200935172 九、發明說明 【發明所屬之技術領域】 本發明係關於回路基板的製造、實裝於電子零件等之 用途所適用的光硬化性熱硬化性樹脂組成物的乾膜，更詳 細而言，係關於在從民生用至產業用印刷電路板、特別是 可撓性印刷電路板上形成設置孔部的光阻層等所適用的光 硬化性熱硬化性樹脂組成物與乾膜。本發明又關於由該相 關的光硬化性熱硬化性樹脂組成物與乾膜形成設置了孔部 的阻焊層而成的印刷電路板。 【先前技術】 因爲最近的半導體零件的急速進歩，電子機器有小型 輕量化、高性能化、多機能化的傾向，隨著此等傾向而印 刷電路板朝高密度化發展。例如導體回路的細線化、高多 層化、或導通孔、盲孔等之小徑化，而且藉由小型晶片零 件的表面實裝之高密度實裝等持續發展。此外，對應於如 此的印刷電路板的高密度化，被稱爲B G A (球閘陣列） 、CSP (晶片尺寸封裝）等之1C封裝登場，取代被稱爲 QFP (四方扁平封裝）、SOP (小外型封裝）等之1C封裝 。於如此的封裝基板或車載用的印刷電路板中，爲了對用 於與封裝基板上的半導體零件連接之墊片等之開口部，施 加用於提昇信賴性之鏟金等，使用阻焊（Solder Resist ) 作爲阻焊，於高密度印刷電路板的製造中，一般而言 -4- 200935172 採用光阻焊（Photo Solder Resist)，此外，由作業性、 膜厚精度、硬化膜表面的平滑性等之觀點而言，一直以來 對於阻焊要求乾膜化。此外，最近係印刷電路板或封裝基 板所使用的芯材朝薄板化發展，例如TAB (捲帶自動接合 )、T-BGA (捲帶球閘陣列封裝）、T-CSP (捲帶晶片尺 寸封裝）、UT-CSP (超薄疊層芯片尺寸封裝）等登場。 使用如此的捲帶狀的芯材時，必須藉由捲繞傳輸（roll-to-roll)法層壓乾膜型的阻焊。 乾膜型的光阻焊，一般而言在被稱爲背面膜（carrier film )的支持體上形成光硬化性熱硬化性樹脂組成物的乾 燥皮膜，或再用覆蓋膜被覆其表面者，以薄片狀或捲筒狀 供給，一邊剝離背面膜或覆蓋膜的其中一方一邊層壓於印 刷電路板上後，進行選擇性地曝光，然後，剝離膜（背面 膜或覆蓋膜）後，藉由進行顯影，形成所定的光阻圖型。 作爲乾膜型的光阻焊，例如提議含有胺基甲酸乙酯（ 甲基）丙烯酸酯化合物之組成物（參考專利文獻1、2) 、含有含羧基的胺基甲酸乙酯（甲基）丙烯酸酯化合物之 組成物（參考專利文獻3、4)等各種的組成物，作爲感 光性樹脂。惟，使用先前技術的光硬化性熱硬化性樹脂組 成物的乾膜形成設置了孔部的光阻圖型時，層合於印刷電 路板上，選擇性曝光後，剝離薄膜（背面膜或覆蓋膜）， 進行顯影時，會有孔部周邊部上有毛邊狀的部分殘留，成 爲小於所定的孔徑之孔部之問題。如上述於孔部周邊部上 有毛邊狀的部分殘留，而孔部的孔徑發生變化時，鍍金等 -5- 200935172 之附著性降低，而對於所得到的印刷電路板的信賴性造成 極大的損害。此外，因爲孔部的孔徑變化狀況，或鍍金等 的附著狀況而變成不良品，故亦會有生產性降低的問題。 另一方面，作爲液狀的光阻焊的光聚合起始劑，以 2 -甲基- l-[4-(甲基硫代）苯基]-2-嗎啉代丙酮-1、2-苄 基-2-二甲基胺基-1-(4-嗎啉代苯基）-丁烷-1-酮等之α-胺基苯乙酮系光聚合起始劑，由硬化深度、解像性、耐熱 性、重霧方面而言，較適合使用（例如參考專利文獻5) 。惟，使用於乾膜型的阻焊時，會發生如上述的問題。 [專利文獻1]特開昭5 7-5 5 9 1 4號公報（專利申請範 圍） [專利文獻2]特開平7-248622號公報（專利申請範 圍） [專利文獻3]特開2000- 1 3 1 836號公報（專利申請範 圍） [專利文獻4]特開2002-229201號公報（專利申請範 圍） [專利文獻5]特開2000-2 1 4584號公報（專利申請範 圍） 【發明內容】 [發明所欲解決之課題] 本發明係鑑於如前述之先前技術的問題而完成，其目 的係提供將乾膜層壓於印刷電路板，選擇性曝光後，剝離 -6- 200935172 薄膜（背面膜或覆蓋膜），顯影後形成設置了孔部的光阻 圖型時，不會有孔部周邊部上有毛邊狀的部分殘留，變成 小於所定的孔徑的孔部之問題，可形成按照所定的曝光圖 型的光阻圖型之光硬化性熱硬化性樹脂組成物的乾膜，並 提供生產性優良且信賴性高的印刷電路板，特別是可撓性 印刷電路板。 此外，本發明之其他目的，係提供即使不使用上述乾 膜，亦可消除在介由薄膜曝光之形成設置有孔部的光阻圖 型時所發生與上述同樣的問題之光硬化性熱硬化性樹脂組 成物。 [用於解決課題之手段] 爲了達成前述目的，依據本發明，提供乾膜，其係用 於形成設置了孔部的光阻圖型之光硬化性熱硬化性樹脂組 成物的乾膜，其特徵係與光硬化性成分及熱硬化性成分一 起含有的作爲光聚合起始劑，使用含磷的光聚合起始劑。 較佳形態，係上述含磷的光聚合起始劑爲醯基膦氧化 物系光聚合起始劑。 此外，依據本發明之其他側面觀，係提供藉由上述乾 膜形成設置了孔部之阻焊層而成的印刷電路板。 此外，本發明爲了達成其他目的，提供光硬化性熱硬 化性樹脂組成物，其係用於介由薄膜曝光之設置了孔部的 光阻圖型的形成方法的光硬化性熱硬化性樹脂組成物，其 特徵係與光硬化性成分及熱硬化性成分一起含有的作爲光 200935172 聚合起始劑，使用含磷的光聚合起始劑。依據本發明，又 提供由相關的光硬化性熱硬化性樹脂組成物形成設置了孔 部的阻焊層而成的印刷電路板。 [發明的效果] 本發明的乾膜，因爲作爲其所使用的光硬化性熱硬化 性樹脂組成物中所含有的光聚合起始劑，爲使用含磷的光 聚合起始劑，故於印刷電路板形成設置了孔部的光阻圖型 時，將乾膜層壓於印刷電路板，選擇性曝光後，剝離薄膜 (背面膜或覆蓋膜），進行顯影時，不會有於孔部周邊部 上有毛邊狀的部分殘留，成爲小於所定的孔徑的孔部之問 題，可形成按照所定的曝光圖型的光阻圖型。其結果，可 提供鍍金等的附著性未降低、生產性優良且信賴性高的印 刷電路板。 Φ [實施發明之最佳形態] 本發明者等人，關於使用光硬化性熱硬化性樹脂組成 物的乾膜作爲感光性樹脂層時所引起的前述現象而進行精 心硏究。結果，認爲如此的現象係由以下的理由所引起。 亦即，將乾膜層壓於印刷電路板時，一邊剝離背面膜或覆 蓋膜之其中一方一邊層壓於印刷電路板上後，進行選擇性 曝光，然後，剝離薄膜（背面膜或覆蓋膜）後，藉由進行 顯影，形成所定的光阻圖型。故，因爲直到薄膜（背面膜 或覆蓋膜）被剝離爲止，被形成於印刷電路板上的光硬化 -8- 200935172 性熱硬化性樹脂組成物之層（乾膜）皆處於上面被薄膜（ 背面膜或覆蓋膜）覆蓋的狀態’故與外面空氣的氧的接觸 受到妨礙，成爲不會因爲氧所造成的聚合阻礙不會發生的 狀態。因此，藉由光罩使活性能量線的照射被遮斷的孔部 圖型的周邊部引起光暈，此外，曝光後，直到剝離薄膜爲 止之間亦不少聚合反應進行，故孔部周邊部上有毛邊狀的 顯影殘留部分發生，成爲小於所定的孔徑的孔部。 本發明者等人，再經過重複檢討關於如此現象的結果 ，發現乾膜所使用的光硬化性熱硬化性樹脂組成物中所含 有的作爲光聚合起始劑，爲使用含磷的光聚合起始劑時， 在於印刷電路板形成設置了孔部的光阻圖型時，不會有如 上述於孔部周邊部上有毛邊狀的部分殘留，成爲小於所定 的孔徑的孔部之問題，可形成按照所定的曝光圖型的光阻 圖型，而完成本發明。其理由很難說是已經很清楚了解， 但認爲含磷的光聚合起始劑作爲聚合阻礙因子進行作用， 故即使在被形成於印刷電路板上的光硬化性熱硬化性樹脂 組成物之層（乾膜）的上面以薄膜（背面膜或覆蓋膜）覆 蓋而妨礙與外面空氣的氧接觸的狀態（不會引起氧阻礙的 狀態），亦阻礙曝光後至剝離薄膜爲止之間的聚合反應的 進行。 具有優異的前述的作用·效果之適當的含磷的光聚合 起始劑’爲具有下述一般式（I)所表示之基的醯基膦氧 化物系光聚合起始劑。 200935172 【化1】 R1 R2—P—G— (I) (式中，R1及R2各自獨立地表示碳數1〜10的直鏈狀或 支鏈狀的烷基、烷氧基、環己基、環戊基、芳基、或者、 〇 被鹵素原子、烷基或烷氧基取代的芳基’惟，R1及尺2的 其中一方可爲R-C( = 〇)-基（其中’ R表示碳數1〜20的烴 基）） 作爲具有上述一般式（I)所表示的基之醯基膦氧化 物系光聚合起始劑的具體例子，可列舉（2,6-二甲氧基苯 甲醯）-2,4,4-戊基膦氧化物、2,4,6-三甲基苯甲醯二苯基 膦氧化物、雙（2,4,6-三甲基苯甲醯）-苯基膦氧化物、雙 (2,6 -二甲氧基苯甲醯）-2,4,4-三甲基-戊基膦氧化物等。 © 作爲市售品，可列舉BASF公司製的LUCIRIN TPO、 LR8953X、Ciba Specialty chemicals 公司製的 IRGACURE8 1 9 等。 . 此外’具有優異的前述的作用.效果之特別適當的含 磷的光聚合起始劑，爲具有下述一般式（II)所表示之基 的醯基膦氧化物系光聚合起始劑。 -10- (II) 200935172 【化2】 R1 R304_C_ (式中，R1及R3各自獨立地表示碳數1〜10的直鏈狀或 支鏈狀的烷基、環己基、環戊基、芳基、或者、被鹵素原 子、烷基或烷氧基取代的芳基，惟，R1及R3的其中一方 © 可爲R-C( = 0)-基（其中，R表示碳數1〜20的烴基）） 作爲具有上述一般式（II)所表示之基的醯基膦氧化 物系光聚合起始劑的具體例子，有乙基-2，4,6-三甲基苯甲 醯苯基次膦酸酯，市售品有 BASF公司製的 LUCIRIN TPO-L。 如前述的含磷的光聚合起始劑的摻合量，相對於後述 之含羧基之感光性樹脂或/及含羧基之樹脂100質量份（ 合計量或單獨使用時爲單獨量，以下相同），適當爲0.1 ® 〜30質量份，較佳爲0.5〜20質量份，更佳爲1〜15質量 份的比例。含磷的光聚合起始劑的摻合比例比上述範圍少 時光硬化性變差，另一方面，比上述範圍多時硬化塗膜的 - 特性變差，此外，保存安定性變差而較不佳。再者，可以 不損及本發明的效果的量的比例，添加習知慣用的光聚合 起始劑或光起始助劑。 接著，說明關於可利用於本發明的乾膜形成的光硬化 性熱硬化性樹脂組成物。本發明所使用的組成物，除了使 -11 - 200935172 用含磷的光聚合起始劑作爲光聚合起始劑以外，可使用先 前技術習知的各種鹼顯影型的光硬化性熱硬化性樹脂組成 物。作爲光硬化性熱硬化性樹脂組成物中的光硬化性成分 ’先前習知的各種含羧基感光性預聚物或具有乙烯性不飽 和雙鍵之光聚合性單體可單獨使用或可組合2種以上使用 。此外’可組合光聚合性單體與鹼可溶性的含羧基之樹脂 ’特別是爲了成爲鹼顯影性的組成物，含有含羧基之樹脂 0 較佳’其本身不含乙烯性不飽和雙鍵的含羧基之樹脂、或 具有乙烯性不飽和雙鍵之感光性的含羧基之樹脂的任一種 皆可使用’並沒有限定特定者，但特別佳爲可使用如以下 所列舉的化合物（寡聚物及聚合物的任一者皆可）。 (1)藉由使（甲基）丙烯酸等之不飽和羧酸（a)， 與苯乙烯、α -甲基苯乙烯、低級烷基（甲基）丙烯酸酯、 異丁烯等之具有不飽和雙鍵的化合物（b)進行共聚合而 得到的含羧基之樹脂。 φ (2)藉由使不飽和羧酸（a)與具有不飽和雙鍵的化 合物（b)之共聚合物的一部分，與具有乙烯基、烯丙基 、（甲基）丙烯醯基等乙烯性不飽和基與環氧基、醯基氯 (acid chloride )等反應性基之化合物，例如（甲基）丙 烯酸縮水甘油酯進行反應，使乙烯性不飽和基作爲側基進 行加成而得到含羧基之感光性樹脂。 (3)使（甲基）丙烯酸縮水甘油酯、(甲基）丙 烯酸甲基縮水甘油酯等之具有環氧基與不飽和雙鍵之化合 物（c)與具有不飽和雙鍵之化合物（b)的共聚合物，與 -12- 200935172 不飽和羧酸（a)進行反應，使所生成的二級的羥基與苯 二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐等之飽和或 不飽和多元酸酐（d)進行反應而得到的含羧基之感光性 樹脂。 (4) 使馬來酸酐、衣康酸等之具有不飽和雙鍵的酸 酐（e)與具有不飽和雙鍵之化合物（b)的共聚合物，與 羥基烷基（甲基）丙烯酸酯等之具有1個羥基與1個以上 乙烯性不飽和雙鍵之化合物（f)進行反應而得到的含羧 基之感光性樹脂。 (5) 使如後述之分子中具有至少2個環氧基之多官 能環氧基化合物（g)或多官能環氧基化合物的羥基再以 環氧氯丙烷進行環氧基化的多官能環氧基樹脂的環氧基、 與（甲基）丙烯酸等之不飽和單羧酸（h)的羧基進行酯 化反應（全酯化或部分酯化，較佳爲全酯化），使所生成 的羥基再與飽和或不飽和多元酸酐（d)進行反應而得到 的含羧基之感光性化合物。 (6) 使具有不飽和雙鍵之化合物（b)與（甲基）丙 烯酸縮水甘油酯的共聚物的環氧基，與碳數2〜17的烷基 羧酸、含芳香族基之烷基羧酸等之1分子中具有1個羧基 ’不具有乙烯性不飽和鍵之有機酸（i)進行反應，使所 生成的二級的羥基與飽和或不飽和多元酸酐（d)進行反 應而得到的含羧基之樹脂。 (7) 藉由脂肪族二異氰酸酯、分支脂肪族二異氰酸 酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸 -13- 200935172 酯（j)、與二羥甲基丙酸、二羥甲基丁烷酸等之含羧基 之二醇化合（k)、及具有聚碳酸酯系多元醇、聚醚系多 元醇、聚酯系多元醇、聚嫌烴系多元醇、丙烧酸系多元醇 、雙酚A系環氧化物加成物二醇、酚性羥基及醇性羥基 之化合物等的二醇化合物（m)的加成聚合反應而得到的 含羧基之胺基甲酸乙酯樹脂。 (8) 藉由二異氰酸酯（j)、與雙酚a型環氧基樹脂 U 、氫化雙酚A型環氧基樹脂 '溴化雙酚A型環氧基樹脂 、雙酚F型環氧樹脂、雙酚s型環氧基樹脂、聯二甲苯酚 型環氧基樹脂、雙酚型環氧基樹脂等之2官能環氧基樹脂 的（甲基）丙烯酸酯或其部分酸酐改性物（η)、含羧基 之二醇化合物（k)、及二醇化合物（m)的加成聚合反 應而得到的感光性之含羧基之胺基甲酸乙酯樹脂。 (9) 前述（7)或（8)的樹脂的合成中，加入羥基 烷基（甲基）丙烯酸酯等之具有1個羥基與1個以上乙烯 0 性不飽和雙鍵之化合物（f)，末端導入不飽和雙鍵的含 羧基之胺基甲酸乙酯樹脂。 (1(ϊ)前述（7)或（8)的樹脂的合成中，加入異佛 爾酮二異氰酸酯與季戊四醇三丙烯酸酯等莫耳反應物等之 分子內具有1個異氰酸酯基與1個以上（甲基）丙烯醯基 之化合物’末端經（甲基）丙烯基化之含羧基之胺基甲酸 乙酯樹脂。 (U)使如後述之分子中具有至少2個的氧雜環丁烷 環之多官能氧雜環丁烷化合物與不飽和單羧酸（h)進行 -14- 200935172 反應’使飽和或不飽和多元酸酐（d)對所得到的改性氧 雜環丁烷化合物中的一級羥基進行反應而得到的含羧基之 感光性樹脂。 (12) 使如後述之2官能環氧基樹脂或2官能氧雜環 丁烷樹脂與二羧酸進行反應，使所生成的1級的羥基加成 飽和或不飽和多元酸酐（d)而得到的含羧基之聚酯樹脂 〇 (13) 使雙環氧基化合物與雙酚類的反應生成物中， 導入不飽和雙鍵，接著與飽和或不飽和多元酸酐（d)進 行反應而得到的含羧基之感光性樹脂。 (14) 使酚醛清漆型酚樹脂、與環氧乙烷、環氧丙烷 、環氧丁院、氧雜環丁院（trimethylene oxide )、四氫呋 喃、四氫吡喃等的環氧化物及/或乙烯碳酸酯、丙烯碳酸 酯、丁烯碳酸酯、2,3-碳酸酯丙基甲基丙烯酸酯等之環狀 碳酸酯的反應生成物與不飽和單羧酸（h)進行反應，所 得到的.反應生成物與飽和或不飽和多元酸酐（d )進行反 應而得到的含羧基之感光性樹脂。 又前述的含羧基之樹脂之中’較佳係前述（7)〜（ 1〇)的樹脂的合成中所使用之具有異氰酸酯基的化合物（ 亦含二異氣酸酯）爲不具苯環的一異氰酸醋時，及前述（ 5) 、（8) 、（12)的樹脂的合成中所使用的多官能及2 官能環氧基樹脂爲雙酚A骨架、雙酚F骨架、聯苯骨架 、聯二甲苯酚骨架之線狀構造的化合物及其氫化化合物時 ，由可撓性等之觀點而言較佳。此外’其他方面而言，前 -15- 200935172 述（7)〜（10)的樹脂及如此等的前述（12)的改性物 ，主鏈上具有胺基甲酸乙酯鍵，對於翹曲而言較佳。此外 ，前述（1) 、（6) 、（7) 、（11) 、（12)以外的樹 脂，因爲於分子內具有感光性基（自由基聚合性不飽和雙 鍵），由光硬化性之觀點而言較佳。 再者，本說明書中，（甲基）丙烯酸酯之意，爲總稱 丙烯酸酯、甲基丙烯酸酯及此等的混合物之用語，關於其 他類似的表現亦相同。 如前述之含羧基之感光性樹脂及含羧基之樹脂，因爲 主鏈（backbone )·聚合物的側鏈上具有多數的游離的羧 基，故可藉由稀鹼水溶液進行顯影。前述含羧基之感光性 樹脂及含羧基之樹脂之酸價，希望爲40〜200mgKOH/g的 範圍，更佳爲45〜120mgKOH/g的範圍。含羧基之感光性 樹脂及含羧基之樹脂的酸價低於40mgKOH/g則鹼顯影變 困難，另一方面，超過2 0 0mgKOH/g則因爲顯影液而使曝 光部的溶解進行，而使線變得比所需要的還要細，依情況 ，曝光部與未曝光部無區別地皆被顯影液溶解剝離，正常 的光阻圖型的形成變困難而較不佳。 此外，前述含羧基之感光性樹脂及含羧基之樹脂的重 量平均分子量，依樹脂骨架而不同，但一般的而言希望爲 2,000〜1 50,000的範圍，更佳爲5,000〜100,000的範圍。 重量平均分子量低於2,000，則會有塗膜的不沾黏性能變 差，曝光後的塗膜的耐濕性變差，顯影時膜減少發生，會 有解析度大且差的狀況。另一方面，重量平均分子量超過 -16- 200935172 1 5 0,000，則會有顯影性顯著地變差，貯藏安定性變差的 狀況。 如此的含羧基之感光性樹脂或/及含羧基之樹脂的摻 合量，希望爲全組成物的20〜70質量％的範圍，較佳爲 30〜60質量％的範圍。少於上述範圍時，因爲塗膜強度 降低而較不佳，另一方面，多於上述範圍時，因爲組成物 的黏性變高，塗佈性等降低而較不佳。 僅使用前述含羧基之樹脂時，因爲其本身不具有乙烯 性不飽和雙鍵，爲了作爲光硬化性熱硬化性樹脂組成物進 行組成，必須再使用光聚合性單體。 作爲前述光聚合性單體，可列舉例如2-羥基乙基丙 烯酸酯、2-羥基丙基丙烯酸酯、季戊四醇三丙烯酸酯、二 季戊四醇五丙烯酸酯等之含有羥基的丙烯酸酯類；聚乙二 醇二丙烯酸酯、聚丙二醇二丙烯酸酯等之水溶性的丙烯酸 酯類；三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、 二季戊四醇六丙烯酸酯等之多元醇之多官能聚酯丙烯酸酯 類；三羥甲基丙烷、氫化雙酚A等之多官能醇或雙酚A、 雙酚等之多元酚的環氧乙烷加成物及/或環氧丙烷加成物 的丙烯酸酯類；上述含有羥基的丙烯酸酯的異氰酸酯改性 物之多官能或單官能聚胺基甲酸乙酯丙烯酸酯；雙酚A 二縮水甘油醚、氫化雙酚A二縮水甘油醚或苯酚酚醛清 漆環氧基樹脂的（甲基）丙烯酸加成物之環氧基丙烯酸酯 類；己內酯改性二三羥甲基丙烷四丙烯酸酯、ε-己內酯改 性二季戊四醇的丙烯酸酯、己內酯改性羥基三甲基乙酸新 -17- 200935172 戊二醇酯二丙烯酸酯等之己內酯改性的丙烯酸酯類、及對 應於上述丙烯酸酯類的甲基丙烯酸酯類等之感光性（甲基 )丙烯酸酯化合物，此等可單獨使用或可組合2種以上使 用。此等中，又以1分子中具有2個以上（甲基）丙烯醯 基之多官能（甲基）丙烯酸酯化合物較佳。此等感光性（ 甲基）丙烯酸酯化合物的使用目的，係使組成物具有光硬 化性。於室溫爲液狀的感光性（甲基）丙烯酸酯化合物， 除了使組成物具有光硬化性之目的以外，使組成物調整至 適用於各種的塗佈方法的黏度，亦產生有助於對鹼水溶液 的溶解性的作用。惟，使用多量於室溫爲液狀的感光性（ 甲基）丙烯酸酯化合物，因爲會有不能得到塗膜的指觸乾 燥性，又塗膜的特性亦惡化的傾向，故多量使用較不佳。 感光性（甲基）丙烯酸酯化合物的摻合量，相對於前述含 羧基之樹脂100質量份爲100質量份以下較佳。此外，前 述含羧基之感光性樹脂中，爲了提高光反應性的目的，可 摻合感光性（甲基）丙烯酸酯化合物。此時，感光性（甲 基）丙烯酸酯化合物的摻合量，相對於感光性樹脂或/及 含羧基之樹脂100質量份，爲100質量份以下較佳。 本發明所使用的光硬化性熱硬化性樹脂組成物，爲了 對硬化皮膜賦予耐熱性，含有熱硬化性成分。較佳的熱硬 化性成分，係分子中具有2個以上環狀醚基及/或環狀硫 代醚基（以下，稱簡爲環狀（硫代）醚基）之熱硬化性樹 脂。此等中又以2官能性的環氧基樹脂較佳，亦可使用其 他二異氰酸酯或其2官能性嵌段異氰酸酯。 -18- 200935172 如此之分子中具有2個以上環狀（硫代）醚基之熱硬 化性成分，有分子中具有2個以上的3、4或5員環的環 狀醚基、或環狀硫代醚基的任一者或2種類的基之化合物 ，可列舉例如分子中具有至少2個以上環氧基之多官能環 氧基化合物、分子中具有至少2個以上氧雜環丁烷基之多 官能氧雜環丁烷化合物、分子中具有2個以上的硫代醚基 之環氧硫化物樹脂等。 作爲前述多官能環氧基化合物的具體例子，可列舉例 如雙酚A型環氧基樹脂、氫化雙酚A型環氧基樹脂、溴 化雙酚A型環氧基樹脂、雙酚F型環氧基樹脂、雙酚S 型環氧基樹脂、酚醛清漆型環氧樹脂、苯酚酚醛清漆型環 氧基樹脂、甲酚酚醛清漆型環氧基樹脂、N-縮水甘油型環 氧基樹脂、雙酚A的酚醛清漆型環氧基樹脂、聯二甲苯 酚型環氧基樹脂、雙酚型環氧基樹脂、螯合型環氧基樹脂 、乙二醛型環氧基樹脂、含胺基的環氧基樹脂、橡膠改性 環氧基樹脂、二環戊二烯苯酚型環氧基樹脂、苯二甲酸二 縮水甘油酯樹脂、雜環的環氧基樹脂、四縮水甘油基二甲 苯醯乙烷樹脂、聚矽氧烷改性環氧樹脂、ε-己內酯改性環 氧基樹脂等。此外’爲了賦予難燃性，可使用磷等之原子 被導入其構造中者。此等環氧基樹脂，藉由熱硬化，提高 硬化皮膜的密著性、耐焊熱性、無電解鍍敷耐性等之特性 。再者’製作乾膜時’環氧基樹脂在將光硬化性熱硬化性 樹脂組成物塗佈於背面膜之前混合較佳。藉由在塗佈前混 合環氧基樹脂’可避免光硬化性熱硬化性樹脂組成物的增 -19- 200935172 黏。 此外’本發明所使用的光硬化性熱硬化性樹脂組成物 中’作爲環氧基樹脂，較佳爲使用於室溫爲固形狀或半固 形狀，較佳爲於稀釋劑（於室溫爲液狀的光聚合性單體或 有機溶劑）爲不溶或難溶性的環氧基樹脂。藉由使用如此 的環氧樹脂’成爲於硬化前的光硬化性熱硬化性樹脂組成 物中，固形狀或半固形狀的環氧基樹脂分散成微粒狀的狀 態。其粒徑係以不會對網版印刷等造成故障的程度較佳。 像這樣，於硬化前的光硬化性熱硬化性樹脂組成物中，固 形狀或半固形狀的環氧基樹脂分散成微粒狀，因爲光硬化 性熱硬化性樹脂組成物的適用期變長而較佳。作爲如此之 於室溫爲固形狀或半固形狀的較佳的環氧基樹脂，可列舉 雙酚S型環氧基樹脂、苯酚酚醛清漆型環氧基樹脂、苯二 甲酸二縮水甘油酯樹脂、雜環的環氧樹脂、聯二甲苯酚型 環氧基樹脂、聯苯型環氧基樹脂、四縮水甘油基二甲苯醯 乙烷樹脂等。 作爲前述多官能氧雜環丁烷化合物，可列舉雙[(3 _ 甲基-3-氧雜環丁烷基甲氧基）甲基]醚、雙[(3-乙基-3-氧雜環丁烷基甲氧基）甲基]醚、1，4-雙[(3-甲基-3-氧雜 環丁烷基甲氧基）甲基]苯、1,4-雙[(3-乙基-3-氧雜環丁 烷基甲氧基）甲基]苯、（3-甲基-3-氧雜環丁烷基）甲基 丙烯酸酯、（3-乙基-3-氧雜環丁烷基）甲基丙烯酸酯、 (3-甲基-3-氧雜環丁烷基）甲基甲基丙烯酸酯、（3-乙 基-3-氧雜環丁烷基）甲基甲基丙烯酸酯或此等的寡聚物 -20- 200935172 或共聚合物等之多官能氧雜環丁烷類之外’可列舉氧雜環 丁烷醇與酚醛清漆樹脂、聚（P·羥基苯乙烯）、cardo型 雙酚類、杯芳烴類、杯間苯二酚芳烴類、或倍半矽氧烷等 之與具有羥基之樹脂的醚化物等。