性樹脂組成物，尤其可提供對於因銅回路之 氧化而變色之具掩蓋性優異的抗焊光阻層。 【先前技術】 通常，抗焊光阻係形成爲保護銅回路。其作用，於另 一方面而言亦有使看不見因銅回路之熱或濕氣產生之變色 、電變色、銅回路上之瑕疵、髒污等作用。 抗焊光阻係塗佈於銅回路所形成的玻璃環氧基材，藉 由曝光而形成畫像，經由顯影、熱硬化，形成其皮膜圖型 。由於基材上有銅回路形成，於此上塗佈或層合了抗焊光 阻時，其光阻膜厚係於基材上爲厚而於銅回路上爲薄的， 於銅回路之邊緣的部分甚至更薄。 在此種抗焊光阻之厚度不同的狀況中，難以從外觀上 掩蓋銅回路。因此，對於抗焊光阻通常有摻合著色劑，藉 著使其濃度變濃而使銅回路之變色等不易看見。 最近的抗焊光阻係以減輕環境負荷的觀點而言，取代 以往之爲綠色著色劑的氯化酞菁綠，而普遍使用不具鹵素 原子的酞菁藍與不具鹵素原子的黃色著色劑使成爲綠色的 抗焊光阻（例如，參照專利文獻1 )。 又，使從外觀上可明確地知爲無鹵素（hal〇gen free 200921272 )者’亦有單獨使用酞菁藍作爲藍色的抗焊光阻來使用。 然而’與以酞菁綠而成之綠色相比，藍色的抗焊光阻 或以藍色著色劑與黃色著色劑而成之綠色抗焊光阻係掩蓋 性弱，且有使無法充分地實現作爲使外觀不良不易看見的 著色劑之功能的情形，如下說明即可明瞭。 亦即’現在的抗焊光阻係以光硬化形成畫像，最終施 以熱硬化處理。此時之處理溫度一般以150 °C進行約30〜 60分鐘，但依基板製造商而溫度或時間不一定。其結果， 尤其處理溫度高之處理時間長的情形，掩蓋性差的藍色的 抗焊光阻係無法掩蓋基板上之因銅回路之氧化而變色的問 題。此問題於使用無鹵素的藍色著色劑與黃色著色劑的綠 色抗焊光阻中亦爲相同，且經發明人等確認爲與酞菁綠相 比係掩蓋性弱。 又，對基板上施予標記油墨（marking ink)時，係於 抗焊光阻之硬化後，進而印刷標記且使之熱硬化，故銅回 路之變色加速，外觀上的問題更爲嚴重。 進而，爲修正抗焊光阻之熱硬化之際時產生之基板的 翹曲，有對基板全體施予壓力與熱的情形，同樣地銅回路 之變色加速。 此種銅回路之變色中，最不好的現象係雖於同一銅回 路上，但僅回路之邊緣（光阻變薄的部分）爲變色的狀態 。此種情形，於基板之檢查或實際組裝之際，由於與檢查 數據不一致，即使爲良品也變成不良。相反地，於銅回路 上可確認變色且均一地辨識其它部分的情形，就不會產生 -6- 200921272 其般不佳的情形。 此種不適的情形係爲依據之前報告指出，尤其取代酞 菁綠而使用不具鹵素原子的酞菁藍等的著色劑的情形（著 色劑之無鹵素化）爲顯著。 〔專利文獻11〕日本特開2000-7974號公報（專利申 請範圍，先前技術） 【發明內容】 〔發明所欲解決之課題〕 因此，本發明係以提供一種著色光硬化性樹脂組成物 ，其可形成對於因銅回路之氧化而變色等之具掩蓋性優異 的抗焊光阻層爲目的。 〔用以解決課題之手段〕 本發明人等專心硏究之結果，發現若藉由作爲著色劑 之至少使用紅色著色劑成爲的著色光硬化性樹脂組成物， 可解決使用無鹵素之著色劑成爲的以往之抗焊光阻之掩蓋 性的上述問題，進而藉由使用無鹵素之紅色著色劑，可謀 求不會使掩蓋性變差且於抗焊光阻層之鹵素含有量的減低 ，遂至完成本發明。 亦即，本發明爲一種可以鹼水溶液顯影之光硬化性樹 脂組成物，其特徵爲含有（A)含有羧酸之樹脂，（B)光 聚合起始劑，（C)分子中具有2個以上乙烯性不飽和基 之化合物，及（D )紅色著色劑。 200921272 本發明之上述光硬化性樹脂組成物係於一態樣中，除 紅色著色劑（D )以外可含有（E 1 )藍色著色劑（例如， 酞菁藍）及/或（E2)黃色著色劑，其色調可得呈藍色、 綠色、紫色或橙色。 又，本發明之光硬化性樹脂組成物係於一態樣中，紅 色著色劑（D)爲不含鹵素及偶氮基中任一者的紅色著色 劑。 又，本發明之光硬化性樹脂組成物係於一態樣中，進 而含有（F )熱硬化性成份。 又，本發明之光硬化性樹脂組成物係於一態樣中，爲 用於塗佈於銅上。 又，本發明係於其它態樣中，將上述光硬化性樹脂組 成物塗佈於載體薄膜，並使其乾燥而得的光硬化性乾薄膜 〇 又，本發明係於其它態樣中，上述光硬化性樹脂組成 物爲藍色、綠色、紫色或橙色的硬化物。 又，本發明係於其它態樣中，上述乾薄膜爲藍色、綠 色、紫色或橙色的硬化物。 又’本發明係於其它態樣中，於形成銅回路之基板上 ’具有由上述硬化物所形成之抗焊光阻層的印刷配線板。 〔發明效果〕 依據本發明，可提供對於因銅回路之氧化而變色之具 掩蓋性優異的藍色、綠色、紫色或橙色的著色抗焊光阻層 -8- 200921272 。尤其作爲替換於掩蓋性有問題之泛用藍色抗焊光阻的藍 色抗焊光阻爲有效。又’藉由本發明所求得之抗焊光阻層 係鹵素含有量極低且塗膜燃燒時之鹵素氣體產生量顯著地 減低。 以下，詳細地說明本發明。 如上述般地’本發明之光硬化性樹脂組成物，其特徵 係作爲著色劑之至少使用紅色著色劑（D )取代以往之含 有鹵素之酞菁綠而成，於一態樣中，除紅色著色劑（D) 以外’尙含有藍色著色劑（E1)及/或黃色著色劑（E2) ’其色調可得呈藍色、綠色、紫色或橙色的光硬化性樹脂 組成物。 因此，首先就本發明之著色劑說明。本發明中，著色 劑可使用習知者’可爲顏料、染料、色素之任一者。但， 以減輕環境負荷以及對人體的影響之觀點而言，以不含鹵 素爲佳。 作爲紅色著色劑（D )，單偶氮系、雙偶氮系、偶氮 沈澱（azo lake)系、苯并咪唑酮系、茈系、二酮基吡咯 并吡咯系、縮合偶氮系、蒽醌系、喹吖啶酮系等，具體地 ，可例舉附加爲如下述的顏色指數（C.I. ; The Society of Dyers and Colourists公司發行）編號者。 -單偶氮系：Pigment Red 1，2,3,4,5,6,8,9，12,14，15, 16,17,21,22,23,31,32,1 12,1 14,146,147,151,170,184,187, 188,193,210,245,253,258,266,267,268,269; -雙偶氮系：Pigment Red 3 7,3 8,4 1 : 200921272 單偶氮沈源（monoazo lake) ) : Pigment Red 48:1， 48:2,48:3,48:4,49:1，49:2,50:1，52:1，52:2,53:1,53:2,57: 1,58 :4,63: 1,63:2,64:1,68 ； -苯并咪唑酮系：Pigment Red 1 7 1,1 75,1 76,1 8 5,208 t -菲系：Solvent Red 1 3 5,1 79 ; Pigment Red 123, 1 49,1 66,1 78, 1 79,1 90,1 94,224 ; -二酮基吡咯并吡咯系：Pigment Red 254,255,264, 270,272 ； -縮合偶氮系：Pigment Red 220,144,166,214,220, 221,242 ； -蒽醌系：Pigment Red 168 ； 177,2 16 ； Solvent Red 149,150,52,207 ； -喹吖啶酮系：Pigment Red 122,202,206,207,209。 雖無特定限定者，但從安全性•無害性之觀點而言， 以不含偶氮基的紅色著色劑較適爲使用。 作爲藍色著色劑（E 1 )係有酞菁系、蒽醌系，顏料系 爲分類於顏料（Pigment )的化合物，具體地，可例舉附 加爲如下述的顏色指數（C.I. ; The Society of Dyers and Colourists公司發行）編號者。 -顏料系：Pigment Blue 15,15:1,15:2,15:3,15:4, 15:6,16,60 ; -染料系：Solvent Blue 35,63,68,70,83,87,94,97, 122，136,67,70 〇 -10- 200921272 上述以外亦可使用金屬取代或無取代的酞菁化合物。 作爲黃色著色劑（E2) ’有單偶氮系、雙偶氮系、縮 合偶氮系、苯并咪唑酮系、異吲哚滿系、恵醌系等，具體 地可例舉附加爲如下述的顔色指數編號者。 -蒽醌系：Solvent Yellow 163,Pigment Yeii〇w 24, 1 08,1 93,147,1 99,202 ； -異 D引 0朵滿系：Pigment Yellow 110,1〇9,139,179,185 » -縮合偶氮系：Pigment Yellow 93,94,95,1 2 8,1 5 5, 166,180 ； -苯并咪哩酮系：Pigment Yellow 120,151,154,156, 175,181 ； -單偶氮系：Pigment Yellowl,2,3,4,5,6,9,10,12,61， 62,62:1，65,73,74,75,97,100,104,105,111,116,167,168,169， 182,183 ； -雙偶氮系：Pigment Yellow 12，1 3,1 4,1 6,1 7,5 5,63, 8 1,83,87,1 26,1 27,1 52,1 70,1 72,1 74,1 76,1 88,1 98。 雖無特定限定者，但從安全性•無害性之觀點而言， 以不含偶氮基的黃色著色劑較適爲使用。 本發明中紅色著色劑、以及藍色著色劑及/或黃色著 色劑摻合率係使所得之光硬化性樹脂組成物或由其硬化皮 膜所成的抗焊光阻層爲所欲之色調，具體地使呈現藍色、 綠色、紫色或橙色而可作充分的比例。 於本發明中，本發明之光硬化性樹脂組成物或其硬化 -11 - 200921272 皮膜呈現藍色、綠色、紫色及橙色係指經由觀察 所觀察時，具有認知彼爲藍色、綠色、紫色及橙 色調者。具體地爲藉由JISZ872 1所規定之方法 化性樹脂組成物及其硬化皮膜之外觀色調.顯示 賽爾色相（Munsell hue )環（財團法人日本色 監修新基本色表系列2蒙賽爾系統日本色硏 有限公司發行；參照圖1 )上，屬於從5 B G至ί 藍色）、從9Υ至未達5BG (綠色）、從3Ρ至未 紫色）、從9R至未達7YR (橙色）之色相範圍 係具有彩度爲1以上未達16;亮度爲1以上未達 係彩度爲2以上未達15;亮度爲2以上未達9者 具體的摻合比例係亦被所使用之著色劑之種 添加劑等之種類影響，無法一槪論述，但一般， 係紅色著色劑（D ):藍色著色劑（Ε1 ):黃色 Ε2 ) = 1 : 〇 〜50: 0〜50。又，爲進行充分的著 色著色劑（D)、藍色著色劑（Ε1)及黃色著色 之合計量之組成物全體量的0.05〜3.0質量％之 摻合爲佳。 本發明中除上述著色劑以外，以調整色調之 加入紫、橙、褐、黑等之著色劑，具體地可列舉 Violet 19 、 23 、 29 、 32 、 36 、 38 、 42 ; Solvent 、3 6 ; C . I.顏料橙1、C . I.顏料橙5、C · I.顏料橙 顏料橙 14、C.I.顏料橙 16、C.I.顏料橙 17、C 24、C.I.顏料橙34、C.I.顏料橙36、C.I.顏料橙 者以肉眼 色程度的 測定光硬 時、於蒙 彩硏究所 事業股份 长達3P ( ：'Μ 7RP ( ，且較佳 I 9、更佳 〇 類或其它 以質量比 著色劑（ 色，以紅 劑（E2 ) 比例進行 目的亦可 Pigment Violet 13 13 ' C.I. .I.顏料橙 38 ' C.I. -12- 200921272 顏料橙40、C.I.顏料橙43、 C.I.顏料橙46、C.I.顔料橙 49、C.I.顏料橙 51、C.I.顏料橙 61、C.I.顏料橙 63、C.I. 顏料橙64' C.I.顏料橙71、C.I.顏料橙73、 C.I.顏料 褐23、C.I.顏料褐25; C.I.顏料黑1、C.I.顏料黑7等 〇 接著，就含有羧酸之樹脂（A)進行說明。 作爲本發明之光硬化性樹脂組成物中所含之含有羧酸 之樹脂（A)，可使用分子中含有羧酸的周知習用的樹脂 化合物。進而，分子中具有乙烯性不飽和雙鍵的含有羧酸 之感光性樹脂（A ’）以光硬化性或耐顯影性層面而言爲較 佳。 具體地，可列舉下述列舉的樹脂。 可列舉如下述（1 )〜（9 )等： (1) 一種含有羧酸之共聚合樹脂，其爲藉由將（甲 基）丙烯酸等之不飽和羧酸、與1種以上之具有其它之不 飽和雙鍵的化合物進行共聚合而求得， (2) —種含有羧酸之感光性樹脂，其於（甲基）丙 烯酸等之不飽和羧酸、與1種以上之具有其它之不飽和雙 鍵的化合物的共聚合物’藉由具有縮水甘油基（甲基）丙 烯酸酯或3,4-環氧環己基甲基（甲基）丙烯酸酯等的環氧 基與不飽和雙鍵的化合物、或（甲基）丙烯酸氯化物等， 經由使乙嫌性不飽和基作爲側基（Pendant)予以加成而求 得， (3) —種感光性之含有羧酸之共聚合樹脂，其爲使 -13- 200921272 具有縮水甘油基（甲基）丙烯酸酯或3，4_環氧環己基甲基 (甲基）丙烯酸酯等的環氧基與不飽和雙鍵的化合物、與 具有其它之不飽和雙鍵之化合物的共聚合物，以（甲基） 丙烯酸等之不飽和羧酸反應，且使生成之二級羥基以多元 酸酐反應而求得， (4) 一種含有羧酸之感光性樹脂，其爲使具有順丁 烯二酸酐等之不飽和雙鍵的酸酐、與具有其它之不飽和雙 鍵之化合物的共聚合物，以具有2-羥基乙基（甲基）丙烯 酸酯等之羥基與不飽和雙鍵的化合物反應而求得， (5) —種含有羧酸之感光性樹脂，其爲使多官能環 氧化合物與不飽和單羧酸反應，且使生成之羥基以飽和或 不飽和多元酸酐反應而求得， (6 ) —種含有羥基及羧酸之感光性樹脂，其爲使聚 乙烯醇衍生物等之含羥基之聚合物，以飽和或不飽和多元 酸酐反應後，使生成之羧酸以一分子中具有環氧基與不飽 和雙鍵的化合物反應而求得， (7) —種含有羧酸之感光性樹脂，其爲使多官能環 氧化合物、不飽和單羧酸、一分子中至少1個醇性羥基與 環氧基反應之具有醇性羥基以外之1個反應性基之化合物 的反應產物，以飽和或不飽和多元酸酐反應而求得， (8) —種含有羧酸之感光性樹脂，其爲使一分子中 具有至少2個氧雜環丁烷環的多官能氧雜環丁烷化合物， 以不飽和單羧酸反應’且對所得之改性氧雜環丁烷樹脂中 的第一級羥基以飽和或不飽和多元酸酐反應而求得，及 -14- 200921272 (9) 一種含有羧酸之感光性樹脂’其爲使多官能環 氧樹脂以不飽和單羧酸反應後，使多元酸酐反應所得的含 有羧酸之樹脂，進而以分子中具有1個環氧乙烷（〇xirane )環與1個以上之乙烯性不飽和基的化合物反應而求得’ 但不限定於此些。 此等例示中較佳者爲上述（2) 、 （5) 、 （7)的含 有羧酸之樹脂，尤其上述（9)的含有羧酸之感光性樹脂 以光硬化性、硬化塗膜特性之面而言爲較佳。 又，本說明書中，（甲基）丙烯酸酯係總稱丙烯酸酯 、甲基丙烯酸酯及彼等之混合物的用語，其它類似之表現 亦相同。 如上述的含有羧酸之樹脂（A)係由於在主幹•聚合 物（backbone polymer)的側鏈具有多數游離的酸基，故 可以鹼水溶液顯影。 又，上述含有羧酸之樹脂（A)的酸値較佳爲40〜 200mgKOH/g的範圍、更佳爲45〜1 20mgKOH/g的範圍。 含有羧酸之樹脂的酸値未達40mgKOH/g時，鹼顯影困難 ，另一方面，超過200mgKOH/g時，爲使藉由顯影液之曝 光部的溶解進行，還必需使線條變細，有時係沒有區別曝 光部與未曝光部便於顯影液中溶解剝離，正常的光阻圖型 之描繪變得困難，故不佳。 又，上述含有羧酸之樹脂（A)的重量平均分子量係 依樹脂骨架而不同，但一般爲2,000〜150,000、進而以 5,000〜！〇〇,〇〇〇的範圍者爲佳。重量平均分子量未達 -15- 200921272 2,000時，無黏性之性能差，曝光後之塗膜的耐濕性差且 顯影時膜減少，解像度很差。另一方面，重量平均分子量 超過1 50,000時，有顯影性明顯變差、貯藏安定性差的情 形。 此種含有羧酸之樹脂（Α)的摻合量係於全組成物中 ，較佳爲20〜60質量％、更佳爲30〜50質量％。比上述 範圍少的情形，塗膜強度降低故不佳。另一方面，比上述 範圍多的情形，黏性變高且塗佈性等降低，故不佳。 接著，就光聚合起始劑（Β)進行說明。 作爲光聚合起始劑（Β )，可例舉如苯乙酮、2,2-二 甲氧基-2-苯基苯乙酮、2，2-二乙氧基-2-苯基苯乙酮、Ρ-二 甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、p-tert-丁基三 氯苯乙酮、1-羥基環己基苯基酮、2-甲基-l-[4-(甲硫基 )苯基]-2-嗎啉代-丙烷-1-酮、2-苄基-2-二甲胺基-1-( 4-嗎琳代苯基）-丁酮-丨、N，N_二甲胺基苯乙酮等的苯乙酮 類；二苯基酮、甲基二苯基酮、2-氯二苯基酮、4,4’_二氯 二苯基酮、4,4’-雙二甲胺基二苯基酮、4,4，-雙二乙胺基二 本基_、米其勒酮（Michler’s ketone) 、4 -苯甲醯基- 4’-甲基二苯基硫化物等的二苯基酮類；苄基；苯甲醯基、苯 偶因甲醚、苯偶因乙醚、苯偶因異丙基醚、苯偶因異丁醚 等的苯偶因醚類；苯乙酮二甲基縮酮、苄基二甲基縮酮等 的縮酮類；噻噸酮、2-氯噻噸酮、2，4-二甲基噻噸酮、 2，4~二乙基噻噸酮、2,4-二異丙基唾噸酮等的噻噸酮類； 2_甲基蒽醌、2-乙基蒽醌、2-tert-丁基蒽醌、1-氯蒽醌、 -16- 200921272 2- 胺基蒽醌、2,3_二苯基蒽醌等的蒽醌類；苯甲醯基過氧 化物、異丙苯過氧化物等的有機過氧化物；2,4,5_三芳基 咪哩二聚物、核黃素四丁酸醋（riboflavin tetra butyrate )、2-毓基苯并咪唑、2-锍基苯并噁唑、2-锍基苯并噻唑 等的硫醇基化合物；2,4,6-參-s-三畊、2,2,2-三溴乙醇、 三溴甲基苯颯等的有機鹵素化合物；2,4,6-三甲基苯醯基 二苯基膦氧化物 '雙（2,4,6-三甲基苯醯基）-苯基膦氧化 物）等。此等化合物可單獨使用，又亦可組合2種以上使 用。 進而，上述光聚合起始劑（B )係可組合1種或2種 以上之如Ν,Ν-二甲胺基苯甲酸乙基酯、N，N-二甲胺基苯 甲酸異戊基酯、戊基-4-二甲胺基苯甲酸酯、三乙胺、三乙 醇胺等的三級胺類、雙（η5-環戊二烯基）-雙（2,6-二氟- 3- (1Η -耻格-1-基）苯基）欽等的駄燒（titanocene)類； 2-(乙醯基肟基甲基）噻噸-9-酮、1,2-辛二酮，1-[4-(苯 硫基）-，2-(〇-苯甲醯基肟）]、乙酮，1-[9-乙基-6-(2-甲 基苯醯基）-9H-咔唑-3-基]-，l-(0-乙醯基肟）等之肟酯類 的光增感劑來使用。 前述光聚合起始劑（B )之較佳的組合係2 -苄基-2 -二 甲胺基-1- ( 4-嗎啉代苯基）-丁酮-1 (例如Ciba Specialty Chemicals 公司製、IRGACURE 369: IRGACURE 爲註冊商 標）與雙（η5 -環戊二烯基）-雙（2,6-二氟-3-(lH-吡咯-l-基）苯基）欽（例如CibaSpecialtyChemicals公司製、 IRGACURE 784 )的組合；2,4,6-三甲基苯醯基二苯基膦氧 200921272 化物（例如BASF製Luc ir in ΤΡΟ )與2-(乙醯基肟基甲 基）噻噸-9-酮（例如 Ciba Specialty Chemicals 公司製、 CGI-3 25 )的組合；或2,4,6-三甲基苯醯基二苯基膦氧化 物（例如8八3?製1^(^1^11丁？0)與雙（2,4,6-三甲基苯醯 基）-苯基膦氧化物（例如Ciba Specialty Chemicals公司 製、IRGACURE 819)等的組合。 又，如上述的光聚合起始劑（B)之使用量之較佳的 範圍，係對於含有羧酸之樹脂（A) 100質量份而言較佳 爲1〜30質量份、更佳爲5〜25質量份的比例。光聚合起 始劑之摻合比例比上述範圍還少的情形，所得之組成物的 光硬化性變差。另一方面，比上述範圍還多時，所得之硬 化塗膜的特性變差，且組成物之保存安定性變差，故不佳 〇 接著，對分子中具有2個以上乙烯性不飽和基的化合 物進行說明。 本發明之光硬化性樹脂組成物中所使用之分子中具有 2個以上乙烯性不飽和基的化合物（C )爲藉由照射活性 能量線，進行光硬化，使前述含有羧酸之樹脂（A)於鹼 水溶液中爲不溶化或幫助不溶化者。此種化合物可列舉乙 二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之乙二醇的 二丙烯酸酯類；己二醇、三羥甲基丙烷、季戊四醇、二季 戊四醇、參-羥基乙基異三聚氰酸酯等的多元醇或此等的 環氧乙烷（ethylene oxide )加成物或環氧丙烷（ Pfopylene oxide)加成物等的多元丙烯酸酯類；苯氧基丙 -18- 200921272 烯酸酯、雙酣A二丙烯酸酯、及此等之苯酚類的環氧乙烷 (ethylene oxide)加成物或環氧丙烷（pr〇pylene 〇xide) 加成物等的多元丙烯酸酯類；甘油二縮水甘油醚、甘油三 縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油基 異三聚氰酸酯等之縮水甘油醚的多元丙烯酸酯類；及三聚 氰胺丙烯酸酯 '及/或對應上述丙烯酸酯的各甲基丙烯酸 酯類等。 