其他’亦可列舉具有氧 雜環丁烷環之不飽和單體與烷基（甲基）丙烯酸酯之共聚 合物等。 作爲前述分子中具有2個以上的環狀硫代醚基之化合 物，可列舉例如日本環氧基樹脂公司製的雙酚A型環氧 硫化物樹脂YL7000等。此外，酚醛清漆型環氧基樹脂的 環氧基的氧原子被硫原子取代的環氧硫化物樹脂等亦可使 用。 前述分子中具有2個以上環狀（硫代）醚基之熱硬化 性成分的摻合量，相對於前述含羧基之感光性樹脂及/或 含羧基之樹脂的羧基1當量’環狀（硫代）醚基較佳爲 0.6〜2.5當量，更佳爲〇.8〜2.0當量的範圍。分子中具有 2個以上環狀（硫代）醚基之熱硬化性成分的摻合量低於 0.6當量時，硬化皮膜中殘留羧基，因爲耐熱性、耐鹼性 、電絕緣性等降低’故較不佳。另一方面’超過2.5當量 時，因爲低分子量的環狀（硫代）醚基殘留於乾燥塗膜， 故塗膜的強度等降低’較不佳。 本發明所使用的光硬化性熱硬化性樹脂組成物，因爲 含有於前述分子中具有2個以上環狀（硫代）醚基之熱硬 化性成分，可含有熱硬化觸媒。作爲如此的熱硬化觸媒， 可列舉例如咪唑、2 -甲基咪唑、2 -乙基咪唑、2 -乙基-4-甲 -21 - 200935172 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-甲基咪唑等之咪唑衍生 物；雙氰胺（dicyandiamide)、节基二甲基胺、4-(二甲 基胺基）-N，N-二甲基苄基胺、4-甲氧基-N，N-二甲基苄基 胺、4-甲基-N，N-二甲基苄基胺等之胺化合物、己二酸二 醯肼、癸二酸二醯肼等之肼化合物；三苯基膦等之磷化合 物等。此外，作爲市售者，可列舉例如四國化成工業公司 製的 2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ (皆爲 咪唑系化合物的商品名）、San-apro 公司製的1；-CAT3 5 03N、U-CAT3502T (皆爲二甲基胺的嵌段異氰酸酯 化合物的商品名）、DBU、DBN、U-CATSA102、U-C AT5 0 02 (皆爲二環式脒化合物及其鹽）等。並不特別限 定於此等，只要是環氧基樹脂或氧雜環丁烷化合物的熱硬 化觸媒、或促進環氧基及/或氧雜環丁烷基與羧基的反應 者即可，可單獨使用或可混合2種以上使用。此外，可使 用鳥糞胺 '甲基胍胺、苯並鳥糞胺、三聚氰胺、2,4-二胺 基-6-甲基丙烯醯基氧基乙基-S-三嗪、2-乙烯基-4,6-二胺 基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪·三聚異氰酸加成 物、2,4-二胺基-6-甲基丙烯醯基氧基乙基-S-三嗪.三聚異 氰酸加成物等之S-三嗪衍生物，較佳係將此等可作爲密 著性賦予劑的作用之化合物與前述熱硬化觸媒倂用。 此等熱硬化觸媒的摻合量，通常的量的比例即足夠， 例如前述分子中具有2個以上環狀（硫代）醚基之熱硬化 性成分1〇〇質量份’較佳爲〇_1〜20質量份，更佳爲0.5 -22- 200935172 〜15.0質量份。 此外，本發明所使用的光硬化性熱硬化性樹脂組成物 ’使前述光硬化性成分或熱硬化性成分溶解，又爲了調整 至適用於塗佈組成物之方法的黏度，可摻合有機溶劑。 作爲有機溶劑，可列舉例如甲基乙基酮、環己酮等之 酮類；甲苯、二甲苯、四甲基苯等之芳香族烴類；乙二醇 單乙基醚、乙二醇單甲基醚、乙二醇單丁基醚、二乙二醇 單乙基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、丙二 醇單甲基醚、丙二醇單乙基醚、二丙二醇二乙基醚、三乙 二醇單乙基醚等之二醇醚類；乙酸乙酯、乙酸丁酯、乙二 醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇單 乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、丙二醇單甲基 醚乙酸酯、二丙二醇單甲基醚乙酸酯等之乙酸酯類；乙醇 、丙醇、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪 族烴；石油醚、石腦油、氫化石腦油、溶劑石腦油等之石 油系溶劑等。此等有機溶劑，可單獨使用或以2種類以上 的混合物使用。有機溶劑的摻合量’可爲因應用途等之任 意的量。 本發明所使用的光硬化性熱硬化性樹脂組成物，含有 吩噻嗪、氫醌、氫醌單甲基醚、t-丁基鄰苯二酚、焦掊酚 等之習知慣用的光聚合禁止劑較佳。藉由使其含有如此的 光聚合禁止劑，使將乾膜層壓於印刷電路板後，從選擇性 曝光至剝離薄膜（背面膜或覆蓋膜）爲止之間的聚合反應 的進行防止更容易進行控制。光聚合禁止劑的摻合量’相 -23- 200935172 對於前述含羧基之感光性樹脂及/或含羧基之樹脂100質 量份，1 〇質量份以下，較佳爲5質量份以下的比例爲適 當。 本發明所使用的光硬化性熱硬化性樹脂組成物中，必 要時，可再摻合單獨或2種以上之硫酸鋇、鈦酸鋇、無定 形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧 化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁 φ 、雲母等之習知慣用的無機塡充劑。此等抑制塗膜的硬化 收縮，爲了提高密著性、硬度等之特性而使用。無機塡充 劑的摻合量，相對於前述含羧基之感光性樹脂及/或含羧 基之樹脂100質量份，爲300質量份以下，較佳爲30〜 200質量份的比例爲適當。 本發明所使用的光硬化性熱硬化性樹脂組成物中，必 要時，可再摻合著色劑。作爲著色劑，可使用酞菁•藍、 酞菁•綠、碘•綠、雙偶氮黃、結晶紫、氧化鈦、碳黑、 Q 萘黑等紅、藍、綠、黃等之慣用習知的著色劑，顏料、染 料、色素的任一者皆可。惟’由環境負擔降低及對人體的 影響之觀點而言，不含有鹵素較佳。 此外’本發明所使用的光硬化性熱硬化性樹脂組成物 中’必要時’可再摻合如微粉二氧化矽、有機膨潤土、蒙 脫石等之習知慣用的增黏劑、聚矽氧烷系、氟系、高分子 系等之消泡劑及/或塗平劑、咪哩系、噻哩系、三哩系等 之砍院偶合劑、磷系難燃劑、銻系難燃劑等之難燃劑等習 知慣用的添加劑類。 -24- 200935172 乾膜化時，將本發明的光硬化性熱硬化性樹脂組成物 用前述有機溶劑稀釋而調整爲適當的黏度，用逗點形狀刮 刀塗佈機（comma coater)、刮板塗佈機、唇口塗佈機、 棒式塗佈機、擠壓塗佈機（squeeze coater)、逆轉輥式 塗佈機、轉送輥塗佈機、照相凹版式塗佈機、噴塗機等以 均勻的厚度塗佈於背面膜（支持體）上，通常以50〜 13(TC的溫度乾燥1〜30分鐘可得到膜。關於塗佈膜厚並 沒有特別的限制，但一般而言乾燥後的膜厚，於1 〇〜1 5 0 "m，較佳爲20〜60"m的範圍適當選擇。乾燥可使用熱 風循環式乾燥爐、IR爐、加熱板、對流烘箱等（使用具 備藉由蒸氣之空氣加熱方式的熱源者，使乾燥機內的熱風 進行向流接觸之方法，或藉由噴嘴吹向支持體之方式）。 作爲背面膜，使用塑膠薄膜，較佳爲使用聚對苯二甲 酸乙二醇酯等之聚酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺 薄膜、聚丙烯薄膜、聚苯乙烯薄膜等之塑膠薄膜。關於背 面膜的厚度並沒有特別的限制，但一般而言於1〇〜150 的範圍適當選擇。 於背面膜上成膜後，爲了防止於膜的表面附著灰塵之 目的，再於膜的表面層合可剝離可能的覆蓋膜（保護薄膜 )° 作爲可剝離的覆蓋膜，可使用例如聚乙烯薄膜、聚四 氟乙烯薄膜、聚丙烯薄膜、經表面處理的紙等，只要是在 剝離覆蓋膜時，膜與覆蓋膜的接著力小於膜與背面膜的接 著力者即可。 -25- 200935172 前述乾膜，係使用熱滾筒壓層機等貼合於基材上（使 前述光硬化性熱硬化性樹脂組成物之層與基材在接觸下進 行貼合）。爲上述薄膜的光硬化性熱硬化性樹脂組成物之 層上，再具備可剝離的覆蓋膜之乾膜時，剝離覆蓋膜（或 背面膜）後，在使上述光硬化性熱硬化性樹脂組成物之層 與基材接觸下使用熱滾筒壓層機等使其貼合。 然後，相對於被貼合於基材上的乾膜（光硬化性熱硬 U 化性樹脂組成物之層），在不剝離薄膜（背面膜或覆蓋膜 )下，進行曝光（活性能量線的照射）。曝光係藉由接觸 式（或非接觸方式），透過形成圓型的光罩而選擇性地藉 由活性能量線進行曝光之方法、或藉由雷射直接曝光機進 行直接圖型曝光之方法的任一者。藉由此曝光，光硬化性 熱硬化性樹脂組成物之層，曝光部（藉由活性能量線照射 的部分）硬化。接著，剝離薄膜（背面膜或覆蓋膜），將 未曝光部藉由稀鹼水溶液（例如0.3〜3%碳酸蘇打水溶液 Q )進行顯影而形成光阻圖型。然後更進一步地，藉由例如 加熱約1 40〜1 80 °C的溫度使其熱硬化，或者藉由活性能量 線的照射後加熱硬化或加熱硬化後活性能量線的照射使其 最終硬化（真硬化），前述含羧基之感光性樹脂或/及含 羧基之樹脂的羧基、與分子中具有2個以上環狀醚基及/ 或環狀硫代醚基之熱硬化性成分進行反應，可形成密著性 、耐焊熱性、耐藥品性、耐吸濕性、無電解金鍍敷耐性、 電絕緣性等之諸特性優異的硬化皮膜。 作爲上述基材，預先形成電路的印刷電路板，特別是 -26- 200935172 可撓性印刷電路板之外，可使用使用紙-酚樹脂、紙-環氧 基樹脂、玻璃布-環氧基樹脂、玻璃·聚醯亞胺、玻璃布，不 織布-環氧基樹脂、玻璃布/紙-環氧基樹脂、合成纖維-環 氧基樹脂、氟樹脂.聚乙烯· PPO ·氰酸酯等之複合材之所 有的等級（FR-4等）的貼銅層合板、或聚醯亞胺薄膜、 PET薄膜、玻璃基板、陶瓷基板、晶圓板等。 作爲上述活性能量線照射所使用的曝光機，只要是搭 載高壓水銀燈、超高壓水銀燈、金屬鹵素燈、水銀短電弧 燈等，於350〜450nm的範圍照射紫外線的裝置即可，而 且亦可使用直接描繪裝置（例如由電腦的CAD數據以直 接雷射描繪影像之雷射直接成像裝置）。作爲直描機的雷 射光源，若使用最大波長爲3 50〜410nm的範圍之雷射光 ，氣體雷射、固體雷射的任一者皆可。影像形成用的曝光 量依膜厚等不同，但一般而言爲20〜1 000m J/cm2，較佳 爲100〜900mJ/cm2的範圍內。 作爲前述顯影方法，可藉由浸漬法、噴淋法、噴霧法 、刷式法等，作爲顯影液，可使用氫氧化鉀、氫氧化鈉、 碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶 液。 【實施方式】 [實施例] 以下，列示實施例等，更具體地說明關於本發明，本 發明並不限定於此等實施例。再者，以下之「份」及「％ -27- 200935172 」，在沒有特別規定下皆爲質量基準。 合成例1 於具備溫度計、攪拌機及回流冷卻器的5L可拆式燒 瓶（speparable flask)中，投入作爲聚合物多元醇之聚己 內酯二醇（DAICEL化學工業公司製PLACCEL208、分子 量830 ) 1，245份、作爲具有羧基之二羥基化合物之二羥 0 甲基丙酸201份、作爲聚異氰酸酯之異佛爾酮二異氰酸酯 777份及作爲具有經基的（甲基）丙稀酸酯之2 -經基乙基 丙烯酸酯119份、而且p-甲氧基酚及二-t-丁基-羥基甲苯 各0.5份。一邊攪拌一邊加熱至60 °C後停止，添加二丁基 錫二月桂酸酯〇·8份。如果反應容器內的溫度開始降低則 再度加熱，以80 °C續續攪拌，用紅外線吸收光譜確認異氰 酸酯基的吸收光譜（2280CHT1 )消失則結束反應，得到黏 稠液體的胺基甲酸乙酯丙烯酸酯化合物。使用卡必醇乙酸 Q 酯調整至不揮發分 50%。得到具有固形物的酸價 47mgKOH/g、不揮發分50%之含羧基的胺基甲酸乙酯（ 甲基）丙烯酸酯化合物。 合成例2 於具備溫度計、氮氣導入裝置兼環氧化物導入裝置及 攪拌裝置之高壓鍋中，裝入酚醛清漆型甲酚樹脂（商品名 「Shonol CRG951」、昭和高分子（股）製、〇H當量： 119.4) 119.4份、氫氧化鉀1·19份及甲苯119.4份，攪拌 -28- 200935172 同時使系統內進行氮氣置換，加熱昇溫。接著，慢慢地滴 下環氧丙院63.8份，以125〜132°C、〇〜4.8kg/cm2進行 16小時反應。然後，冷卻至室溫，於此反應溶液中添加 混合89%磷酸1.56份而中和氫氧化鉀，得到不揮發分 62.1%、羥基價爲182.2g/eq.之酚醛清漆型甲酚樹脂的環 氧丙烷反應溶液。此爲酚性羥基每1當量加成平均1.08 莫耳的環氧化物者。 將所得到的酚醛清漆型甲酚樹脂的環氧化物反應溶液 293.0份、丙烯酸43.2份、甲烷磺酸11.53份、甲基氫醌 0.18份及甲苯252.9份，裝入至具備攪拌機、溫度計及空 氣吹入管之反應器，以l〇ml/分鐘的速度吹入空氣，一邊 攪拌一邊以1 1 〇 °C進行1 2小時反應。經由反應所生成的水 ，作爲與甲苯的共沸混合物，12.6份的水蒸餾出去。然後 ，冷卻至室溫，將所得到的反應溶液用1 5 %氫氧化鈉水 溶液3 5.3 5份中和，接著進行水洗。然後，用蒸發器將甲 苯以二乙二醇單乙基醚乙酸酯118.1份置換同時蒸餾去除 ，得到酚醛清漆型丙烯酸酯樹脂溶液。接著，將所得到的 酚醛清漆型丙烯酸酯樹脂溶液3 32.5份及三苯基膦1.22 份，裝入至具備攪拌器、溫度計及空氣吹入管的反應器， 將空氣以10ml/分鐘的速度吹入，一邊攪拌一邊慢慢地加 入四氫苯二甲酸酐6 0.8份，以95〜101 °C進行6小時反應 ，冷卻後取出。如此作法所得到的含羧基之感光性樹脂’ 爲不揮發分70.6%、固形物的酸價87.7mgKOH/g。 -29- 200935172 合成例3 將甲酚酚醛清漆型環氧基樹脂的ECON-104S (日本 化藥公司製、環氧基當量=22 0 ) 220份（1當量）裝入至 附有攪拌機及冷卻器的四口燒瓶，加入丙二醇單甲基醚乙 酸酯20 7.2份，加熱溶解。接著，加入作爲聚合禁止劑之 甲基氫醌0.46份、與作爲反應觸媒之三苯基膦1.38份。 將此混合物加熱至95〜105 °C，慢慢地滴下丙烯酸50.4份 (0.7當量）、P-羥基苯乙基醇41.5份（0.3當量），進 行16小時反應。將此反應物（羥基：1.3當量）冷卻至 80〜90°C爲止，加入四氫苯二甲酸酐73.0份（0.48當量 )，進行8小時反應，冷卻後取出。如此作法所得到的含 羧基之感光性樹脂，爲不揮發分65%、固形物的酸價 70mgKOH/g。 合成例4 使雙酚F型環氧基樹脂（環氧基當量=950、軟化點 8 5°C、平均聚合度n = 6.2 ) 3 80份與環氧氯丙烷925份溶 解於二甲基亞碾4 62.5份後，攪拌下以70 °C將純度98.5% NaOH 60.9份（1.5莫耳）分成100份添加。添加後再以 7 0 °C進行3小時反應，反應終了後，加入水25 0份進行水 洗，油水分離後，從油層在減壓下蒸餾回收二甲基亞颯的 大半部分及過剩的未反應環氧氯丙烷，將含有残留的副產 物鹽與二甲基亞颯之反應生成物溶解於甲基異丁基酮75 0 份，再加入30% NaOH水溶液10份，以70°C進行1小時 -30- 200935172 反應。反應終了後，加入水200份進行2次水洗，油水分 離後，從油層蒸餾回收甲基異丁基酮，得到環氧基當量 =3 1 0、軟化點69°C的多官能環氧基樹脂。所得到的多官 能環氧基樹脂，由環氧基當量計算，則前述出發物質雙酚 F型環氧基樹脂中醇性羥基6.2個中約5個經環氧基化者 。將此多官能環氧基樹脂310份及丙二醇單甲基醚乙酸酯 2 82份裝入至附有攪拌機及回流冷卻器的四口燒瓶中，以 9 0 °C進行加熱·攪拌、溶解。將所得到的溶液一度冷卻至 6 0°C爲止，加入丙烯酸72份、甲基氫醌0.5份、三苯基 膦2份，加熱至100 °C，使其反應約60小時，得到酸價爲 0.2mgKOH/g的反應物。於其中加入四氫苯二甲酸酐140 份，加熱至 90°C ，進行反應至固形分酸價成爲 100mgKOH/g爲止，得到含有65%固形分之溶液。 合成例5 將甲酚酚醛清漆型環氧基樹脂（EPICLON N-695、大 日本油墨化學工業公司製、環氧基當量220) 330份，裝 入至具備氣體導入管、攪拌裝置、冷卻管及溫度計的燒瓶 中，加入卡必醇乙酸酯340份，加熱溶解，加入氫醌0.46 份、與三苯基膦1.38份。使此混合物加熱至95〜105 °C， 慢慢地滴下丙烯酸108份，進行16小時反應。使此反應 生成物，冷卻至80〜90°C爲止，加入四氫苯二甲酸酐68 份，進行8小時反應，使其冷卻。得到固形物的酸價 50mgKOH/g、不揮發分60%之含羧基的感光性樹月旨。 200935172 <光硬化性熱硬化性樹脂組成物的調製> (1)光聚合起始劑的檢討 使用前述合成例1及合成例2所得到的清漆之表1所 示的慘合成分，用3輥硏磨機進行混練，得到光硬化性熱 硬化性樹脂組成物的主劑。此外，將表2所示的各成分進 行慘合•攪拌後，用3輥機進行分散•混練，調製硬化劑 [表1] 組成價量份） 實施例1 比較例1 比較例2 合成例1的清漆 140 140 140 合成例2的清漆 46 46 46 TPO*1 10 • 10 Irg-907*2 _ 10 • Irg-369*3 _ 10 噻吩嗪 0.2 0.2 0.2 酞菁•藍 0.6 0.6 0.6 黃色顏料*4 0.6 0.6 0.6 BYK-380N*5 4 4 4 備 考 * 1:2,4,6-三甲基苯甲醯苯基膦氧化物(BASF日本公司製） *2:2-甲基-1-[4-(甲基硫代)苯基]-2-嗎琳代丙酮-l(Ciba Specialty chemicals公司製） *3:2-节基-2-二甲基胺基-1-(4-嗎琳代苯基)-丁院-1-酮(Ciba Specialty chemicals 公 司製） Μ:蒽醌系黃色顏料 *5:塗平劑(ΒΥΚ日本(股)製） -32- 200935172 [表2] 硬化劑組成(質量份） RE306清漆” 37 DA-600*2 20 三聚氰胺 3 合計 60 備 考 * 1:使苯酚酚醛清漆型環氧樹脂(日本火藥(股)製)RE-306溶解於丙二醇單甲基醚 而成爲不揮發分爲90%之清漆。 *2:三洋化成公司製的多官能丙烯酸酯的混合物(商品名:NEOMER-DA-600) (2 )含羧基之感光性樹脂的檢討 使用前述合成例1〜5所得到的清漆之表3所示的摻 合成分，用3輥硏磨機進行混練，得到光硬化性熱硬化性 樹脂組成物的主劑。此外，將表2所示的各成分進行摻合 •攪拌後，用3輥機進行分散•混練，調製硬化劑。 -33- 200935172 [表3] Ο *1:2,4,6-三甲基苯甲醯苯基膦氧化物(BASF日本公司製） „ *2:2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮(Ciba Specialty chemicals公司製) 1 *3:蒽醌系黃色顔料 考*4:塗平劑(BYK日本(股)製） _(質量份） 實施例 比較例 2 3 4 5 6 3 4 5 6 7 感 光 性 樹 脂 合成例1 200 - - — — 200 - - — — 合成例2 — 164 一 — - - 154 - '- — 合成例3 — - 154 — - - — 154 — — 合成例4 — 一 — 161 - - — — 161 — 合成例5 — - 一 — 156 - 一 一 一 ' 156 光聚合 起始劑 Τ Ρ 〇 * 1 10 10 10 10 10 — - — — Irg—369* 2 10 10 10 10 10 噻吩嗪 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 酞菁.藍 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 黃色顔料*3 0.6 0.6 0.6 0.6 0,6 0.6 0,6 0.6 0,6 0.6 B YK- 3 8 0 N*4 4 4 4 4 4 4 4 4 4 4 (3 )含磷的光聚合起始劑的檢討 使用前述合成例1及合成例2所得到的各清漆之表4 所示的摻合成分，用3輥硏磨機進行混練’得到光硬化性 熱硬化性樹脂組成物的主劑。此外，將表2所示的各成分 Ο 進行摻合·攪拌後，用3輥機進行分散•混練’使用調製 硬化劑。 -34- 200935172 [表4] 組成(質量份） 實施例 7 8 9 感光性樹脂 合成例1的清漆 140 140 140 合成例2的清漆 46 46 46 光聚合起始劑 ΤΡΟ*1 10 - - TPO-L*2 祕 10 - Irg-819*3 _ — 10 噻吩嗪 0.2 0.2 0.2 酞菁•藍 0.6 0.6 0.6 黃色顔料·4 0.6 0.6 0.6 ΒΥΚ-380Ν*5 4 4 4 * 1:2,4,6-三甲基苯甲醯二苯基鱗氧化物(BASF曰本公司製） *2:乙基-2,4,6-三甲基苯甲醯苯基次膦酸酯(BASF日本公司製） *3:雙(2,4,6-三甲基苯甲醯)-苯基膦氧化物(Ciba Specialty chemicals公司製) Μ麵系黃色顔料 *5:塗平劑(ΒΥΚ日本(股)製)__________ <乾膜的製作> 將前述表1、表3及表4所示的實施例1〜9及比較 例1〜7的各主劑與表2所示的硬化劑，各自以羧基：環 氧基成爲1 : 1 . 5的比例進行混合，調製光硬化性熱硬化 性樹脂組成物。將所得到的各光硬化性熱硬化性樹脂組成 物，使用塗佈機，塗佈於PET薄膜（三菱聚酯公司製 R310: 16/zm)使其各自乾燥後膜厚成爲30/zm，以40〜 l〇〇t使其乾燥而得到乾膜。 <評估基板的製作> 將形成回路的FR-4基板進行抛光硏磨後，將用上述 -35- 200935172 方法所製作的各乾膜使用真空層壓機（名機製作所公司製 MVLP-500 )以 0.8 MPa、80 °C、1 分鐘、133.3Pa 的條件進 行加熱層壓而製作各評估基板。 (1 )光聚合起始劑的評估結果 於使用前述表1的主劑與表2的硬化劑而得到的各評 估基板，介由kodak Νο·2的step tablet進行曝光，剝離 背面膜後，藉由3 (TC的1質量％碳酸鈉水溶液以噴壓 0.2Mpa進行60秒顯影時，所殘留的step tablet的圖型爲 3段時作爲最適曝光量。 接著，對前述各評估基板，墊上形成直徑8 0μιη的圓 形的遮光部分的負型遮罩，以最適曝光量剛進行曝光後、 5分鐘後、10分鐘後、15分鐘後，剝離背面膜，藉由 3 0°C的1質量％碳酸鈉水溶液以噴壓0.2MPa進行60秒顯 影。將所得到的光阻圖型的形狀以目視及顯微鏡照片依下 述的評估基準進行評估。其結果列示於表5及圖1〜3。 〇：無孔部的開口徑的收縮、毛邊的發生等。 △:孔部的開口徑僅稍微收縮。 x :孔部發生毛邊。 -36- 200935172 [表5] 實施例1 比較例1 比較例2 所使用的光聚合起始劑 TOP Irg-907 Irg-369 於剛曝光後剝離背面膜 評估結果 〇 〇 Δ 參考圖 a-1 b-1 c-1 於曝光5分鐘後剝離背面 膜 結果 〇 Δ X 參考圖 a-2 b-2 c-2 於曝光10分鐘後剝離背 面膜 評估結果 〇 X X 參考圖 a-3 b-3 c-3 於曝光15分鐘後剝離背 面膜 評估結果 〇 X X 參考圖 a-4 b-4 c-4 (2)含羧基之感光性樹脂的評估結果 於使用前述表3的主劑與表2的硬化劑而得到的各評 估基板，介由kodak No.2的step tablet進行曝光，剝離 背面膜後，藉由30 °C的1質量％碳酸鈉水溶液以噴壓 0.2Mpa進行60秒顯影時，所殘留的step tablet的圖型爲 3段時作爲最適曝光量。 