又’列舉可使甲酚酚醛清漆型環氧樹脂等的多官能環 氧樹脂以丙烯酸反應的環氧丙烯酸酯樹脂、或進而使其環 氧丙烯酸酯樹脂之羥基以季戊四醇三丙烯酸酯等的羥基丙 烯酸酯與異佛酮二異氰酸酯等的二異氰酸酯的半胺基甲酸 酯化合物反應的環氧胺基甲酸酯丙烯酸酯化合物等。此種 環氧丙烯酸酯系樹脂係不會使指觸乾燥性降低且可使光硬 化性提高。 此種分子中具有2個以上乙烯性不飽和基之化合物（ C )的摻合比例，係對前述含有羧酸之樹脂（A ) 1 00質量 份而言爲5〜1 00質量份、更佳爲1〜70質量份的比例。 前述摻合量低於5質量份的情形，光硬化性降低且藉由照 射活性能量線後之鹼顯影係難以形成圖型’故不佳。另一 方面，超過100質量份時，因對鹼水溶液之溶解性降低且 塗膜變脆，而不佳。 接著，對熱硬化性成份（F )進行說明。 爲對本發明之光硬化性樹脂組成物賦予耐熱性，而可 加入熱硬化性成份（F )。尤其佳者爲分子中具有2個以 -19- 200921272 上之環狀醚基及/或環狀硫醚基（以下，簡稱爲環狀（硫 代）醚基）的熱硬化性成份（F )。 此種分子中具有2個以上之環狀（硫代）醚基的熱硬 化性成份（F)，爲分子中具有3、4或5員環的環狀醚基 、或環狀硫醚基中之任一者，或者爲具有2個以上之2種 類的基的化合物，例如可列舉分子內至少具有2個以上之 環氧基的化合物，亦即多官能環氧化合物（F-1):分子 內至少具有2個以上之氧雜環丁基的化合物，亦即多官能 氧雜環丁烷化合物（F-2);分子內至少具有2個以上之 硫醚基的化合物，亦即表硫化物樹脂（episulfide resin ) (F-3 )等。 前述多官能環氧化合物（F-1 )，可列舉如 japan Epoxy Re s i n s 公司製之 EPIΚ ΟTE 8 2 8、EPIKO TE 8 3 4、 EPIKOTE 1001 > EPIKOTE 1004，大日本油墨化學工業公 司製之 EPICLON 840、EPICLON 850、EPICLON 1 050、 EPICLON 20 5 5，東都化成公司製之 EPOTOHTO YD-011、 YD-013、YD-127、YD-128，Dow Chemical 公司製之 D.E.R.317 、 D.E.R.331 、 D.E.R.661 、 D.E.R.664 ; Ciba Specialty Chemicals 公司之 Araldite 6071、Araldite 6084 、Araldite GY250、Araldite GY260，住友化學工業公司製 之 Sumi-Epoxy ESA-011、ESA-014、ELA-115、E L A -1 2 8 ;旭化成工業公司製之 A.E.R.330、A.E.R.331、A.E.R.661 、A. E.R. 6 64等（皆商品名）的雙酚A型環氧樹脂；japan Epoxy Resins公司製之EPIKOTE YL903，大日本油墨化學 -20- 200921272 工業公司製之EPICLON 152、EPICLON 165，東都化成公 司製之 EPOTOHTO YDB-400、YDB-500，Dow Chemical 公司製之 D.E.R.542，Ciba Specialty Chemicals 公司製之 Araldite 8011，住友化學工業公司製之 Sumi-Epoxy ESB-400、ESB-700，旭化成工業公司製之 A.E.R.711、 A.E.R.714等（皆商品名）的溴化環氧樹脂；japari Epoxy Resins 公司製之 EPIKOTE 152、EPIKOTE 154、Dow Chemical公司製之D.E.N.431、D.E.N.438，大曰本油墨化 學工業公司製之 EPICLON N-730、EPICLON N-770、 EPICLON N- 865，東都化成公司製之 EPOTOHTO YDCN-701、YDCN-704，Ciba Specialty Chemicals 公司製之 Araldite ECN 1 23 5 ' Araldite ECN 1 273 ' Araldite ECN1299 、Araldite XPY3 07，日本化藥公司製之 EPPN-201、 EOCN-1025、EOCN-1020、EOCN-104S、RE-306，住友化 學工業公司製之 Sumi-Epoxy ESCN-195X、ESCN-220，旭 日化成工業公司製之A.E.R. ECN-235、ECN-299等（皆商 品名）的酚醛清漆型環氧樹脂；大日本油墨化學工業公司 製之 EPICLON 830，Japan Epoxy Resins 公司製之 EPIKOTE 807，東都化成公司製之 EPOTOHTO YDF-170、 YD F -1 7 5 ' YDF-2004 > Ciba Specialty Chemicals 公司製之 Araldite XPY306等（皆商品名）的雙酚F型環氧樹脂； 東都化成公司製之 EPOTOHTO ST-2004、ST-2007、ST-3 000 (商品名）等的氫化雙酚 A型環氧樹脂；Japan Epoxy Resins公司製之EPIKOTE 604，東都化成公司製之 -21 - 200921272 ΕΡΟΤΟΗΤΟ ΥΗ-434，Ciba Specialty Chemicals 公司製之 Araldite MY720，住友化學工業公司製之 Sumi-Epoxy ELM-120等（皆商品名）的縮水甘油基胺型環氧樹脂；BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color-light-curable resin composition of a halogen-free indocyanine green. More specifically, the present invention relates to a colored photocurable resin composition containing no halogen-containing phthalocyanine green, and particularly provides a solder resist layer excellent in masking property due to oxidation of a copper circuit. [Prior Art] Generally, a solder resist photoresist is formed to protect a copper loop. On the other hand, it also has the effect of discoloration, electrochromism, smashing of the copper circuit, and dirt caused by the heat or moisture of the copper circuit. The solder resist is applied to a glass epoxy substrate formed by a copper circuit, and an image is formed by exposure, and the film pattern is formed by development and heat curing. Since a copper circuit is formed on the substrate, when the solder resist is coated or laminated thereon, the thickness of the photoresist film is thick on the substrate and thin on the copper circuit, at the edge of the copper circuit. The part is even thinner. In the case where the thickness of such solder resist is different, it is difficult to mask the copper circuit from the appearance. Therefore, for the solder resist, a coloring agent is usually blended, and the discoloration of the copper circuit or the like is hard to see by making the concentration thick. Recently, the solder resist is a green phthalocyanine green which is a green coloring agent in view of reducing the environmental load, and a phthalocyanine blue having no halogen atom and a yellow coloring agent having no halogen atom are generally used. Green solder resist (for example, refer to Patent Document 1). Further, it is also known that the halogen-free (hal〇gen free 200921272) is clearly used in appearance, and phthalocyanine blue is used alone as a blue solder resist. However, compared to the green color made of phthalocyanine green, the blue solder resist or the green solder resist with a blue colorant and a yellow colorant is weakly masked and cannot be sufficiently The case where the function as a coloring agent which is difficult to see when the appearance is poor is realized, and the following description will be apparent. That is, the current solder resist is formed by photohardening, and finally subjected to heat hardening treatment. The treatment temperature at this time is usually about 150 to 60 minutes at 150 ° C, but the temperature or time is not necessarily determined by the substrate manufacturer. As a result, in particular, in the case where the processing time with a high processing temperature is long, the blue solder resist resist having poor masking property cannot cover the problem of discoloration on the substrate due to oxidation of the copper circuit. This problem is also the same in the green solder resist resist using a halogen-free blue colorant and a yellow colorant, and it has been confirmed by the inventors that the masking property is weaker than that of the phthalocyanine green. Further, when a marking ink is applied to the substrate, after the solder resist is cured, the mark is printed and thermally cured, so that the discoloration of the copper circuit is accelerated, and the appearance problem is further serious. Further, in order to correct the warpage of the substrate when the solder resist is thermally hardened, pressure and heat are applied to the entire substrate, and the discoloration of the copper circuit is accelerated in the same manner. The most unfavorable phenomenon in the discoloration of such a copper circuit is that it is on the same copper circuit, but only the edge of the circuit (the portion where the photoresist is thinned) is in a state of discoloration. In this case, when the substrate is inspected or actually assembled, it is inconsistent with the inspection data, and it becomes defective even if it is good. Conversely, in the case where the discoloration can be confirmed on the copper circuit and the other portions are uniformly recognized, there is no such a bad situation as -6-200921272. The case of such discomfort is based on the case where a coloring agent such as phthalocyanine blue which does not have a halogen atom is used in place of phthalocyanine green (a halogen-free coloring agent) is remarkable. [Problem to be Solved by the Invention] Accordingly, the present invention provides a colored photocurable resin composition. It is intended to form a solder resist layer having excellent masking properties such as discoloration due to oxidation of a copper circuit. [Means for Solving the Problem] As a result of intensive investigations by the present inventors, it has been found that the use of a halogen-free coloring agent can be solved by using a coloring photocurable resin composition which is at least a red coloring agent as a coloring agent. The above problem of the masking property of the conventional solder resist is further improved by using a halogen-free red coloring agent, and the masking property is not deteriorated, and the halogen content of the solder resist layer is reduced. The present invention has been completed. That is, the present invention is a photocurable resin composition which can be developed with an aqueous alkali solution, and is characterized by containing (A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, and (C) having two or more molecules. a compound of an ethylenically unsaturated group, and (D) a red colorant. 