接著，對前述各評估基板，墊上形成直徑8 0 μιη的圓 形的遮光部分的負型遮罩，以最適曝光量剛進行曝光後、 10分鐘後、30分鐘後，剝離背面膜，藉由30 °C的1質量 %碳酸鈉水溶液以噴壓〇.2MPa進行60秒顯影。將所得到 的光阻圖型的形狀以目視及顯微鏡照片依下述的評估基準 進行評估。其結果列示於表6。 〇：無孔部的開口徑的收縮、毛邊的發生等。 △:孔部的開口徑僅稍微收縮。 :孔部發生毛邊。 -37- 200935172 [表6][Technical Field] The present invention relates to a dry film of a photocurable thermosetting resin composition which is applied to the manufacture of a circuit board and is applied to an electronic component or the like. More specifically, A photocurable thermosetting resin composition and a dry film which are applied to a photoresist layer provided with a hole portion from a consumer circuit to an industrial printed circuit board, in particular, a flexible printed circuit board. Further, the present invention relates to a printed circuit board in which a solder resist layer provided with a hole portion is formed of the related photocurable thermosetting resin composition and a dry film. [Prior Art] Electronic devices are becoming lighter, lighter, higher-performance, and more versatile due to the rapid advancement of semiconductor devices. With these trends, printed circuit boards are becoming more dense. For example, the thinning of the conductor loop, the high stratification, or the reduction of the diameter of the via holes and the blind vias, and the continuous development of the high-density mounting of the surface mounting of the small wafer parts. In addition, in response to the high density of such printed circuit boards, 1C packages called BGA (Ball Gate Array) and CSP (Chip Size Package) are on the way, instead of being called QFP (Quad Flat Package), SOP (Small). 1C package such as external package). In such a package substrate or a printed circuit board for a vehicle, a solder mask for improving reliability is used for opening a gasket or the like for connection to a semiconductor component on a package substrate, and a solder resist is used. Resist) As a solder resist, in the manufacture of high-density printed circuit boards, -4-200935172 is generally used for photo soldering (Photo Solder Resist), in addition to workability, film thickness accuracy, smoothness of the surface of the cured film, etc. From the viewpoint of the above, it has been required to dry film for solder resist. In addition, the core materials used in recent printed circuit boards or package substrates are becoming thinner, such as TAB (Tape Automated Bonding), T-BGA (Tape Ball Array Package), T-CSP (Tape-Chip Size Package) ), UT-CSP (ultra-thin laminated chip size package) and other debut. When such a tape-shaped core material is used, it is necessary to laminate a dry film type solder resist by a roll-to-roll method. The dry film type solder resist is generally formed by forming a dried film of a photocurable thermosetting resin composition on a support called a carrier film or covering the surface with a cover film. In a sheet or roll form, one of the back film or the cover film is peeled off from the printed circuit board, and then selectively exposed, and then the film (back film or cover film) is peeled off. Develop to form a defined pattern of photoresist. As the dry film type photo solder resist, for example, a composition containing an ethyl urethane (meth) acrylate compound (refer to Patent Documents 1 and 2) and a carboxyl group-containing urethane (meth) acrylate are proposed. Various compositions such as a composition of an ester compound (refer to Patent Documents 3 and 4) are used as a photosensitive resin. However, when a dry film of the prior art photocurable thermosetting resin composition is used to form a photoresist pattern in which a hole portion is provided, it is laminated on a printed circuit board, and after selective exposure, the film is peeled off (back film or cover) In the case of development, there is a problem that a burr-like portion remains on the peripheral portion of the hole portion and becomes a hole portion smaller than a predetermined hole diameter. As described above, the burr-like portion remains on the peripheral portion of the hole portion, and when the hole diameter of the hole portion changes, the adhesion of gold plating or the like -5 to 200935172 is lowered, and the reliability of the obtained printed circuit board is greatly impaired. . Further, since the pore diameter of the hole portion changes or the adhesion of gold plating or the like becomes a defective product, there is a problem that productivity is lowered. On the other hand, as a photopolymerization initiator for liquid photoresist welding, 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2- α-Aminoacetophenone photopolymerization initiator such as benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, which has a depth of hardening and solution It is suitable for use in terms of image, heat resistance and heavy fog (for example, refer to Patent Document 5). However, when used for dry film type solder mask, the above problems occur. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 7-248622 (Patent Application Scope) [Patent Document 3] JP-A-2000- 1 Japanese Laid-Open Patent Publication No. JP-A-2002-229201 (Patent Application) [Patent Document 5] JP-A-2000-2 1 4584 (Patent Application) [Problems to be Solved by the Invention] The present invention has been made in view of the problems of the prior art as described above, and the object thereof is to provide a dry film laminated on a printed circuit board, and after selective exposure, peeling off a film of -6-200935172 (back film) Or a cover film), when forming a photoresist pattern in which a hole portion is formed after development, there is no problem that a burr-like portion remains on the peripheral portion of the hole portion, and a hole portion smaller than a predetermined hole diameter is formed, and the film can be formed according to the predetermined shape. A dry film of a photo-curable thermosetting resin composition of a resist pattern of a pattern is exposed, and a printed circuit board having excellent productivity and high reliability, particularly a flexible printed circuit board, is provided. Further, another object of the present invention is to provide a photocurable thermosetting which causes the same problem as described above when forming a photoresist pattern in which a hole portion is formed by exposure of a film without using the above dry film. Resin composition. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, a dry film for forming a dry film of a photo-curable thermosetting resin composition having a resist pattern of a hole portion is provided. A photopolymerization initiator containing a phosphorus is used as a photopolymerization initiator in combination with a photocurable component and a thermosetting component. In a preferred embodiment, the phosphorus-containing photopolymerization initiator is a mercaptophosphine oxide photopolymerization initiator. Further, according to another aspect of the present invention, a printed circuit board in which a solder resist layer provided with a hole portion is formed by the above dry film is provided. Further, in order to achieve other objects, the present invention provides a photocurable thermosetting resin composition which is used for a photocurable thermosetting resin which is formed by a method of forming a photoresist pattern in which a hole portion is exposed by a film. The material is characterized in that it is a polymerization initiator of light 200935172 which is contained together with a photocurable component and a thermosetting component, and a photopolymerization initiator containing phosphorus is used. According to the present invention, a printed circuit board in which a solder resist layer provided with a hole portion is formed of a related photocurable thermosetting resin composition is provided. [Effects of the Invention] The dry film of the present invention is a photopolymerization initiator contained in the photocurable thermosetting resin composition used therein, and is a photopolymerization initiator containing phosphorus, so that it is printed. When the circuit board forms a photoresist pattern in which the hole portion is formed, the dry film is laminated on the printed circuit board, and after selective exposure, the film (back film or cover film) is peeled off, and when developed, it does not exist around the hole portion. A portion having a burr-like portion remains on the portion and becomes a hole portion smaller than a predetermined aperture, and a resist pattern according to a predetermined exposure pattern can be formed. As a result, it is possible to provide a printed circuit board having improved adhesion such as gold plating, excellent productivity, and high reliability. Φ [Best Mode for Carrying Out the Invention] The inventors of the present invention have intensively studied the above-mentioned phenomenon caused by using a dry film of a photocurable thermosetting resin composition as a photosensitive resin layer. As a result, it is considered that such a phenomenon is caused by the following reasons. That is, when the dry film is laminated on a printed circuit board, one side of the back film or the cover film is peeled off and laminated on the printed circuit board, and then selectively exposed, and then the film (back film or cover film) is peeled off. Thereafter, a predetermined photoresist pattern is formed by performing development. Therefore, since the film (back film or cover film) is peeled off, the layer (dry film) of the photohardenable resin composition formed on the printed circuit board is on the film (back) When the mask or the cover film is covered, the contact with the oxygen of the outside air is hindered, and the polymerization inhibition by oxygen does not