200921272 The photocurable resin composition of the present invention is in one aspect, and may contain (E 1 ) a blue colorant (for example, phthalocyanine blue) and/or (E2) yellow in addition to the red colorant (D). A colorant whose color tone can be blue, green, purple or orange. Further, the photocurable resin composition of the present invention is in one aspect, and the red colorant (D) is a red colorant which does not contain any of a halogen and an azo group. Further, the photocurable resin composition of the present invention is contained in one aspect and further contains (F) a thermosetting component. Further, the photocurable resin composition of the present invention is used in one aspect for coating on copper. Further, in another aspect of the invention, the photocurable resin composition is applied to a carrier film and dried to obtain a photocurable dry film, and the present invention is in another aspect, The photocurable resin composition is a cured product of blue, green, purple or orange. Further, in another aspect of the invention, the dry film is a cured product of blue, green, purple or orange. Further, the present invention is a printed wiring board having a solder resist layer formed of the above cured material on a substrate on which a copper circuit is formed in another aspect. [Effect of the Invention] According to the present invention, it is possible to provide a blue, green, violet or orange colored solder resist layer -8-200921272 which is excellent in masking property due to oxidation of a copper circuit. In particular, it is effective as a blue solder resist resist which is replaced with a general-purpose blue solder resist resist having a problem of masking. Further, the solder resist layer obtained by the present invention has an extremely low halogen content and a markedly reduced amount of halogen gas generated when the coating film is burned. Hereinafter, the present invention will be described in detail. As described above, the photocurable resin composition of the present invention is characterized in that at least a red coloring agent (D) is used as a coloring agent in place of a conventional halogen-containing phthalocyanine green, and in one aspect, in addition to red In addition to the colorant (D), '尙 contains a blue colorant (E1) and/or a yellow colorant (E2)', and the color tone thereof is a photocurable resin composition of blue, green, purple or orange. Therefore, the coloring agent of the present invention will first be described. In the present invention, the colorant may be any of a pigment, a dye, and a pigment by using a conventional one. However, in terms of reducing environmental load and affecting the human body, it is preferred that halogen is not contained. As a red coloring agent (D), monoazo type, bisazo type, azo lake type, benzimidazolone type, fluorene type, diketopyrrolopyrrole type, condensed azo type, hydrazine Specifically, the oxime system, the quinacridone system, and the like may be exemplified by a color index (CI; The Society of Dyers and Colourists, Inc.) number as follows. - monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15, 16,17,21,22,23,31,32,1 12,1 14,146,147,151,170,184,187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269; - bisazo system: Pigment Red 3 7, 3 8, 4 1 : 200921272 monoazo lake : Pigment Red 48:1, 48:2, 48:3, 48:4,49 :1,49:2,50:1,52:1,52:2,53:1,53:2,57: 1,58 :4,63: 1,63:2,64:1,68 ; Benzimidazolone series: Pigment Red 1 7 1,1 75,1 76,1 8 5,208 t-phenanthrene series: Solvent Red 1 3 5,1 79 ; Pigment Red 123, 1 49,1 66,1 78, 1 79 , 1 90,1 94,224; -dionepyrrolopyrrole: Pigment Red 254,255,264, 270,272; -condensed azo system: Pigment Red 220,144,166,214,220, 221,242; -lanthanide: Pigment Red 168; 177,2 16 ; Solvent Red 149, 150, 52, 207; - quinacridone system: Pigment Red 122, 202, 206, 207, 209. Although it is not particularly limited, it is preferable to use a red coloring agent which does not contain an azo group from the viewpoint of safety and harmlessness. The blue coloring agent (E 1 ) is a phthalocyanine-based or an anthraquinone-based, and the pigment is a compound classified as a pigment. Specifically, a color index (CI; The Society of Dyers and Colourists issued the number. - Pigment system: Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60; - Dye system: Solvent Blue 35, 63, 68, 70, 83, 87, 94,97,122,136,67,70 〇-10- 200921272 A metal-substituted or unsubstituted phthalocyanine compound can also be used in addition to the above. The yellow coloring agent (E2) 'is a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindane type, an anthraquinone type, etc., and specifically may be added as follows The color index number. - 蒽醌 system: Solvent Yellow 163, Pigment Yeii〇w 24, 1 08,1 93,147,1 99,202 ; -Different D-introduction 0 full line: Pigment Yellow 110,1〇9,139,179,185 » -condensed azo system: Pigment Yellow 93 , 94,95,1 2 8,1 5 5, 166,180 ; -Benzimenone: Pigment Yellow 120,151,154,156, 175,181 ; -monoazo system: Pigment Yellowl, 2,3,4,5,6,9, 10,12,61, 62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169, 182,183; - bisazo system: Pigment Yellow 12,1 3,1 4,1 6,1 7,5 5,63 , 8, 1,83,87,1 26,1 27,1 52,1 70,1 72,1 74,1 76,1 88,1 98. Although it is not particularly limited, it is preferable to use a yellow coloring agent which does not contain an azo group from the viewpoint of safety and harmlessness. In the present invention, the blending ratio of the red colorant and the blue colorant and/or the yellow colorant is such that the obtained photocurable resin composition or the solder resist layer formed of the cured film is a desired color tone. Specifically, it can be made blue, green, purple or orange in a sufficient ratio. In the present invention, the photocurable resin composition of the present invention or the hardened -11 - 200921272 film exhibits a blue color, a green color, a purple color, and an orange color means that when observed, the cognition is blue, green, purple, and Orange tone. Specifically, the appearance of the resin composition and the hardened film specified by JIS Z872 1 shows the Munsell hue ring (the color of the new color table series 2 Munsell system Japan) Color 硏 Co., Ltd. issued; refer to Figure 1), from 5 BG to ί blue), from 9 Υ to less than 5BG (green), from 3 Ρ to not purple), from 9R to less than 7YR (orange) The range has a chroma of 1 or more and less than 16; a brightness of 1 or more does not reach a chroma of 2 or more and less than 15; and a brightness of 2 or more and less than 9 is a specific blending ratio which is also used by the coloring agent. The influence of various types of additives, etc., cannot be discussed at all, but generally, red coloring agent (D): blue coloring agent (Ε1): yellow Ε 2) = 1 : 〇~50: 0~50. Further, it is preferred to blend 0.05 to 3.0% by mass of the total amount of the composition of the total amount of the coloring agent (D), the blue coloring agent (Ε1), and the yellow coloring. In the present invention, in addition to the above coloring agent, a coloring agent such as violet, orange, brown, black or the like is added to adjust the color tone, and specifically, Violet 19, 23, 29, 32, 36, 38, 42; Solvent, 3 6; C. I. Pigment Orange 1, C. I. Pigment Orange 5, C · I. Pigment Orange Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, C 24, CI Pigment Orange 34, CI Pigment Orange 36, CI The pigment orange is measured by the degree of the naked eye. When the light is hard, the stock of the company is up to 3P ( : 'Μ 7RP (and preferably I 9 , better 〇 or other mass ratio colorant ( color For the purpose of red agent (E2) ratio Pigment Violet 13 13 ' CI .I. Pigment Orange 38 ' CI -12- 200921272 Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64' CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7 etc. Next, the resin (A) containing a carboxylic acid will be described. As a photocurable resin composition of the present invention A carboxylic acid-containing resin (A) containing a carboxylic acid in the molecule can be used, and a carboxylic acid-containing photosensitive resin (A ') having an ethylenically unsaturated double bond in the molecule can be used. The resin is exemplified as the following. (1) to (9) and the like: (1) A carboxylic acid-containing copolymer resin It is obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with one or more compounds having other unsaturated double bonds, and (2) the sensitivity of the carboxylic acid. a resin, which is a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and a compound having one or more other unsaturated double bonds, by having a glycidyl (meth) acrylate or 3, A compound having an epoxy group such as 4-epoxycyclohexylmethyl (meth) acrylate and an unsaturated double bond, or a (meth)acrylic acid chloride or the like, which has a bivalent unsaturated group as a pendant group (Pendant) ) obtained by adding, (3) a kind of photosensitivity a carboxylic acid-containing copolymerized resin which has an epoxy group and an unsaturated group such as glycidyl (meth) acrylate or 3, 4-epoxycyclohexylmethyl (meth) acrylate from 13 to 2009 21272 a compound of a double bond and a copolymer of a compound having another unsaturated double bond, which is reacted with an unsaturated carboxylic acid such as (meth)acrylic acid, and which is obtained by reacting a secondary hydroxyl group formed with a polybasic acid anhydride ( 4) A photosensitive resin containing a carboxylic acid, which is a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having another unsaturated double bond, to have 2-hydroxyl A hydroxyl group-containing (meth) acrylate or the like is reacted with a compound having an unsaturated double bond, and (5) is a photosensitive resin containing a carboxylic acid, which is a reaction of a polyfunctional epoxy compound with an unsaturated monocarboxylic acid. And the generated hydroxyl group is obtained by reacting a saturated or