occur. Therefore, the peripheral portion of the pattern of the hole pattern in which the irradiation of the active energy ray is blocked by the reticle causes halation, and after the exposure, a large amount of polymerization reaction proceeds until the film is peeled off, so that the peripheral portion of the hole portion is formed. A developing residue portion having a burr shape is formed to become a hole portion having a predetermined hole diameter. The inventors of the present invention have repeatedly reviewed the results of such a phenomenon, and found that the photopolymerization initiator contained in the photocurable thermosetting resin composition used for the dry film is a photopolymerization using phosphorus. In the case of forming a photoresist pattern in which a hole portion is formed in a printed circuit board, there is no problem that a portion having a burr shape on the peripheral portion of the hole portion remains as described above, and a hole portion smaller than a predetermined hole diameter is formed. The present invention has been completed in accordance with a photoresist pattern of a predetermined exposure pattern. The reason for this is difficult to say, but it is considered that the photopolymerization initiator containing phosphorus acts as a polymerization inhibitor, so that even in the layer of the photocurable thermosetting resin composition formed on the printed circuit board The upper surface of the (dry film) is covered with a film (back film or cover film) to prevent contact with oxygen of the outside air (a state in which oxygen is not inhibited), and also hinders polymerization between after exposure to the release film. get on. A suitable phosphorus-containing photopolymerization initiator which has the above-mentioned effects and effects is a mercaptophosphine oxide-based photopolymerization initiator having a group represented by the following general formula (I). 200935172 R1 R2—P—G— (I) (wherein R 1 and R 2 each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, or the like. An aryl group in which a cyclopentyl group, an aryl group, or an anthracene is substituted by a halogen atom, an alkyl group or an alkoxy group, wherein one of R1 and the ruler 2 may be an RC(=〇)- group (wherein R represents a carbon number) Hydrocarbyl group of 1 to 20)) Specific examples of the mercaptophosphine oxide-based photopolymerization initiator having the group represented by the above general formula (I) include (2,6-dimethoxybenzidine). -2,4,4-pentylphosphine oxide, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide)-phenyl Phosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. © Commercially available products include LUCIRIN TPO, LR8953X manufactured by BASF Corporation, and IRGACURE 8 1 9 manufactured by Ciba Specialty Chemicals. . In addition, it has excellent aforementioned effects. A phosphorus-containing photopolymerization initiator which is particularly suitable for the effect is a mercaptophosphine oxide-based photopolymerization initiator having a group represented by the following general formula (II). -10- (II) 200935172 [Chem. 2] R1 R304_C_ (wherein R1 and R3 each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, or an aryl group; Or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group, but one of R1 and R3 may be an RC(=0)- group (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms)) Specific examples of the mercaptophosphine oxide-based photopolymerization initiator having the group represented by the above general formula (II) include ethyl-2,4,6-trimethylbenzimidylphenylphosphinate Commercially available products are LUCIRIN TPO-L manufactured by BASF Corporation. The blending amount of the phosphorus-containing photopolymerization initiator is 100 parts by mass based on the carboxyl group-containing photosensitive resin or/and the carboxyl group-containing resin described later (the total amount is the same as the total amount used alone or in the following, the same applies hereinafter) , appropriate as 0. 1 ® to 30 parts by mass, preferably 0. 5 to 20 parts by mass, more preferably 1 to 15 parts by mass. When the blending ratio of the phosphoric acid-containing photopolymerization initiator is less than the above range, the photocurability is deteriorated. On the other hand, when the ratio is more than the above range, the properties of the cured coating film are deteriorated, and the storage stability is deteriorated and less. good. Further, a conventional photopolymerization initiator or photoinitiator may be added in a proportion which does not impair the effects of the present invention. Next, a photocurable thermosetting resin composition which can be used for the formation of a dry film of the present invention will be described. In the composition used in the present invention, in addition to the use of a phosphorus-containing photopolymerization initiator as a photopolymerization initiator, -11 - 200935172, various alkali-developable photocurable thermosetting resins known in the prior art can be used. Composition. As the photocurable component in the photocurable thermosetting resin composition, various conventional carboxyl group-containing photosensitive prepolymers or photopolymerizable monomers having ethylenically unsaturated double bonds may be used singly or in combination 2 More than one kind. Further, 'the photopolymerizable monomer and the alkali-soluble carboxyl group-containing resin' are particularly required for the alkali-developable composition, and the carboxyl group-containing resin 0 preferably contains no ethylenically unsaturated double bond. Any one of a carboxyl group-containing resin or a photosensitive carboxyl group-containing resin having an ethylenically unsaturated double bond can be used without particular limitation, but it is particularly preferred to use a compound as exemplified below (oligomer and Any of the polymers can be used). (1) By having an unsaturated carboxylic acid (a) such as (meth)acrylic acid, an unsaturated double bond with styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene or the like The compound (b) is a carboxyl group-containing resin obtained by copolymerization. Φ (2) by a part of a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond, and an ethylene having a vinyl group, an allyl group, or a (meth) acrylonitrile group The unsaturated group is reacted with a compound such as an epoxy group or an acid chloride, for example, glycidyl (meth)acrylate, and an ethylenically unsaturated group is added as a side group to obtain a A photosensitive resin of a carboxyl group. (3) A compound (c) having an epoxy group and an unsaturated double bond, such as glycidyl (meth)acrylate or methyl glycidyl (meth)acrylate, and a compound having an unsaturated double bond (b) Copolymer, reacted with -12-200935172 unsaturated carboxylic acid (a) to saturate the resulting secondary hydroxyl group with phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Or a carboxyl group-containing photosensitive resin obtained by conducting a reaction with an unsaturated polybasic acid anhydride (d). (4) A copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride or itaconic acid and a compound (b) having an unsaturated double bond, and a hydroxyalkyl (meth) acrylate or the like. A carboxyl group-containing photosensitive resin obtained by reacting a compound (f) having one hydroxyl group and one or more ethylenically unsaturated double bonds. (5) A polyfunctional ring in which a polyfunctional epoxy group (g) having at least two epoxy groups in a molecule described later or a hydroxyl group of a polyfunctional epoxy compound is epoxylated with epichlorohydrin The epoxy group of the oxy resin is esterified with a carboxyl group of an unsaturated monocarboxylic acid (h) such as (meth)acrylic acid (fully esterified or partially esterified, preferably fully esterified) to produce A carboxyl group-containing photosensitive compound obtained by reacting a hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d). (6) an epoxy group of a copolymer of a compound (b) having an unsaturated double bond and glycidyl (meth)acrylate, an alkylcarboxylic acid having 2 to 17 carbon atoms, an alkyl group having an aromatic group An organic acid (i) having one carboxyl group and having no ethylenic unsaturated bond in one molecule such as a carboxylic acid is reacted to obtain a secondary hydroxyl group formed by reacting with a saturated or unsaturated polybasic acid anhydride (d). a carboxyl group-containing resin. (7) Diisocyanate-13- 200935172 ester (j), such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, and dimethylolpropionic acid, a carboxyl group-containing diol compound (k) such as hydroxymethylbutanoic acid, and a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a poly-hydrocarbon-based polyol, and a propyl sulphate-based A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound (m) such as a polyol, a bisphenol A epoxide adduct diol, a phenolic hydroxyl group or an alcoholic hydroxyl group . (8) By diisocyanate (j), bisphenol a type epoxy resin U, hydrogenated bisphenol A type epoxy resin 'brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin (meth) acrylate of a bifunctional epoxy resin such as a bisphenol s type epoxy resin, a bixylenol type epoxy resin, or a bisphenol type epoxy resin, or a partial acid anhydride modified product thereof ( Photosensitive carboxyl group-containing urethane resin obtained by addition polymerization of η), a carboxyl group-containing diol compound (k), and a diol compound (m). (9) In the synthesis of the resin of the above (7) or (8), a compound (f) having one hydroxyl group and one or more ethylenically unsaturated double bonds such as a hydroxyalkyl (meth) acrylate is added. A carboxyl group-containing urethane resin having an unsaturated double bond introduced at