unsaturated polybasic acid anhydride, and (6) is a photosensitive resin containing a hydroxyl group and a carboxylic acid, and is a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative. Saturated or unsaturated polybasic anhydride After that, the produced carboxylic acid is obtained by reacting a compound having an epoxy group and an unsaturated double bond in one molecule, and (7) a photosensitive resin containing a carboxylic acid, which is a polyfunctional epoxy compound, a reaction product of an unsaturated monocarboxylic acid, a compound having at least one alcoholic hydroxyl group in one molecule and a reactive group having an alcoholic hydroxyl group, which is reacted with an epoxy group, is obtained by reacting a saturated or unsaturated polybasic acid anhydride. (8) A photosensitive resin containing a carboxylic acid, which is a polyfunctional oxetane compound having at least two oxetane rings in one molecule, reacted with an unsaturated monocarboxylic acid' and obtained The first-stage hydroxyl group in the modified oxetane resin is obtained by reacting a saturated or unsaturated polybasic acid anhydride, and -14-200921272 (9) a photosensitive resin containing a carboxylic acid, which is a polyfunctional ring After the oxy resin is reacted with an unsaturated monocarboxylic acid, the carboxylic acid-containing resin obtained by reacting the polybasic acid anhydride further has one ethylene oxide (〇xirane) ring and one or more ethylenically unsaturated groups in the molecule. Compound reaction to obtain 'but not limited to this some. In the above examples, the carboxylic acid-containing resin of the above (2), (5), and (7) is preferable, and the carboxylic acid-containing photosensitive resin of the above (9) is preferably photocurable or cured. In terms of surface, it is preferred. Further, in the present specification, the terms (meth)acrylates, which are collectively referred to as acrylates, methacrylates, and the like, have the same behaviors. The carboxylic acid-containing resin (A) as described above is developed in an aqueous alkali solution because it has a large number of free acid groups in the side chain of the backbone polymer. Further, the acid hydrazine of the carboxylic acid-containing resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably 45 to 1 20 mgKOH/g. When the acid hydrazine of the carboxylic acid-containing resin is less than 40 mgKOH/g, alkali development is difficult. On the other hand, when it exceeds 200 mgKOH/g, it is necessary to make the line thinner by the dissolution of the exposed portion of the developer. In the case where the exposed portion and the unexposed portion are not distinguished from each other, the dissolution and peeling in the developer are facilitated, and the drawing of the normal photoresist pattern becomes difficult, which is not preferable. Further, the weight average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, but is generally 2,000 to 150,000, and further 5,000 〜! Hey, the range of 〇〇〇 is better. When the weight average molecular weight is less than -15-200921272 2,000, the non-stick property is poor, the moisture resistance of the film after exposure is poor, and the film is reduced during development, and the resolution is poor. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is poor. The blending amount of the carboxylic acid-containing resin (yttrium) is in the total composition, preferably 20 to 60% by mass, more preferably 30 to 50% by mass. When the amount is less than the above range, the film strength is lowered, which is not preferable. On the other hand, in the case of more than the above range, the viscosity is high and the coatability and the like are lowered, which is not preferable. Next, the photopolymerization initiator (Β) will be described. The photopolymerization initiator (Β) may, for example, be acetophenone, 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxy-2-phenylbenzene. Ketone, Ρ-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-l -[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morphinylphenyl)-butyl Acetophenones such as ketone-oxime, N,N-dimethylaminoacetophenone, diphenyl ketone, methyl diphenyl ketone, 2-chlorodiphenyl ketone, 4,4'-dichloro Phenyl ketone, 4,4'-bisdimethylaminodiphenyl ketone, 4,4,-bisdiethylaminodicarbyl, Michler's ketone, 4-benzylidene- Diphenyl ketones such as 4'-methyldiphenyl sulfide; benzyl; benzamidine, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutylene a benzoin ether such as ether; a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthiophene Tons of ketone, 2,4~diethylthioxanthone, 2,4-diisopropylstilbene Oxime ketones; 2_methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, -16- 200921272 2-amino hydrazine, 2, 3 Anthraquinones such as diphenylhydrazine; organic peroxides such as benzammonium peroxide and cumene peroxide; 2,4,5-triarylimidin dimer, riboflavin Thiol-based compound such as riboflavin tetra butyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-gin-s - an organic halogen compound such as three tillage, 2,2,2-tribromoethanol, tribromomethylphenylhydrazine; 2,4,6-trimethylphenylnonyldiphenylphosphine oxide 'double (2,4 , 6-trimethylphenyl fluorenyl)-phenylphosphine oxide) and the like. These compounds may be used singly or in combination of two or more. Further, the photopolymerization initiator (B) may be used in combination of one or more kinds of ethyl phthalate such as hydrazine, hydrazine-dimethylaminobenzoic acid, and isoamyl N,N-dimethylaminobenzoate. a tertiary amine such as pentyl-4-dimethylaminobenzoate, triethylamine or triethanolamine, bis(η5-cyclopentadienyl)-bis(2,6-difluoro-3- (1Η-Shame-1-yl)phenyl) 等 ti ti ti ti ti ti ti ti ti ti ti ti ti 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- -[4-(phenylthio)-,2-(indolyl-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoinyl)-9H-indole A photo sensitizer of an oxime ester such as oxazol-3-yl]-, 1-(0-ethenyl fluorene) is used. A preferred combination of the above photopolymerization initiator (B) is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (for example, manufactured by Ciba Specialty Chemicals Co., Ltd. , IRGACURE 369: IRGACURE is a registered trademark) and bis(η5-cyclopentadienyl)-bis(2,6-difluoro-3-(lH-pyrrole-l-yl)phenyl) chin (for example, manufactured by Ciba Specialty Chemicals Co., Ltd.) , IRGACURE 784) combination; 2,4,6-trimethylphenylnonyldiphenylphosphine oxide 200921272 (eg, Luc ir in BA by BASF) and 2-(ethyl fluorenylmethyl) thioxene - a combination of 9-ketone (for example, CGI Specialty Chemicals Co., Ltd., CGI-3 25 ); or 2,4,6-trimethylphenylnonyldiphenylphosphine oxide (for example, 8 8 3? 1^(^1) ^11丁?0) in combination with bis(2,4,6-trimethylphenylhydrazino)-phenylphosphine oxide (for example, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819), etc. Further, photopolymerization as described above The preferred range of the amount of the starting agent (B) is preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (A). Ratio of blending ratio of photopolymerization initiator In the case where the range is small, the photohardenability of the obtained composition is deteriorated. On the other hand, when the amount is more than the above range, the properties of the obtained cured coating film are deteriorated, and the storage stability of the composition is deteriorated. The compound having two or more ethylenically unsaturated groups in the molecule is described. The compound having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention (C) The photo-hardening of the carboxylic acid-containing resin (A) is insolubilized or helps to dissolve in the aqueous alkali solution by irradiation with an active energy ray. Examples of such a compound include ethylene glycol and methoxytetraethylene glycol. a diacrylate of ethylene glycol such as polyethylene glycol or propylene glycol; a polyol such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol or cis-hydroxyethyl isocyanurate or the like a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide (Pfopylene oxide) adduct; phenoxypropane-18-200921272 enoate, biguanide A diacrylate, And so on a polyvalent acrylate such as an epoxide ethylene oxide adduct or a propylene oxide (pr〇pylene 〇xide) adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trishydroxyl a polyacrylate of a glycidyl ether such as a propane triglycidyl ether or a triglycidyl isocyanurate; and a melamine acrylate and/or a methacrylate corresponding to the above acrylate. Further, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin is reacted with acrylic acid or a hydroxyl group such as pentaerythritol triacrylate in which a hydroxyl group of the epoxy acrylate resin is further exemplified An epoxy urethane acrylate compound obtained by reacting an ester with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin does not deteriorate