its end. (1) In the synthesis of the resin of the above (7) or (8), one or more isocyanate groups are contained in the molecule such as a molar reaction product such as isophorone diisocyanate or pentaerythritol triacrylate. A methyl group-containing carboxy group-containing urethane resin which is terminated by a (meth) acrylated compound (U) having at least two oxetane rings in a molecule as described later. The polyfunctional oxetane compound reacts with the unsaturated monocarboxylic acid (h) in the range of -14 to 200935172 to 'make the saturated or unsaturated polybasic acid anhydride (d) to the primary hydroxyl group in the modified oxetane compound obtained. A carboxyl group-containing photosensitive resin obtained by the reaction. (12) A bifunctional epoxy resin or a bifunctional oxetane resin, which will be described later, is reacted with a dicarboxylic acid to form a hydroxyl group of the first order formed. a carboxyl group-containing polyester resin ruthenium (13) obtained by forming a saturated or unsaturated polybasic acid anhydride (d), which introduces an unsaturated double bond into a reaction product of a bisepoxy compound and a bisphenol, followed by saturation or not A carboxyl group obtained by reacting a saturated polybasic acid anhydride (d) Photosensitive resin (14) An epoxide such as a novolac type phenol resin and ethylene oxide, propylene oxide, butyl epoxide, trimethylene oxide, tetrahydrofuran or tetrahydropyran And/or a reaction product of a cyclic carbonate such as ethylene carbonate, propylene carbonate, butylene carbonate or 2,3-carbonate propyl methacrylate, and an unsaturated monocarboxylic acid (h), The resulting. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride (d). Further, among the above-mentioned carboxyl group-containing resins, a compound having an isocyanate group (also containing a diison acid ester) used in the synthesis of the resin of the above (7) to (1 fluorene) is preferably a benzene ring-free one. In the isocyanic acid vinegar, the polyfunctional and bifunctional epoxy resin used in the synthesis of the resins of the above (5), (8), and (12) is a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton. In the case of a compound having a linear structure of a bixylenol skeleton and a hydrogenated compound thereof, it is preferred from the viewpoint of flexibility and the like. Further, in other respects, the resin of (7) to (10) and the modified product of the above (12), such as the above, have a urethane bond in the main chain for warpage. Better words. In addition, the resin other than the above (1), (6), (7), (11), and (12) has a photosensitive group (radical polymerizable unsaturated double bond) in the molecule, and is photocurable. It is preferable from the viewpoint. Further, in the present specification, the meaning of (meth) acrylate is collectively referred to as acrylate, methacrylate, and the like, and the similar performance is the same. The carboxyl group-containing photosensitive resin and the carboxyl group-containing resin have a large number of free carboxyl groups in the side chain of the backbone and the polymer, and thus can be developed by a dilute aqueous alkali solution. The acid value of the carboxyl group-containing photosensitive resin and the carboxyl group-containing resin is desirably in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing photosensitive resin and the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development becomes difficult. On the other hand, when it exceeds 200 mg KOH/g, dissolution of the exposed portion proceeds due to the developer, and the line is made. It becomes finer than necessary, and depending on the case, the exposed portion and the unexposed portion are dissolved and peeled off by the developer without distinction, and formation of a normal photoresist pattern becomes difficult and is not preferable. Further, the weight average molecular weight of the carboxyl group-containing photosensitive resin and the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the non-sticking property of the coating film is deteriorated, the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced during development, and the resolution is large and poor. On the other hand, when the weight average molecular weight exceeds -16 - 200935172 1 5 0,000, the developability is remarkably deteriorated, and the storage stability is deteriorated. The blending amount of the carboxyl group-containing photosensitive resin or/and the carboxyl group-containing resin is desirably 20 to 70% by mass of the total composition, preferably 30 to 60% by mass. When the amount is less than the above range, the coating film strength is lowered, and on the other hand, when it is more than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered, which is not preferable. When only the above-mentioned carboxyl group-containing resin is used, since it does not have an ethylenically unsaturated double bond per se, it is necessary to use a photopolymerizable monomer in order to form a composition as a photocurable thermosetting resin composition. Examples of the photopolymerizable monomer include hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; and polyethylene glycol; a water-soluble acrylate such as diacrylate or polypropylene glycol diacrylate; a polyfunctional polyester acrylate of a polyol such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate; a polyfunctional alcohol such as trimethylolpropane or hydrogenated bisphenol A; an oxirane adduct of a polyphenol such as bisphenol A or bisphenol; and/or an acrylate of a propylene oxide adduct; a polyfunctional or monofunctional polyurethane acrylate of a hydroxy acrylate isocyanate modification; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin ( Epoxy acrylates of methyl)acrylic acid adducts; caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolactone-modified acrylate of dipentaerythritol, Lactone-modified hydroxytrimethylacetic acid new-17-200935172 hexyl lactone-modified acrylate such as pentanediol ester diacrylate, and photosensitivity of methacrylates corresponding to the above acrylates The (meth) acrylate compound may be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acrylonitrile groups in one molecule is preferred. The purpose of use of these photosensitive (meth) acrylate compounds is to make the composition photohardenable. The photosensitive (meth) acrylate compound which is liquid at room temperature, in addition to the purpose of making the composition photocurable, adjusts the composition to a viscosity suitable for various coating methods, and also contributes to The effect of the solubility of the aqueous alkali solution. However, when a photosensitive (meth) acrylate compound which is liquid at room temperature is used, since the dryness of the coating film is not obtained, and the characteristics of the coating film are also deteriorated, the use of a large amount is poor. . The blending amount of the photosensitive (meth) acrylate compound is preferably 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. Further, in the above-mentioned carboxyl group-containing photosensitive resin, a photosensitive (meth) acrylate compound may be blended for the purpose of improving photoreactivity. In this case, the blending amount of the photosensitive (meth) acrylate compound is preferably 100 parts by mass or less based on 100 parts by mass of the photosensitive resin or/and the carboxyl group-containing resin. The photocurable thermosetting resin composition used in the present invention contains a thermosetting component in order to impart heat resistance to the cured film. A preferred thermosetting component is a thermosetting resin having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in the molecule. Among these, a bifunctional epoxy resin is preferred, and other diisocyanates or bifunctional block isocyanates thereof may also be used. -18- 200935172 A thermosetting component having two or more cyclic (thio)ether groups in the molecule, and having a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule or a ring Examples of the compound of the thioether group or the compound of the two types include a polyfunctional epoxy compound having at least two or more epoxy groups in the molecule, and at least two or more oxetane groups in the molecule. A polyfunctional oxetane compound, an epoxy sulfide resin having two or more thioether groups in the molecule, and the like. Specific examples of the polyfunctional epoxy compound include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, and a bisphenol F type ring. Oxygen resin, bisphenol S type epoxy resin, novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, double Phenolic A phenolic epoxide type epoxy resin, bixylenol type epoxy resin, bisphenol type epoxy resin, chelating epoxy resin, glyoxal type epoxy resin, and amine group-containing Epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylene oxime An alkane resin, a polyoxyalkylene modified epoxy resin, an ε-caprolactone modified epoxy resin, or the like. Further, in order to impart flame retardancy, an atom such as phosphorus may be introduced into the structure. These epoxy resins are thermally cured to improve the properties of the cured film, such as adhesion, solder heat resistance, and electroless plating resistance. Further, when the dry film is produced, the epoxy resin is preferably mixed before applying the photocurable thermosetting resin composition to the back film. The adhesion of the photocurable thermosetting resin composition can be avoided by mixing the epoxy resin before coating. Further, 'the photocurable thermosetting resin composition used in the present invention' is preferably used as an epoxy resin in a solid or semi-solid shape at room temperature, preferably in a diluent (at room temperature). The liquid photopolymerizable monomer or organic solvent) is an insoluble or poorly soluble epoxy resin. By using such an epoxy resin, the photocurable thermosetting resin composition before curing is a solid or semi-solid epoxy resin dispersed in a particulate form. The particle size is preferably such that it does not cause malfunction to screen printing or the like. In the photocurable thermosetting resin composition before curing, the epoxy resin having a solid or semi-solid shape is dispersed in the form of fine particles, and the application period of the photocurable thermosetting resin composition is long. Preferably. Preferred examples of the epoxy group-containing resin having a solid or semi-solid shape at room temperature include bisphenol S-type epoxy resin, phenol novolac type epoxy resin, and diglycidyl phthalate resin. A heterocyclic epoxy resin, a bixylenol type epoxy resin, a biphenyl type epoxy resin, a tetraglycidyl xylene oxirane resin, or the like. Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether and bis[(3-ethyl-3-oxa) Cyclobutane methoxy)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-oxo Heterocyclobutane)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl Examples of methacrylate or such oligomers -20-200935172 or polyfunctional oxetane other than copolymers include oxetane and novolak resins, and poly(P-hydroxyl groups). A styrene), a cardo type bisphenol, a calixarene, a cup-resorcinol arene, or a sesquioxane or the like, and an ether compound of a resin having a hydroxyl group. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. Examples of the compound having two or more cyclic thioether groups in the above-mentioned molecule include bisphenol A type epoxy sulfide resin YL7000 manufactured by Nippon Epoxy Resins Co., Ltd., and the like. Further, an epoxy sulfide resin in which an oxygen atom of an epoxy group of a novolac type epoxy resin is substituted with a sulfur atom can also be used. The blending amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin and/or the carboxyl group-containing resin. The ether group is preferably 0. 6~2. 5 equivalents, more preferably 〇. 8~2. A range of 0 equivalents. The amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is less than 0. At 6 equivalents, the carboxyl group remains in the hardened film, which is less preferable because of lower heat resistance, alkali resistance, electrical insulation, and the like. On the other hand, 'more than 2. In the case of 5 equivalents, since the low molecular weight cyclic (thio)ether group remains on the dried coating film, the strength of the coating film is lowered, which is less preferable. The photocurable thermosetting resin composition used in the present invention may contain a thermosetting catalyst because it contains a thermosetting component having two or more cyclic (thio)ether groups in the molecule. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl-21 - 200935172 imidazole, 2-phenylimidazole, 4-phenylene Imidazole derivatives such as imidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide Dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N An amine compound such as N-dimethylbenzylamine, an anthracene acid adipate or a phosphonium azelate or the like; a phosphorus compound such as triphenylphosphine or the like. In addition, as a commercial product, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all the brand name of an imidazole type compound) manufactured by Shikoku Kasei Kogyo Co., Ltd., and 1 by San-apro Co., Ltd. CAT3 5 03N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, UC AT5 0 02 (all of which are bicyclic guanidine compounds and salts thereof). It is not particularly limited thereto, and may be any one of a thermosetting catalyst of an epoxy resin or an oxetane compound or a reaction promoting an epoxy group and/or an oxetane group and a carboxyl group. It can be used alone or in combination of two or more. In addition, guanamine amine, methyl guanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl can be used. -4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·trimeric isocyanate adduct, 2,4-diamino-6 -Methyl propylene decyloxyethyl-S-triazine. The S-triazine derivative such as a trimeric isocyanate adduct is preferably used as a compound which functions as a tackifier and the above-mentioned thermosetting catalyst. The blending amount of the thermosetting catalyst is usually sufficient, and for example, the thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably 1 part by mass. _1 to 20 parts by mass, more preferably 0. 5 -22- 200935172 ~15. 0 parts by mass. Further, the photocurable thermosetting resin composition used in the present invention dissolves the photocurable component or the thermosetting component, and can be blended with an organic solvent in order to adjust the viscosity to a method suitable for coating the composition. . Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether and ethylene glycol monomethyl Ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, a glycol ether such as dipropylene glycol diethyl ether or triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate An acetate such as ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These organic solvents may be used singly or in combination of two or more kinds. The blending amount of the organic solvent ' can be any amount depending on the use or the like. The photocurable thermosetting resin composition used in the present invention contains conventional photopolymerization of phenothiazine, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol or the like. The inhibiting agent is preferred. By including such a photopolymerization inhibiting agent, it is easier to carry out the polymerization reaction from selective exposure to the release film (back film or cover film) after laminating the dry film on the printed circuit board. control. The blending amount of the photopolymerization inhibiting agent' phase-23-200935172 is preferably 1 part by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing photosensitive resin and/or carboxyl group-containing resin. . In the photocurable thermosetting resin composition used in the present invention, if necessary, two or more kinds of barium sulfate, barium titanate, amorphous ceria, crystalline ceria, and molten two may be further blended. Conventional inorganic chelating agents such as cerium oxide, spherical cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide φ, mica, and the like. These are used to suppress the hardening shrinkage of the coating film and to improve the properties such as adhesion and hardness. The blending amount of the inorganic chelating agent is preferably 300 parts by mass or less, preferably 30 to 200 parts by mass, per 100 parts by mass of the carboxyl group-containing photosensitive resin and/or carboxyl group-containing resin. In the photocurable thermosetting resin composition used in the present invention, a colorant may be further blended as necessary. As the coloring agent, conventionally known as red, blue, green, yellow, etc. such as phthalocyanine blue, phthalocyanine green, iodine green, bisazo yellow, crystal violet, titanium oxide, carbon black, and Q naphthalene black can be used. Any of the coloring agents, pigments, dyes, and pigments. However, it is preferable that halogen is not contained from the viewpoint of a reduction in environmental burden and an influence on the human body. Further, the photocurable thermosetting resin composition used in the present invention may be re-blended with a conventionally used tackifier such as fine powder of cerium oxide, organic bentonite, montmorillonite or the like, if necessary. Defoaming agent and/or coating agent such as alkane, fluorine or polymer, etc., a mower coupling agent such as a bismuth system, a thiazine system, a triterpenoid system, a phosphorus-based flame retardant, and a lanthanum-based flame retardant Conventional additives such as flame retardants. -24- 200935172 When the film is dried, the photocurable thermosetting resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to a suitable viscosity, and coated with a comma coater or a squeegee. Cloth machine, lip coater, bar coater, squeeze coater, reverse roll coater, transfer roll coater, gravure coater, sprayer, etc. The thickness is applied to the back film (support), and a film is usually obtained by drying at a temperature of 50 to 13 (TC for 1 to 30 minutes. The film thickness is not particularly limited, but generally the film after drying Thick, suitable for the range of 1 〇~1 5 0 "m, preferably 20~60" m. Drying can use hot air circulating drying oven, IR furnace, heating plate, convection oven, etc. The heat source of the air heating method is a method in which the hot air in the dryer is brought into contact with the flow, or is blown toward the support by the nozzle.) As the back film, a plastic film is used, preferably polyterephthalic acid is used. Polyester film such as ethylene glycol ester, polyfluorene A plastic film such as an amine film, a polyimide film, a polypropylene film, or a polystyrene film. The thickness of the back film is not particularly limited, but is generally selected in the range of 1 〇 to 150 °. After film formation on the back film, in order to prevent dust from adhering to the surface of the film, a possible cover film (protective film) may be peeled off on the surface of the film. As a peelable cover film, for example, a polyethylene film may be used. A PTFE film, a polypropylene film, a surface-treated paper, or the like may be used as long as the adhesion between the film and the cover film is smaller than the adhesion between the film and the back film when the cover film is peeled off. -25- 200935172 The film is bonded to a substrate by using a hot roll laminator or the like (the layer of the photocurable thermosetting resin composition is bonded to the substrate under contact), and is photocurable thermosetting of the film. When a dry film of a peelable cover film is further provided on the layer of the resin composition, after the cover film (or the back film) is peeled off, the layer of the photocurable thermosetting resin composition is brought into contact with the substrate. The film is bonded to the film by a hot roll laminator or the like. Then, the film is not peeled off with respect to the dry film (the layer of the photocurable thermosetting resin composition) bonded to the substrate. Or exposure (exposure of active energy rays) under exposure film. Exposure is a method of selectively exposing by active energy rays through a contact type (or non-contact method) by forming a circular mask. Or any of the methods of direct pattern exposure by a laser direct exposure machine. By this exposure, the layer of the photocurable thermosetting resin composition is exposed, and the exposed portion (the portion irradiated by the active energy ray) hardens. Then, the film is peeled off (back film or cover film), and the unexposed portion is passed through a dilute aqueous alkali solution (for example, 0. 