the finger-drying property and can improve the light hardenability. The blending ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the carboxylic acid-containing resin (A). It is a ratio of 1 to 70 parts by mass. When the blending amount is less than 5 parts by mass, the photocurability is lowered and the alkali developing system which irradiates the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered and the coating film becomes brittle, which is not preferable. Next, the thermosetting component (F) will be described. In order to impart heat resistance to the photocurable resin composition of the present invention, a thermosetting component (F) may be added. Particularly preferred is a thermosetting component (F) having two cyclic ether groups and/or cyclic thioether groups (hereinafter, abbreviated as cyclic (thio)ether groups) on the range of -19-200921272. . The thermosetting component (F) having two or more cyclic (thio)ether groups in such a molecule is a cyclic ether group having a ring of 3, 4 or 5 members in the molecule, or a cyclic thioether group. Any one of the compounds having two or more types of the group may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (F-1): a molecule a compound having at least two or more oxetanyl groups, that is, a polyfunctional oxetane compound (F-2); a compound having at least two or more thioether groups in the molecule, that is, a surface sulfide Resin (episulfide resin) (F-3). The polyfunctional epoxy compound (F-1) may, for example, be EPIΚ 8TE 8 2 8 manufactured by japan Epoxy Resins Co., Ltd., EPIKO TE 8 3 4, EPIKOTE 1001 > EPIKOTE 1004, EPICLON manufactured by Dainippon Ink Chemical Industry Co., Ltd. 840, EPICLON 850, EPICLON 1 050, EPICLON 20 5 5, EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, manufactured by Dow Chemical Co., Ltd. DER664; Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 from Ciba Specialty Chemicals, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA -1 2 8 from Sumitomo Chemical Industries Co., Ltd.; Asahi Kasei Industrial Co., Ltd. Bisphenol A type epoxy resin of AER330, AER331, AER661, AER 6 64, etc. (all trade names); EPIKOTE YL903 manufactured by Japan Epoxy Resins Co., Ltd., Dainippon Ink Chemistry -20- 200921272 EPICLON 152, EPICLON 165, EPOTOHTO YDB-400, YDB-500 manufactured by Dongdu Chemical Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Araldite 80 manufactured by Ciba Specialty Chemicals 11. Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, Ltd., AER711, AER714, etc. (both trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.; EPIKOTE 152 manufactured by Japari Epoxy Resins Co., Ltd. , EPIKOTE 154, DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by Otsuka Ink Chemical Industry Co., Ltd., ETOPOHTO YDCN-701, YDCN manufactured by Dongdu Chemical Co., Ltd. -704, Araldite ECN 1 23 5 'Araldite ECN 1 273 ' from Ciba Specialty Chemicals, Inc. Araldite ECN1299, Araldite XPY3 07, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE, manufactured by Nippon Kayaku Co., Ltd. -306, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Aurora Chemicals Co., Ltd. AER ECN-235, ECN-299, etc. (all trade names) novolac type epoxy resin; EPICLON 830 manufactured by Ink Chemical Industry Co., Ltd., EPIKOTE 807 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTO YDF-170, YD F -1 7 5 ' YDF-2004 > Ciba Specialty Chemicals, manufactured by Toho Chemical Co., Ltd. Bisphenol F-type epoxy resin such as Araldite XPY306 (all trade names); hydrogenated bisphenol A epoxy resin such as EPOTOHTO ST-2004, ST-2007, ST-3 000 (trade name) manufactured by Dongdu Chemical Co., Ltd. Resin; EPIKOTE 604 manufactured by Japan Epoxy Resins Co., Ltd., manufactured by Tosho Kasei Co., Ltd.-21 - 200921272 ΕΡΟΤΟΗΤΟ 434-434, Araldite MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. Name) glycidylamine type epoxy resin;
Ciba Specialty Chemicals 公司製之 Araldite CY-3 50 (商 品名）等的海因（hydantoin)型環氧樹脂；DAICEL化學 工業公司製之 CELLOXIDE 2 02 1 ， Ciba SpecialtyHydantoin type epoxy resin such as Araldite CY-3 50 (commodity name) manufactured by Ciba Specialty Chemicals Co., Ltd.; CELLOXIDE 2 02 1 manufactured by DAICEL Chemical Industry Co., Ltd., Ciba Specialty
Chemicals 公司製之 Araldite CY175、CY179 等（皆商品 名）的脂環式環氧樹脂；Japan Epoxy Resins公司製之 YL-93 3，Dow Chemical 公司製之 T.E.N.、EPPN-501、 EPPN-5 02等（皆商品名）的三羥基苯基甲烷型環氧樹脂 ;Japan Epoxy Resins 公司製之 YL-6056、YX-4000、YL-6121 (皆商品名）等的聯二甲苯酚型或雙酚型環氧樹脂或 彼等的混合物；日本化藥公司製EBP S-200，旭電化工業 公司製EPX-30，大曰本油墨化學工業公司製之EXA-1514 (商品名）等的雙酚 S型環氧樹脂；Japan Epoxy Resins 公司製之EPIKOTE 157S (商品名）等的雙酣A酧醛清漆 型環氧樹脂；Japan Epoxy Resins公司製之£?1〖0丁珏丫1>-931，Ciba Specialty Chemicals 公司製之 Araldite 163 等 (皆商品名）的四酚乙烷型環氧樹脂；ciba sPecialty Chemicals公司製之Araldite PT810’日產化學工業公司製 之TEP 1C等（皆商品名）的雜環環氧樹脂；日本油脂公司 製BLEMMER DGT等的二縮水甘油基酞酸酯樹脂；東都化 成公司製ZX- 1 0 63等的四縮水甘油基二甲苯酚乙烷（ glycidyl xylenoyl ethane)樹脂；新日鐵化學公司製ESN- -22- 200921272 190、ESN-3 60，大曰本油墨化學工業公司製 HP-4032、 EXA-4 75 0、EXA-4700等的含有萘基之環氧樹脂；大日本 油墨化學工業公司製HP-7200、HP-72〇OH等之具有二環 戊二烯骨架的環氧樹脂；日本油脂公司製CP-50S、CP-5 0M等的縮水甘油基甲基丙烯酸酯共聚合系環氧樹脂；進 而環己基順丁烯二醯亞胺與縮水甘油基甲基丙烯酸酯的共 聚合環氧樹脂；環氧改性之聚丁二烯橡膠衍生物（例如 DAICEL化學工業製PB-3600等）、CTBN改性環氧樹脂 (例如東都化成公司製之YR-102、YR-45〇等）等，但不 限定於此。此等環氧樹脂係可單獨或組合2種以上使用。 此等之中尤其以酚醛清漆型環氧樹脂、雜環環氧樹脂、雙 酚A型環氧樹脂或彼等之混合物爲佳。 前述多官能氧雜環丁烷化合物（F-2 )，係可列舉雙[ (3-甲基-3-氧雜環丁基甲氧基）甲基]醚、雙[(3-乙基-3· 氧雜環丁基甲氧基）甲基]醚、1，4_雙[(3-甲基-3-氧雜環 丁基甲氧基）甲基]苯、1，4-雙[(3-乙基-3-氧雜環丁基甲 氧基）甲基]苯、（3-甲基-3-氧雜環丁基）甲基丙烯酸酯 、（3-乙基-3-氧雜環丁基）甲基丙烯酸酯、（3-甲基-3-氧雜環丁基）甲基甲基丙烯酸酯、（3-乙基-3-氧雜環丁基 )甲基甲基丙烯酸酯、或彼等之寡聚物或共聚合物等的多 官能氧雜環丁烷類，其它還有氧雜環丁烷醇與酚醛清漆樹 脂、聚（p -經基苯乙嫌）、卡魯特型（cardo type)型雙 酚類、杯芳烴（calixarene )類、杯間苯二酚芳烴（ calixresorcinarene ) 類、或與具有倍半砂氧院 （ -23- 200921272 silsesquioxane)等之羥基的樹脂的醚化物等。其它’亦可 列舉具有氧雜環丁院環的不飽和單體與院基（甲基）丙嫌 酸酯的共聚合物等。 前述分子中具有2個以上之環狀硫醚基的化合物（F- 3)，係可列舉如Japan Epoxy Resins公司製之雙酣A型 表硫化物樹脂γ L 7 0 〇 〇等。又’使用同樣的合成方法’亦 可使用酚醛清漆型環氧樹脂之環氧基的氧原子取代爲硫原 子的表硫化物樹脂。 前述分子中具有2個以上之環狀（硫代）醚基的熱硬 化性成分（F )的摻合比例’係對於前述含有羧酸之樹脂 (A)的羧基1當量，較佳爲0.6〜2.5當量、更佳爲〇-8 〜2.0當量的範圍。分子中具有2個以上之環狀（硫代） 醚基的熱硬化性成分（F )的摻合量，未達0.6時抗:焊光 阻膜中有羧基殘留，且耐熱性、耐鹼性、電氣絕緣性等降 低，故不佳。一方面，超過2.5當量時，因低分子量的環 狀（硫代）醚基殘留在乾燥塗膜，塗膜的強度等降低’故 不佳。 本發明之光硬化性樹脂中，使用上述分子中具有2個 以上之環狀（硫代）醚基的熱硬化成分（F )時’以含有 熱硬化觸媒（G )爲佳。該種熱硬化觸媒（G )，可列舉 如咪唑、2 -甲基咪唑、2 -乙基咪唑、2 -乙基-4-甲基咪唑、 2 -苯基咪唑、4 -苯基咪唑、1-氰基乙基-2-苯基咪唑、1-( 2 -氰基乙基）-2 -乙基_4_甲基咪唑等的咪唑衍生物；二氰 二胺（dicyan di amide)、苄基二甲胺、4-(二甲胺基）_ -24- 200921272 Ν,Ν-二甲基苄胺、4-甲氧基-N，N-二甲基苄胺、4-甲基-N，N-二甲基苄胺等的胺化合物；己二酸二醯肼、癸二酸二 醯肼等的肼化合物；三苯基膦等的磷化合物等，又市售品 如四國化成工業公司製之 2MZ-A、2MZ-OK、2PHZ、 2P4BHZ、2P4MHZ (皆咪唑系化合物的商品名）,SAN-APRO 公司製之 U-CAT3503N、U-CAT3502T (皆二甲胺之 嵌段異氰酸酯化合物的商品名），DBU、DBN、U-CATSA102、U-CAT5002 (皆雙環脒化合物及其鹽）等。 尤其’不限定於此等的’亦可使用環氧樹脂或氧雜環丁烷 化合物的熱硬化觸媒，或亦可爲促進環氧基及/或氧雜環 丁基基與羧基的反應者，單獨或混合2種以上使用亦無妨 。又’亦可使用胍胺（guanamine )、乙醯胍胺、苯并胍 胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三 畊、2_乙烯基_4,6-二胺基-S-三Π并、2-乙烯基-4,6-二胺基-S-三畊·異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧 基乙基-S-三_ .異三聚氰酸加成物等的s-三D并衍生物， 較佳係將此等作爲密著性賦予劑亦具機能的化合物與前述 熱硬化觸媒倂用。 此等熱硬化觸媒的摻合量係一般量的比例即足夠，例 如，對於含有羧酸之樹脂（A)或分子中具有2個以上之 環狀（硫代）醚基的熱硬化性成分（F ) 1 0 0質量份，較 佳爲0.1〜20質量份、更佳爲0.5〜15.0質量份。 本發明之光硬化性樹脂組成物係爲提高其塗膜的物理 強度等’而視需要可摻合塡充劑。此種塡充劑，可使用周 -25- 200921272 知習用的無機或有機塡充劑，尤其較佳使用硫酸鋇、球狀 二氧化矽及滑石。進而，亦可使用具有1個以上之乙烯性 不飽和基的化合物或前述多官能環氧樹脂（E1)中分散奈 米二氧化矽之Hanse-Chemie公司製的NANOCRYL (商品 名）XP 0396、XP 0596、XP 073 3、XP 0746、XP 0765、 XP 0768、XP 0953、XP 0954、XP 1045 (皆製品等級名） 或 Hanse-Chemie 公司製的 NANOPOX (商品名）XP 0516 、XP 0 5 25、XP 03 14 (皆製品等級名）。此等可單獨或摻 合2種以上。 此等塡充劑的摻合量對於上述含有羧酸之樹脂（A) 100質量份，較佳爲300質量份以下、更佳爲0.1〜300質 量份、特佳爲0.1〜150質量份。塡充劑的摻合量超過300 質量份時，感光性組成物的黏度變高且印刷性降低、硬化 物變脆而不佳。 進而，本發明之光硬化性樹脂組成物係爲上述含有羧 酸之樹脂（A)的合成或組成物之調整、或爲塗佈於基板 、載體薄膜的黏度調整而可使用有機溶劑。 此種有機溶劑，可列舉酮類、芳香族烴類、乙二醇醚 類、乙二醇醚醋酸酯類、酯類、醇類、脂肪族烴、石油系 溶劑等。更具體地，甲基乙基酮、環己酮等的酮類；甲苯 、二甲苯、四甲基苯等的芳香族烴類；溶纖劑、甲基溶纖 劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙 二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、 三乙二醇單乙基醚等的乙二醇醚類；乙酸乙酯、乙酸丁酯 -26- 200921272 、二丙二醇甲基醚醋酸酯、丙二醇甲基醚醋酸酯、 乙基醚醋酸酯、丙二醇丁基醚醋酸酯等的酯類；乙 醇、乙二醇、丙二醇等的醇類；辛烷、癸烷等的脂 ;石油醚、石腦油、氫化石腦油、溶劑石腦油等的 溶劑等。此種有機溶劑可單獨或以2種以上的混合 用。 本發明之光硬化性樹脂組成物進而視需要可摻 二酚、對苯二酚單甲基醚、第三丁基兒茶酚、焦掊 噻嗪等之周知習用的熱聚合禁止劑；微粉末二氧化 機膨潤土、蒙脫石等之周知習用的增黏劑、聚矽氧 氟系、高分子系等之消泡劑及/或調平劑、咪唑系 系、三唑系等的矽烷偶合劑、抗氧劑、防鏽劑等周 的添加劑類。 接著，對使用本發明之光硬化性樹脂組成物所 薄膜、硬化物、以及具有由該硬化物所成之抗焊光 印刷配線板進行說明。 本發明所述之光硬化性樹脂組成物係藉由常用 由塗佈於載體薄膜，並使其乾燥而可得光硬化性的 。本發明所述之光硬化性樹脂組成物或此乾薄膜係 經光硬化而得。光硬化係亦可以藉由紫外線曝光裝 行，雷射發射光源尤其藉由波長爲3 50〜41 Onm的 使之硬化。本發明所述之印刷配線板係經此方式的 後，再經熱硬化而得。 具體地係進行如以下的方式，可形成乾薄膜、 丙二醇 醇、丙 肪族烴 石油系 物被使 合對苯 酚、吩 矽、有 烷系、 、噻唑 知習用 得的乾 阻層的 手段經 乾薄膜 於銅上 置來進 雷射光 光硬化 硬化物 -27- 200921272 、印刷配線板。即亦，本發明之光硬化性樹脂組成物係例 如以前述有機溶劑調整爲適於塗佈方法的黏度，於基材上 藉由浸塗法、流塗法、輥塗法、棒塗法、網版印刷法、簾 塗法等方法進行塗佈，以約6 0〜1 0 0 t的溫度使組成物中 所含的有機溶劑揮發乾燥（假乾燥），可形成無黏性（ tack-free)的塗膜。又’將上述組成物塗佈於載體薄膜上 ，藉由使之乾燥爲薄膜型式而捲取貼合於基材上可形成樹 脂絕緣層。其後，藉由接觸式（或非接觸方式），經由形 成圖型的光罩，藉由活性能量線選擇性地曝光或藉由雷射 直接（Laser direct)曝光機直接圖型曝光，而未曝光部分 藉由稀鹼水溶液（例如0.3〜3 %碳酸鹼水溶液）予以顯影 形成光阻圖型。進而含有熱硬化成分（F )之組成物的情 形，例如於約1 40〜1 80 °C的溫度進行加熱藉由使其熱硬化 ，使前述含有羧酸之樹脂（A)的羧基與分子中具有2個 以上環狀（硫代）醚基的熱硬化性成分（F )反應，可形 成具耐熱性、耐藥品性、耐吸濕性、密著性、電氣特性等 諸特性優異的硬化塗膜。 又，即使不含熱硬化性成分（F )的情形，經由熱處 理，使曝光時未反應的狀態下而殘留之乙烯性不飽和鍵進 行熱自由基聚合，且爲提昇塗膜特性，亦可依目的.用途 來進行熱處理（熱硬化）。 上述基材，可列舉使用紙苯酣、紙環氧、玻璃布環氧 、玻璃聚醯亞胺、玻璃布/不織布環氧、玻璃布/紙環氧、 合成纖維環氧、氟·聚乙烯· PPO ·氰酯（cyanate ester -28- 200921272 )等的高頻電路用覆銅層合版等材質者之所有的等級（ FR-4等）的覆銅層合版、其它之聚醯亞胺薄膜、PET薄膜 、玻璃基板、陶瓷基板、晶圓板等。 