3 to 3% aqueous solution of soda carbonate Q) Developed to form a photoresist pattern. Further, it is further hardened by, for example, heating at a temperature of about 140 to 180 ° C, or is finally hardened by irradiation of an active energy ray after heat hardening or heat hardening. The curing may be carried out by reacting a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin carboxyl group with a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group in the molecule. A hardened film excellent in properties such as adhesion, solder heat resistance, chemical resistance, moisture absorption resistance, electroless gold plating resistance, and electrical insulating properties. As the above-mentioned substrate, a printed circuit board in which a circuit is formed in advance, in particular, a flexible printed circuit board of -26-200935172, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin can be used. , glass · polyimine, glass cloth, non-woven fabric - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin. A copper-clad laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like of all grades (FR-4, etc.) of a composite material such as polyethylene, PPO, and cyanate. The exposure machine used for the active energy ray irradiation may be a device that emits ultraviolet light in a range of 350 to 450 nm, as long as it is equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like. A rendering device (for example, a laser direct imaging device that draws an image directly from a CAD data of a computer). As the laser light source of the direct-drawing machine, if laser light having a maximum wavelength of 3 50 to 410 nm is used, either a gas laser or a solid laser can be used. The exposure amount for image formation differs depending on the film thickness or the like, but is generally in the range of 20 to 1 000 m J/cm 2 , preferably 100 to 900 mJ/cm 2 . As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, or the like can be used. An aqueous solution of an alkali such as ammonia or an amine. [Embodiment] [Embodiment] Hereinafter, the present invention will be described more specifically with reference to examples and the like, and the present invention is not limited to the embodiments. In addition, the following "parts" and "% -27- 200935172" are quality benchmarks unless otherwise specified. Synthesis Example 1 Polycaprolactone diol (PLACCEL 208, manufactured by DAICEL Chemical Industry Co., Ltd., molecular weight 830) 1, which is a polymer polyol, was placed in a 5 L seperable flask equipped with a thermometer, a stirrer, and a reflux condenser. 245 parts, 201 parts of dihydroxy 0-methylpropionic acid as a dihydroxy compound having a carboxyl group, 777 parts of isophorone diisocyanate as a polyisocyanate, and 2 as a (meth) acrylate having a trans group. 119 parts by radical ethyl acrylate, and p-methoxyphenol and di-t-butyl-hydroxytoluene each 0. 5 servings. After heating to 60 ° C while stirring, the mixture was stopped, and 8 parts of dibutyltin dilaurate bismuth was added. If the temperature in the reaction vessel starts to decrease, it is heated again, and the mixture is continuously stirred at 80 ° C. The absorption spectrum of the isocyanate group (2280 CHT1 ) disappears by infrared absorption spectrum, and the reaction is terminated to obtain a viscous liquid urethane acrylate compound. . The carbitol acetic acid Q ester was adjusted to a non-volatile content of 50%. A carboxyl group-containing ethyl urethane (meth) acrylate compound having an acid value of 47 mg KOH/g and a nonvolatile content of 50% was obtained. Synthesis Example 2 A phenol cresol type cresol resin (trade name "Shonol CRG951", Showa Polymer Co., Ltd., 〇H equivalent) was placed in a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device. : 119. 4) 119. 4 parts, potassium hydroxide 1.19 parts and toluene 119. 4 parts, stirring -28- 200935172 At the same time, the system is replaced with nitrogen and heated to heat. Then, slowly drop the epoxy propylene courtyard 63. 8 parts, with 125~132 °C, 〇~4. The reaction was carried out for 16 hours at 8 kg/cm2. Then, it was cooled to room temperature, and 89% phosphoric acid was added to the reaction solution. 56 parts and neutralized potassium hydroxide to obtain a non-volatile fraction 62. 1%, the hydroxyl value is 182. 2g/eq. A cyclopropane reaction solution of a novolac type cresol resin. This is an average of 1. 08 Moer's epoxide. The epoxide reaction solution of the obtained novolac type cresol resin is 293. 0 parts, acrylic 43. 2 parts, methanesulfonic acid 11. 53 parts, methylhydroquinone 0. 18 parts and toluene 252. Nine parts were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 1 〇ml/min, and stirred at 1 1 〇 °C for 12 hours while stirring. The water formed by the reaction, as an azeotrope with toluene, 12. 6 parts of water were distilled off. Then, it was cooled to room temperature, and the obtained reaction solution was treated with a 15% aqueous sodium hydroxide solution. 3 5 parts of neutralization, followed by water washing. Then, the toluene is diacetate monoethyl ether acetate 118. One part of the substitution was simultaneously distilled off to obtain a novolac type acrylate resin solution. Next, the obtained novolac type acrylate resin solution 3 32. 5 parts and triphenylphosphine 1. 22 parts were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min, and tetrahydrophthalic anhydride 60 was slowly added while stirring. 8 parts were reacted at 95 to 101 ° C for 6 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin obtained by this method is a nonvolatile matter of 70. 6%, the acid value of solids 87. 7 mg KOH / g. -29- 200935172 Synthesis Example 3 ECON-104S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 22 0) 220 parts (1 equivalent) of a cresol novolac type epoxy resin was charged to a mixer and cooled. a four-necked flask, adding propylene glycol monomethyl ether acetate 20 7. 2 parts, dissolved by heating. Next, methylhydroquinone as a polymerization inhibitor is added. 46 parts, with triphenylphosphine as a reaction catalyst 38 servings. The mixture was heated to 95~105 ° C, and the acrylic acid was slowly dropped. 4 copies (0. 7 equivalents), P-hydroxyphenylethyl alcohol 41. 5 copies (0. 3 equivalents), 16 hours reaction. This reactant (hydroxyl: 1. 3 equivalents) cooled to 80~90 ° C, adding tetrahydrophthalic anhydride 73. 0 copies (0. 48 equivalents), the reaction was carried out for 8 hours, and it was taken out after cooling. The carboxyl group-containing photosensitive resin obtained in this manner had a nonvolatile content of 65% and an acid value of 70 mgKOH/g of the solid matter. Synthesis Example 4 A bisphenol F type epoxy resin (epoxy equivalent = 950, softening point 85 ° C, average degree of polymerization n = 6. 2) 3 80 parts and 925 parts of epichlorohydrin are dissolved in dimethyl yam 4 62. After 5 parts, the purity is 98 ° C at 70 ° C under stirring. 5% NaOH 60. 9 copies (1. 5 moles are divided into 100 parts to add. After the addition, the reaction was carried out at 70 ° C for 3 hours. After the reaction was completed, 25 parts of water was added for washing with water. After separation of the oil and water, most of the dimethyl sulfoxide was recovered from the oil layer under reduced pressure and excess unreacted. Epoxychloropropane, the reaction product containing residual by-product salt and dimethyl hydrazine is dissolved in 75 parts of methyl isobutyl ketone, and then 10 parts of 30% aqueous NaOH solution is added, and the mixture is carried out at 70 ° C for 1 hour. -30- 200935172 Reaction. After the completion of the reaction, 200 parts of water was added for 2 times of water washing, and after separation of oil and water, methyl isobutyl ketone was distilled from the oil layer to obtain a polyfunctional epoxy resin having an epoxy equivalent = 3 1 0 and a softening point of 69 ° C. . The obtained polyfunctional epoxy resin is calculated from the epoxy equivalent, and the above-mentioned starting material is an alcoholic hydroxyl group in the bisphenol F-type epoxy resin. About 5 of the 2 are epoxylated. 310 parts of the polyfunctional epoxy resin and 2 82 parts of propylene glycol monomethyl ether acetate were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and heated, stirred, and dissolved at 90 °C. The obtained solution was once cooled to 60 ° C, and 72 parts of acrylic acid and methylhydroquinone 0 were added. 5 parts, 2 parts of triphenylphosphine, heated to 100 ° C, and allowed to react for about 60 hours to obtain an acid value of 0. 2 mg KOH / g of reactant. 