塗佈本發明之光硬化性樹脂組成物後進行之揮發乾燥 ，係可使用熱風循環式乾燥爐、IR爐、熱板、對流爐等（ 使用備有以蒸氣之空氣加熱方式的熱源且使乾燥機內的熱 風向流接觸的方法及藉由噴嘴噴向支撐體的方式）來進行 〇 如以下方式地塗佈本發明的光硬化性樹脂組成物，於 揮發乾燥後，對所得之塗膜，進行曝光（照射活性能量線 )。塗膜係曝光部（藉由活性能量線所照射的部分）硬化 〇 照射上述活性能量線所使用的曝光機係可使用採用雷 射直接描繪裝置（雷射直接成像（Laser direct imaging) 裝置）、搭載金屬鹵化物燈的曝光機、搭載（超）高壓水 銀燈的曝光機、搭載水銀短弧燈的曝光機、或（超）高壓 水銀燈等的紫外線燈的直接描繪裝置。活性能量線若使用 最大波長於3 5 0〜4 lOnm之範圍的雷射光，亦可爲氣體雷 射、固體雷射任一者。又’其曝光量依膜厚等而不同，一 般可使爲5〜200mJ/cm2、較佳爲5〜100mJ/cm2、進而較 佳爲5〜50mJ/cm2的範圍內。上述直接描繪裝置，可使用 例如日本Orbotech公司製、PENTAX公司製等商品，最大 波長若發射爲3 50〜410nm之雷射光的裝置，亦可使用任 一之裝置。 -29- 200921272 前述顯影方法可藉由浸漬法、噴淋法、噴霧法、 法等；作爲顯影液，可使用氫氧化鉀、氫氧化鈉、碳 、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼水溶液。 【實施方式】 [實施例] 以下，示實施例及比較例對本發明具體地說明， 明固然不限定於下述實施例。又，以下出現之「份」 特別限定則全部表示「質量份」。 <含有羧酸之樹脂的合成> 依照下述合成例製作本發明之含有羧酸之樹脂< 〇 將甲酚酚醛清漆型環氧樹脂（大日本油墨化學工 股）製、“EPICLON”（註冊商標）N-69 5、環氧當量 )220份倒入附攪拌機及回流冷卻器的四口燒瓶中， 入卡必醇醋酸酯2 1 4份，進行加熱溶解。接著加入聚 制劑之對苯二酚0.46份、與反應觸媒之三苯基膦1 ·: 。將此混合物於95 °C〜105 °C進行加熱，且徐緩地滴 烯酸72份，使之反應16小時。冷卻此反應產物至 9 0°C，且加入四氫鄰苯二甲酸酐份’使之反應8 ，於冷卻後，取出反應溶液（稱作清漆（A-1 ))。 進行所得之含有羧酸之樹脂係固形物之酸値爲 mgKOH/g、不揮發份65%。 刷洗 酸納 本發 係無 A ) 業（ 220 且加 合抑 8份 下丙 8 0〜 小時 如此 -30- 100 200921272 <實施例1〜7及比較例1〜2 > 前述含有羧酸之樹脂的合成中所得的清漆（A-1)， 與表1示之成分，以同表中記載之摻合比例，以3支輥進 行混練求得光硬化性樹脂組成物。 -31 - 200921272 (N 〇 1 1 1 vo o o m ο 寸 in 〇 m 2 — 隹 lg| Hi 3 S ° ^ ^ e E 3 g w ^ g 〇 君恶旯ilJ骚 b.s Λ b ^ 3 CS Li li? 3 ^ w 11 ^ if Γ**·* 00 On »~-h 兴关*兴*关* 〇 1 1 1 o 晒 rn ο vn 〇 m 實施例 154 〇 〇 CN 1 1 ITi 〇 ir> o 1 Ο (Τ) Ο m 〇 m 〇 1 1 Ο o ο 〇 f—Η m ο 寸 ^Ti 〇 〇 T-H cn 〇 1 1 »—Η Ο o T-H 1 ΓΛ Ο 寸 ^Τ) 〇 τ·Η m g <4 |g| u u ^ ^ 匿o锆 h 齩S褰莽=写s 111 ml 匾^觀芒扫扫— K)ua〇| i gu 梢含eS .1.1 ·& ^ g,11°yyy^ 1 c/ϋ m vn ό 并 并 并关关并 寸 Η 〇 τ·^ 1 'P-H 〇 I 'O o σν ο ο »—Η rn Ο 寸 〇 ro m 1—Η 〇 Ψ < 〇 1 I p I ο 寸 们 ο m CN 〇 1 〇 1 1 Ο m ο 寸 ο m ^Η 〇 »—Ή 1 〇 1 1 I m ο 寸 ο r—^ m 組成(質量份） 清漆(Α-1) 光聚合起始劑(ΒΓ1 含有乙烯性不飽和基之化合物(c-ir2 紅色著色劑(D-lf3 紅色著色劑(D-2)"4 紅色著色劑(D-3；r5 藍色著色劑(E-l)+6 黃色著色劑(E-2f 7 多官能環氧化合物(F-i-ir8 多官能環氧化合物(F-l-2)#9 熱硬化觸媒(G-1)*10 熱硬化觸媒(G-2)”1 有機溶劑*12 硫酸鋇*13 聚矽氧烷系消泡劑 備註 -32 - 200921272 對實施例1〜7及比較例1〜2的光硬化性樹脂組成物 ’依照下述評估基準來評估性能及特性。結果示於表2。 性能評價： 〈最適曝光量/感度〉 拋光輕（buff roll)硏磨銅厚35μιη之回路圖型基板 後’經水洗、乾燥後，藉由網版印刷法於其全面塗佈實施 例1〜7及比較例1〜2之光硬化性樹脂組成物，於8 0 °c之 熱風循環式乾燥爐使其乾燥60分鐘。乾燥後，使用搭載 金屬鹵化燈的曝光裝置，介由Step tablet ( Kodak No.2) 進行曝光，使以6 0秒進行顯影（3 0 °C、0 · 2 Μ P a、1質量％ 碳酸鈉水溶液）之際殘存之Step tablet的圖型爲7段時作 爲最適曝光量。 〈解像性〉 拋光輥硏磨線/距爲300/300、銅厚35μηι之回路圖型 基板後’經水洗、乾燥後，藉由網版印刷法塗佈實施例1 〜7及比較例1〜2之光硬化性樹脂組成物，於8〇。(：之熱 風循環式乾燥爐使其乾燥30分鐘。乾燥後，使用搭載金 屬鹵化燈的曝光裝置，進行曝光。曝光圖型係使用於間距 部描繪20/30/40/50/60/70/80/90/1 00μιη之線條的直描用數 據或光罩。曝光量係使成爲光硬化性樹脂組成物之最適曝 光量地照射活性能量線。曝光後，藉由3 0。(：之1質量％碳 酸鈉水溶液來進行顯影，描繪圖型，經由1 5 〇 °C X 6 0分鐘 -33- 200921272 的熱硬化處理求得硬化塗膜。 使用調整爲200倍的光學顯微鏡來求出所得之抗焊光 阻用感光性樹脂組成物之硬化塗膜的最小殘存線條。 特性試驗= (評價基板之製作）於形成有圖型之銅箔基板上， 以網版印刷法全面塗佈上述實施例1〜4及比較例1〜2之 組成物，於80t進行20分鐘乾燥，且放冷至室溫。對此 基板使用搭載金屬鹵化燈的曝光裝置，以最適曝光量曝光 抗焊光阻圖型，將 30°C之l%Na2C03水溶液以噴壓 2 kg/cm2的條件進行60秒鐘顯影，得到光阻圖型。將此基 板於UV輸送爐中以累積曝光量lOOOmJ/cm2的條件照射紫 外線後，於1 50°C加熱60分鐘後使之硬化。對所得之印刷 基板（評價基板）如以下地進行評價特性。 〈塗膜之色〉 對上述實施例及比較例之抗焊光阻，以目視判斷硬化 物之顏色。 〈銅回路變色〉 進而將評價基板於1 5 0 °c加熱2小時，如以下地判斷 銅回路上之變色程度。 〇〇：完全沒有變色。 〇：與初期相比多少有變色，但完全沒有光阻之薄的 -34- 200921272 部分與厚的部分的差別。 △:察見有變色，但沒有光阻之薄的部分與厚的部分 的差別。 X:察見光阻之薄的部分有變色，與厚的部分差別顯 著。 〈焊料耐熱性〉 將已塗佈松香（rosin )系助焊劑（fiux )的評價基板 浸漬於事先設定在2 6 0 °C的焊料槽，以變性酒精洗淨助焊 劑後，對以目視觀察之光阻層的膨脹.剝離進行評價。判 定基準如下。 ◦:即使重複3次以上1 0秒鐘浸漬亦不見有剝離。 △:若重複3次以上1 0秒鐘浸漬則有少許剝離。 X :於3次以內1 0秒鐘浸漬則於光阻層有膨脹、剝離 〈耐無電解鍍金性〉 使用市售品之無電解鑛鎳浴及無電解鍍金浴，以鎳 〇·5μηι、金0·0 3μιη之條件進行鍍敷，藉由進行膠帶剝除以 評價光阻層之剝離有無或鍍敷滲入有無，之後，以前述焊 料耐熱性的試驗條件，浸漬於焊料槽1 〇秒鐘，於洗淨、 乾燥後’藉由進行膠帶剝除以評價光阻層之剝離有無。判 定基準如下。 〇：完全不見有變化。 -35- 200921272 △:鍍敷後察見些許滲入且察見焊料耐熱後之剝離。 X :鍍敷後有剝離。 〈耐電蝕性〉 取代銅箔基板而使用IPC B-25之梳型電極B試樣（ coupon )，以上述條件製作評價基板，對此梳型電極外加 DC 1 00V之偏壓電壓，於85°C、85%R.H.的恆溫恆濕槽中 確認1,0 00小時後之遷移（migration )有無。判定基準如 以下。 〇：完全不見有變化者。 △:僅些許變化者。 X :遷移產生者。 〈耐酸性〉 將評價基板於室溫下浸漬於i〇vo1%h2so4水溶液中 3 0分鐘，確認滲入或塗膜之溶出，進而確認以膠帶剝除之 剝離。判定基準如下。 〇：無滲入、溶出、剝離。 △:確認有少許滲入、溶出或剝離。 X :確認有大量滲入、溶出或剝離。 -36- 200921272 〔表2〕 性能·特性 實施例 比較例 1 2 3 4 5 6 7 1 2 硬化塗膜的色調 紅 橙 藍 綠 藍 綠 紫 藍 綠 感度(mJ/cm2) 300 300 300 300 300 300 300 300 300 解像性(μιη) 50 50 50 50 50 50 50 70 60 銅回路之變色試驗 〇〇 〇〇 〇 〇〇 〇 〇〇 〇〇 X Δ 焊料耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐電蝕性 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐無電解鍍金性 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐酸性 〇 〇 〇 〇 〇 〇 〇 〇 〇 【圖式簡單說明】 〔圖1〕示蒙賽爾色相（Munsellhue)環的圖。 -37-An alicyclic epoxy resin of Araldite CY175, CY179, etc. (all trade names) manufactured by Chemicals Co., Ltd.; YL-93 3 manufactured by Japan Epoxy Resins Co., Ltd., TEN, EPPN-501, EPPN-5 02 manufactured by Dow Chemical Co., Ltd., etc. Trihydroxyphenylmethane type epoxy resin, all of which are trade names; bis- xylenol type or bisphenol type epoxy such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Japan Epoxy Resins Co., Ltd. Resin or a mixture of them; EBP S-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy such as EXA-1514 (trade name) manufactured by Otsuka Ink Chemical Industry Co., Ltd. Resin; bismuth A aldehyde varnish type epoxy resin such as EPIKOTE 157S (trade name) manufactured by Japan Epoxy Resins Co., Ltd.; Japan Epoxy Resins Co., Ltd. KK110珏丫1>-931, Ciba Specialty Chemicals a tetraphenol ethane type epoxy resin such as Araldite 163 (all trade names); a heterocyclic epoxy resin of TEP 1C (all trade name) manufactured by Ribal PT810' manufactured by Ciba sPecialty Chemicals Co., Ltd.; Japanese oil company BLEMMER DGT, etc. A diglycidyl phthalate resin; a glycidyl xylenoyl ethane resin such as ZX- 1 0 63 manufactured by Dongdu Chemical Co., Ltd.; ESN--22-200921272 190 manufactured by Nippon Steel Chemical Co., Ltd. ESN-3 60, epoxy resin containing naphthalene based on HP-4032, EXA-4 75 0, EXA-4700, manufactured by Otsuka Ink Chemical Industry Co., Ltd.; HP-7200, HP-72 manufactured by Dainippon Ink Chemical Industry Co., Ltd. An epoxy resin having a dicyclopentadiene skeleton such as 〇OH; a glycidyl methacrylate copolymerized epoxy resin such as CP-50S or CP-5 0M manufactured by Nippon Oil Co., Ltd.; and further cyclohexyl-n-butene Copolymerized epoxy resin of diimine and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resin ( For example, YR-102, YR-45, etc. manufactured by Dongdu Chemical Co., Ltd., etc., but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable. The polyfunctional oxetane compound (F-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3·). Oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-) 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylic acid Ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, or oligomerization thereof Polyfunctional oxetane such as a substance or a copolymer, and other oxetane and novolak resins, poly(p-pyridylbenzene), cardo type a bisphenol, a calixarene, a calixresorcinarene, or an etherified product of a resin having a hydroxyl group such as a sesquifer (-23-200921272 silsesquioxane). Others may also be exemplified by a copolymer of an unsaturated monomer having an oxetane ring and a poly(meth)propionate. The compound (F-3) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bismuth A-type sulfide resin γ L 7 0 〇 制 manufactured by Japan Epoxy Resins Co., Ltd. Further, the same synthesis method can be used, and the oxygen atom of the epoxy group of the novolac type epoxy resin can be used instead of the surface sulfide resin of the sulfur atom. The blending ratio of the thermosetting component (F) having two or more cyclic (thio)ether groups in the molecule is 1 equivalent to the carboxyl group of the carboxylic acid-containing resin (A), preferably 0.6 to 1. 2.5 equivalents, more preferably in the range of 〇-8 to 2.0 equivalents. When the amount of the thermosetting component (F) having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the resistance is: the carboxyl group remains in the solder resist film, and the heat resistance and alkali resistance are , electrical insulation, etc. are reduced, so it is not good. On the other hand, when it exceeds 2.5 equivalents, the low molecular weight cyclic (thio)ether group remains on the dried coating film, and the strength of the coating film is lowered, which is not preferable. In the photocurable resin of the present invention, when the thermosetting component (F) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain the thermosetting catalyst (G). Examples of the thermosetting catalyst (G) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, An imidazole derivative such as 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyan di amide; Benzyl dimethylamine, 4-(dimethylamino)_-24- 200921272 Ν, Ν-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl- An amine compound such as N,N-dimethylbenzylamine; an anthracene compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine; and a commercially available product such as Shikoku Kasei 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of imidazole-based compound) manufactured by Industrial Co., Ltd., U-CAT3503N, U-CAT3502T (all block isocyanate compound of dimethylamine) manufactured by SAN-APRO Co., Ltd. Trade name), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic guanidine compounds and their salts). In particular, it is also possible to use a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction for promoting an epoxy group and/or an oxetanyl group and a carboxyl group. It is also possible to use two or more kinds alone or in combination. Also 'can also use guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-three tillage, 2_ethylene _4,6-Diamino-S-triazinium, 2-vinyl-4,6-diamino-S-triple, isomeric cyanide adduct, 2,4-diamine -6-Methyl propylene oxiranylethyl-S-tris. s-tri-D-derivatives such as isomeric cyanuric acid adducts, and preferably these are also used as adhesion imparting agents. The compound is used in combination with the aforementioned thermosetting catalyst. It is sufficient that the blending amount of the thermosetting catalyst is a ratio of a general amount, for example, a resin containing a carboxylic acid (A) or a thermosetting component having two or more cyclic (thio)ether groups in the molecule. (F) 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. The photocurable resin composition of the present invention is such that the physical strength of the coating film is improved, and the chelating agent can be blended as needed. As such a chelating agent, an inorganic or organic hydrating agent known in the art can be used, and barium sulfate, spheroidal cerium oxide and talc are particularly preferably used. Further, a compound having one or more ethylenically unsaturated groups or a NANOCRYL (trade name) XP 0396, XP manufactured by Hanse-Chemie Co., Ltd. in which the nano-sized cerium oxide is dispersed in the polyfunctional epoxy resin (E1) may be used. 0596, XP 073 3, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade name) or NANOPOX (trade name) XP 0516, XP 0 5 25, XP made by Hanse-Chemie 03 14 (All product grade name). These may be used alone or in combination of two or more. The blending amount of the above-mentioned chelating agent is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (A). When the blending amount of the chelating agent exceeds 300 parts by mass, the viscosity of the photosensitive composition becomes high, the printability is lowered, and the hardened material becomes brittle. Further, the photocurable resin composition of the present invention is an organic solvent which is used for the adjustment of the synthesis or composition of the carboxylic acid-containing resin (A) or the viscosity adjustment applied to the substrate or the carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbene a glycol ether such as an alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether or triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate -26- 200921272, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, ethylene glycol, An alcohol such as propylene glycol; a fat such as octane or decane; a solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. Such an organic solvent may be used singly or in combination of two or more kinds. The photocurable resin composition of the present invention may further contain a thermal polymerization inhibitor which may be blended with diphenol, hydroquinone monomethyl ether, tert-butylcatechol, pyrothiazine or the like as needed; fine powder Deodorizers such as bentonites and montmorillonites, defoamers such as polyfluorinated fluorinated polymers and polymers, and/or leveling agents, decane coupling agents such as imidazole systems and triazoles. , antioxidants, rust inhibitors and other additives. Next, a film, a cured product, and a solder resist printed wiring board formed of the cured product using the photocurable resin composition of the present invention will be described. The photocurable resin composition of the present invention is photocurable by being applied to a carrier film and dried. The photocurable resin composition of the present invention or the dry film is obtained by photohardening. The photohardening system can also be mounted by ultraviolet exposure, and the laser emitting light source is hardened, in particular, by a wavelength of 3 50 to 41 Onm. The printed wiring board according to the present invention is obtained by this method and then thermally hardened. Specifically, the method of forming a dry film, a propylene glycol alcohol, or a propylene hydrocarbon petroleum product by dry-resisting a layer of a phenol, a benzene, an alkane, or a thiazole is carried out as follows. The film is placed on the copper to enter the laser light hardening cured material -27- 200921272, printed wiring board. In other words, the photocurable resin composition of the present invention is adjusted to have a viscosity suitable for the coating method, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or the like. Coating by a screen printing method, a curtain coating method, or the like, the organic solvent contained in the composition is volatilized and dried (pseudo-drying) at a temperature of about 60 to 100 ton to form a tack-free The coating film. Further, the above composition is applied onto a carrier film, and the resin insulating layer is formed by being wound and bonded to a substrate by drying it into a film type. Thereafter, by contact (or non-contact), through the formation of the pattern of the mask, selective exposure by active energy lines or direct exposure by laser direct exposure machine, but not The exposed portion is developed by a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous alkali carbonate solution) to form a photoresist pattern. Further, in the case where the composition of the thermosetting component (F) is contained, for example, heating is carried out at a temperature of about 1 40 to 1 80 ° C to thermally cure the carboxyl group and the molecule of the carboxylic acid-containing resin (A). The thermosetting component (F) having two or more cyclic (thio)ether groups reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. . In addition, even if the thermosetting component (F) is not contained, the ethylenic unsaturated bond remaining in the unreacted state during the exposure is thermally polymerized by heat treatment, and the film properties can be improved. Purpose. Use for heat treatment (thermosetting). Examples of the substrate include paper benzoquinone, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene. A copper-clad laminate of all grades (FR-4, etc.) of a material such as a copper-clad laminate for high-frequency circuits such as cyanate ester (cyanate ester -28-200921272), and other polyimide film , PET film, glass substrate, ceramic substrate, wafer board, etc. After the photocurable resin composition of the present invention is applied and volatilized and dried, a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like can be used (a heat source having a steam-heated air method is used and dried) The photocurable resin composition of the present invention is applied as follows by the method of contacting the hot air in the machine and the method of spraying the nozzle onto the support, and after volatilizing and drying, the obtained coating film is obtained. Exposure (irradiation of active energy lines) is performed. The coating system exposed portion (the portion irradiated by the active energy ray) is hardened, and the exposure machine used for illuminating the active energy ray is a laser direct drawing device (Laser direct imaging device). An exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short-arc lamp, or a direct drawing device for an ultraviolet lamp such as an (ultra) high-pressure mercury lamp. If the active energy ray uses laser light having a maximum wavelength in the range of 305 to 4 lOnm, it may be either a gas laser or a solid laser. Further, the amount of exposure varies depending on the film thickness and the like, and is usually in the range of 5 to 200 mJ/cm 2 , preferably 5 to 100 mJ/cm 2 , and more preferably 5 to 50 mJ/cm 2 . As the direct drawing device, for example, a product manufactured by Orbotech Co., Ltd., PENTAX Corporation, or the like, and a device having a maximum wavelength of 3 to 50 nm of laser light can be used, and any device can be used. -29- 200921272 The above development method can be carried out by dipping method, spraying method, spraying method, method, etc.; as developing solution, potassium hydroxide, sodium hydroxide, carbon, potassium carbonate, sodium phosphate, sodium citrate, ammonia can be used. An aqueous alkali solution such as an amine. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, and it is to be understood that the following examples are not limited thereto. In addition, the "parts" that appear below are specifically limited to "mass parts". <Synthesis of a carboxylic acid-containing resin> The carboxylic acid-containing resin of the present invention was produced according to the following synthesis example; 〇 cresol novolac type epoxy resin (Daily Ink Chemicals Co., Ltd.), "EPICLON" (registered trademark) N-69 5, epoxy equivalent) 220 parts were poured into a four-necked flask equipped with a stirrer and a reflux condenser, and 2,4 parts of carbitol acetate was added thereto, and dissolved by heating. Next, 0.46 parts of hydroquinone and a triphenylphosphine 1 ·: with a reaction catalyst were added. The mixture was heated at 95 ° C to 105 ° C, and 72 parts of the acid was slowly added to react for 16 hours. The reaction product was cooled to 90 ° C, and tetrahydrophthalic anhydride portion was added to react 8 , and after cooling, the reaction solution (referred to as varnish (A-1 )) was taken out. The acid hydrate of the obtained carboxylic acid-containing resin-based solid matter was mgKOH/g and the nonvolatile content was 65%. Brushed soda hairline without A) (220 and plus 8 parts of propylene 80 0 hours, -30-100 200921272 <Examples 1 to 7 and Comparative Examples 1 to 2 > The carboxylic acid-containing resin The varnish (A-1) obtained by the synthesis and the components shown in Table 1 were kneaded by three rolls at the blending ratios shown in the same table to obtain a photocurable resin composition. -31 - 200921272 (N 〇1 1 1 vo oom ο inch in 〇m 2 — 隹lg| Hi 3 S ° ^ ^ e E 3 gw ^ g 〇君旯 ilJ sai bs Λ b ^ 3 CS Li li? 3 ^ w 11 ^ if Γ **·* 00 On »~-h Xingguan*Xing*Off* 〇1 1 1 o Sun rn ο vn 〇m Example 〇〇CN 1 1 ITi 〇ir> o 1 Ο (Τ) Ο m 〇m 〇1 1 Ο o ο 〇f—Η m ο inch^Ti 〇〇TH cn 〇1 1 »—Η Ο o TH 1 ΓΛ Ο Τ^Τ) 〇τ·Η mg <4 |g| uu ^ ^ o Zirconium h 齩S褰莽=write s 111 ml 匾^观芒扫扫—K) ua〇| i gu tip containing eS .1.1 ·& ^ g,11°yyy^ 1 c/ϋ m vn ό And Guan Guan and inch Η ·τ·^ 1 'PH 〇I 'O o σν ο ο »—Η rn Ο inch inch ro m 1— Η 〇Ψ < 〇1 I p I ο 寸 ο m CN 〇1 〇1 1 Ο m ο inchο m ^Η 〇»—Ή 1 〇1 1 I m ο inch ο r—^ m Composition (mass parts ) varnish (Α-1) photopolymerization initiator (ΒΓ1 compound containing ethylenically unsaturated group (c-ir2 red colorant (D-lf3 red colorant (D-2)"4 red colorant (D- 3;r5 blue colorant (El)+6 yellow colorant (E-2f 7 polyfunctional epoxy compound (Fi-ir8 polyfunctional epoxy compound (Fl-2) #9 thermosetting catalyst (G-1) *10 Thermal Hardening Catalyst (G-2)"1 Organic Solvent*12 Barium Sulfate*13 Polyoxane Defoamer Remarks-32 - 200921272 Photocurability of Examples 1 to 7 and Comparative Examples 1 to 2 The resin composition' was evaluated for performance and characteristics in accordance with the following evaluation criteria. The results are shown in Table 2. Performance evaluation: <Optimum exposure amount/sensitivity> Polishing light (buff roll) honing a copper-thickness 35 μm η loop pattern substrate, after being washed with water, dried, and fully coated by Examples 1 to 7 by screen printing The photocurable resin compositions of Comparative Examples 1 and 2 were dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, an exposure apparatus equipped with a metal halide lamp was used for exposure by Step tablet (Kodak No. 2) to develop in 60 seconds (30 ° C, 0 · 2 Μ P a, 1 mass% sodium carbonate) When the pattern of the Step tablet remaining in the case of the aqueous solution is 7 segments, it is an optimum exposure amount. <Resolution> After the polishing roll honing line/the circuit pattern substrate having a distance of 300/300 and a copper thickness of 35 μm, 'after washing with water, drying, coating Examples 1 to 7 and Comparative Example 1 by screen printing method ~2 photocurable resin composition at 8 〇. (: The hot air circulation type drying oven was dried for 30 minutes. After drying, exposure was performed using an exposure apparatus equipped with a metal halide lamp. The exposure pattern was used for drawing the pitch portion 20/30/40/50/60/70/ The data or mask for direct drawing of the line of 80/90/1 00μιη. The exposure amount is such that the active energy ray is irradiated to the optimum exposure amount of the photocurable resin composition. After exposure, by 30. (1: 1) The mass% sodium carbonate aqueous solution was used for development, and the pattern was drawn, and the cured coating film was obtained by thermal hardening treatment at 15 ° C C 60 min - 33 - 2009 21272. The obtained anti-reflection was obtained by using an optical microscope adjusted to 200 times. The minimum residual line of the cured coating film for the photosensitive resin composition for soldering resistance. Characteristic test = (Production of evaluation substrate) On the copper foil substrate on which the pattern was formed, the above-described Example 1 was completely coated by screen printing. The composition of ~4 and Comparative Examples 1 to 2 was dried at 80 t for 20 minutes, and allowed to cool to room temperature. The substrate was exposed to a solder resist pattern with an optimum exposure amount using an exposure apparatus equipped with a metal halide lamp. A 30% aqueous solution of 1% Na2CO3 at 30 ° C The film was developed under the conditions of 2 kg/cm 2 for 60 seconds to obtain a photoresist pattern. The substrate was irradiated with ultraviolet light under the conditions of a cumulative exposure amount of 1000 mJ/cm 2 in a UV transfer furnace, and then heated at 150 ° C for 60 minutes. The obtained printed circuit board (evaluation substrate) was evaluated for the following characteristics. <Color of coating film> The color of the cured product was visually judged against the solder resists of the above examples and comparative examples. Further, the evaluation substrate was heated at 150 ° C for 2 hours, and the degree of discoloration on the copper circuit was judged as follows. 〇〇: There was no discoloration at all. 〇: There was some discoloration compared with the initial stage, but there was no thin film at all. -34- 200921272 The difference between the part and the thick part. △: The difference between the thin part and the thick part which has no discoloration is observed. X: The thin part of the photoresist is discolored, and thick. <The solder heat resistance> The evaluation substrate coated with the rosin flux (fiux) was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with denatured alcohol. Visually observed The expansion of the resist layer and the peeling were evaluated. The criteria for the determination were as follows. ◦: No peeling occurred even if the immersion was repeated three or more times for 10 seconds. △: If the immersion was repeated three times or more for 10 seconds, there was a slight peeling. After immersing for 10 times within 10 seconds, it is swelled and peeled off in the photoresist layer. <Anti-electroless gold plating resistance> The commercially available electroless nickel bath and electroless gold plating bath are used, and nickel 〇·5μηι, gold 0·0 The plating was performed under the conditions of 3 μm, and the peeling of the photoresist layer or the presence or absence of plating penetration was evaluated by tape stripping, and then immersed in the solder bath for 1 second under the test conditions of the solder heat resistance, and then washed. After drying, tape stripping was performed to evaluate the presence or absence of peeling of the photoresist layer. The criteria are as follows. Hey: There is no change at all. -35- 200921272 △: After plating, some infiltration was observed and the peeling of the solder after heat resistance was observed. X: Peeled after plating. <Electrical corrosion resistance> An evaluation substrate was produced under the above conditions using a comb-shaped electrode B coupon of IPC B-25 instead of a copper foil substrate, and a bias voltage of DC 100 V was applied to the comb-shaped electrode at 85°. In C, 85% RH constant temperature and humidity tank, the presence or absence of migration after 1,00 hours was confirmed. The criteria for judgment are as follows. 〇: There are no changes at all. △: Only a few changes. X: Migration generator. <Acid resistance> The evaluation substrate was immersed in an aqueous solution of i〇vo1%h2so4 at room temperature for 30 minutes, and the elution or the elution of the coating film was confirmed, and the peeling by tape removal was confirmed. The judgment criteria are as follows. 〇: No penetration, dissolution, or peeling. △: It was confirmed that there was little infiltration, dissolution or peeling. X : A large amount of infiltration, dissolution or peeling was confirmed. -36- 200921272 [Table 2] Performance and Characteristics Example Comparative Example 1 2 3 4 5 6 7 1 2 Hardened coating film color red orange blue green blue green purple blue green sensitivity (mJ/cm2) 300 300 300 300 300 300 300 300 300 Resolving power (μιη) 50 50 50 50 50 50 50 70 60 Discoloration test of copper circuit 〇〇〇〇〇〇〇〇〇〇〇〇X Δ Solder heat resistance 〇〇〇〇〇〇〇〇〇Electrical resistance蚀 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 无 无 无 无 无 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 A map of the hue (Munsellhue) ring. -37-