140 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C to carry out a reaction until the solid content of the acid was 100 mgKOH/g to obtain a solution containing 65% solids. Synthesis Example 5 330 parts of a cresol novolac type epoxy resin (EPICLON N-695, manufactured by Dainippon Ink and Chemicals, Ltd., epoxy equivalent 220) was placed in a gas introduction tube, a stirring device, and a cooling tube. In the flask of the thermometer, 340 parts of carbitol acetate was added, dissolved by heating, and hydroquinone was added. 46 parts, with triphenylphosphine 1. 38 servings. The mixture was heated to 95 to 105 ° C, and 108 parts of acrylic acid was slowly dropped to carry out a reaction for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 68 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted for 8 hours to be cooled. A photosensitive resin having a pH of 50 mg KOH/g of a solid matter and a carboxyl group having a nonvolatile content of 60% was obtained. 200935172 <Preparation of Photocurable Thermosetting Resin Composition> (1) Review of Photopolymerization Initiator The composition shown in Table 1 of the varnish obtained in the above Synthesis Example 1 and Synthesis Example 2 was used, and 3 was used. The roll honing machine kneads to obtain a main component of the photocurable thermosetting resin composition. In addition, the components shown in Table 2 were mixed and stirred, and then dispersed and kneaded by a 3-roller to prepare a curing agent [Table 1] Composition valence) Example 1 Comparative Example 1 Comparative Example 2 Synthesis Example 1 Varnish 140 140 140 Varnish of Synthesis Example 46 46 46 TPO*1 10 • 10 Irg-907*2 _ 10 • Irg-369*3 _ 10 Thiophene 0.2 0.2 0.2 Phthalocyanine • Blue 0.6 0.6 0.6 Yellow Pigment*4 0.6 0.6 0.6 BYK-380N*5 4 4 4 Preparation test 1: 1:2,4,6-trimethylbenzimidyl phenylphosphine oxide (BASF Japan) *2: 2-methyl-1-[4 -(Methylthio)phenyl]-2-morphinylacetone-l (manufactured by Ciba Specialty Chemicals Co., Ltd.) *3: 2-benzyl-2-dimethylamino-1-(4-) Phenyl)-butylidene-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd.) Μ: lanthanide yellow pigment*5: coating agent (manufactured by Nippon Co., Ltd.) -32- 200935172 [Table 2] Hardener composition ( Parts by mass) RE306 varnish" 37 DA-600*2 20 Melamine 3 Total 60 Remarks* 1: Dissolve phenol novolac type epoxy resin (made by Nippon Gunpowder Co., Ltd.) RE-306 in propylene glycol monomethyl ether Volamel is divided into 90% varnish. *2: Sanyo Huacheng A mixture of polyfunctional acrylates (trade name: NEOMER-DA-600) (2) Review of photosensitive resin containing a carboxyl group The mixture was kneaded by a 3-roll honing machine to obtain a main component of the photocurable thermosetting resin composition. Further, each component shown in Table 2 was blended and stirred, and then dispersed and kneaded by a 3-roller. Modification of hardener. -33- 200935172 [Table 3] Ο *1: 2,4,6-trimethylbenzimidyl phenylphosphine oxide (BASF Japan) „ *2: 2-Benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 *3: lanthanide yellow pigment test *4: coating agent (BYK Japan) (Stock) _ (parts by mass) Example Comparative Example 2 3 4 5 6 3 4 5 6 7 Photosensitive resin Synthesis Example 1 200 - - - - 200 - - - - Synthesis Example 2 - 164 One - - - 154 - '- - Synthesis Example 3 - - 154 - - - - 154 - Synthesis Example 4 - A - 161 - - - - 161 - Synthesis Example 5 - - One - 156 - One-to-one '156 Photopolymerization initiator Τ Ρ 〇* 1 10 10 10 10 10 — — — — — — — — — — — — — — — 0.6 0,6 0.6 0,6 0.6 0,6 0.6 B YK- 3 8 0 N*4 4 4 4 4 4 4 4 4 4 4 (3) Review of the photopolymerization initiator containing phosphorus using the aforementioned Synthesis Example 1 The blended component shown in Table 4 of each varnish obtained in Synthesis Example 2 was kneaded by a 3-roll honing machine to obtain a main component of the photocurable thermosetting resin composition. Further, each component Ο shown in Table 2 was blended and stirred, and then dispersed and kneaded by a 3-roller to use a curing hardener. -34- 200935172 [Table 4] Composition (parts by mass) Example 7 8 9 Photosensitive Resin Synthetic Example 1 Varnish 140 140 140 Synthetic Example 2 Varnish 46 46 46 Photopolymerization Initiator ΤΡΟ*1 10 - - TPO- L*2 Secret 10 - Irg-819*3 _ — 10 Thiophene 0.2 0.2 0.2 Phthalocyanine • Blue 0.6 0.6 0.6 Yellow pigment · 4 0.6 0.6 0.6 ΒΥΚ-380Ν*5 4 4 4 * 1:2,4,6- Trimethyl benzamidine diphenyl scale oxide (manufactured by BASF Co., Ltd.) *2: Ethyl-2,4,6-trimethylbenzimidylphenylphosphinate (manufactured by BASF Japan) * 3: bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) ΜSkin yellow pigment*5: screeding agent (manufactured by Japan Co., Ltd.) __________ <Production of dry film> Each of the main components of Examples 1 to 9 and Comparative Examples 1 to 7 shown in Tables 1, 3 and 4 and the curing agent shown in Table 2 were each a carboxyl group: ring The oxy group was mixed at a ratio of 1:1.5 to prepare a photocurable thermosetting resin composition. Each of the obtained photocurable thermosetting resin compositions was applied to a PET film (R310: 16/zm manufactured by Mitsubishi Polyester Co., Ltd.) using a coater and dried to a thickness of 30/zm. 40~l〇〇t was dried to obtain a dry film. <Production of Evaluation Substrate> After the FR-4 substrate in which the circuit was formed was subjected to polishing honing, a vacuum laminator (MVLP-500 manufactured by Nihon Seisakusho Co., Ltd.) was used for each dry film produced by the above-mentioned method -35-200935172 Each of the evaluation substrates was produced by heat lamination under the conditions of 0.8 MPa, 80 ° C, 1 minute, and 133.3 Pa. (1) Evaluation results of the photopolymerization initiator The evaluation substrates obtained by using the main component of Table 1 and the hardener of Table 2 were exposed by a step tablet of kodak Νο. 2, and after peeling off the back film, When 3 (the 1% by mass of sodium carbonate aqueous solution of TC was used for 20 seconds at a spray pressure of 0.2 MPa for 60 seconds, the pattern of the remaining step tablet was three stages as the optimum exposure amount. Next, the diameter of the pad was formed on each of the evaluation substrates described above. A negative mask of a circular light-shielding portion of 80 μm, immediately after exposure, 5 minutes, 10 minutes, and 15 minutes after the optimum exposure amount, peeling off the back film by 1% by mass of carbonic acid at 30 ° C The sodium aqueous solution was developed by a spray pressure of 0.2 MPa for 60 seconds, and the shape of the obtained photoresist pattern was evaluated by visual observation and micrograph according to the following evaluation criteria. The results are shown in Table 5 and Figs. 1 to 3. : shrinkage of the opening diameter of the non-hole portion, occurrence of burrs, etc. Δ: The opening diameter of the hole portion is only slightly contracted. x : The hole portion is burred. -36- 200935172 [Table 5] Example 1 Comparative Example 1 Comparative Example 2 The photopolymerization initiator TOP Irg-907 Irg-369 was used. Peeling back film evaluation results after exposure 〇〇 Δ Refer to Figure a-1 b-1 c-1 Stripping back film after 5 minutes of exposure 〇 Δ X Refer to Figure a-2 b-2 c-2 After peeling for 10 minutes Back film evaluation results 〇XX Refer to Figure a-3 b-3 c-3 Peeling back film evaluation results after 15 minutes of exposure 〇XX Refer to Figure a-4 b-4 c-4 (2) Photosensitive resin containing carboxyl group As a result of the evaluation, each of the evaluation substrates obtained by using the main agent of Table 3 and the hardener of Table 2 was exposed through a step tablet of Kodak No. 2, and after peeling off the back film, 1% by mass of carbonic acid at 30 ° C was used. When the sodium aqueous solution was developed by a spray pressure of 0.2 MPa for 60 seconds, the pattern of the remaining step tablet was three stages, and the optimum exposure amount was obtained. Next, a circular light-shielding portion having a diameter of 80 μm was formed on the evaluation substrate. The negative mask was peeled off immediately after exposure to the optimum exposure amount, 10 minutes later, and 30 minutes later, and the film was peeled off by a 1% by mass aqueous sodium carbonate solution at 30 ° C for 60 seconds at a spray pressure of .2 MPa. The shape of the obtained photoresist pattern is visually and microscopically photographed as follows The evaluation criteria are evaluated. The results are shown in Table 6. 〇: Shrinkage of the opening diameter of the non-porous portion, occurrence of burrs, etc. △: The opening diameter of the hole portion is only slightly shrunk: The burr is formed in the hole portion. -37- 200935172 [Table 6]
實施例 比較例 2 3 4 5 6 3 4 5 6 7 所使用的清漆的 合成例 1 2 3 4 5 1 2 3 4 5 於剛曝光後剝離 背面膜 〇 〇 〇 〇 〇 X Δ 〇 Δ △ 於曝光15分鐘後 剝離背面膜 〇 〇 〇 〇 〇 X X X X X 於曝光30分鐘後 剝離背面膜 〇 〇 〇 〇 Δ X X X X XEXAMPLES Comparative Example 2 3 4 5 6 3 4 5 6 7 Synthesis Example 1 of varnish used 2 3 4 5 1 2 3 4 5 Stripped back surface film 〇〇〇〇〇X Δ 〇Δ Δ immediately after exposure After 15 minutes, the back film 〇〇〇〇〇XXXXX was peeled off and the back film 〇〇〇〇Δ XXXXX was peeled off after 30 minutes of exposure.
(3)含磷的光聚合起始劑的評估結果 於使用前述表4的主劑與表2的硬化劑而得到的各評 估基板，介由kodak No.2的step tablet進行曝光，剝離 背面膜後，藉由30°C的1質量％碳酸鈉水溶液以噴壓 0.2Mpa進行60秒顯影時，所殘留的step tablet的圖型爲 3段時作爲最適曝光量。 接著，對前述各評估基板，墊上形成直徑80μιη的圓 形的遮光部分的負型遮罩，以最適曝光量剛進行曝光後、 1〇分鐘後、30分鐘後，剝離背面膜，藉由30°C的1質量 %碳酸鈉水溶液以噴壓0.2MPa進行60秒顯影。將所得到 的光阻圖型的形狀以目視及顯微鏡照片依下述的評估基準 進行評估。其結果列示於表7。 〇：無孔部的開口徑的收縮、毛邊的發生等。 △:孔部的開口徑僅稍微收縮。 -38- 200935172 X :孔部發生毛邊。 [表7] 實施例 7 8 9 所使用的光聚合起始劑 ΤΡΟ TPO-L Irg-819 於剛曝光後剝離背面膜 〇 〇 〇 於曝光15分鐘後剝離背面膜 〇 〇 〇 於曝光30分鐘後剝離背面膜 〇 〇 〇 由表5及圖1〜圖3可清楚的了解，使用含磷的光聚 合起始劑之實施例1，即使剛曝光後、及從曝光後放置至 剝離背面膜進行顯影時，孔部的形狀，約按照設計，未觀 察到孔部的開口徑的收縮或毛邊等的發生。另一方面，使 用液狀的光阻焊且一般所使用的α-胺基苯乙酮系光聚合 起始劑之比較例1及比較例2，觀察到孔部的收縮或毛邊 的發生。 此外，由表6可清楚的了解，即使改變含羧基之感光 @ 性樹脂，使用含磷的光聚合起始劑之乾膜（實施例2〜6 )，比使用一般所使用的α -胺基苯乙酮系光聚合起始劑 之乾膜（比較例3〜7 )，孔部的形狀較安定。 而且，由表7可清楚的了解，即使改變含磷的光聚合 起始劑的種類，孔部的形狀按照設計，未觀察到孔部的開 口徑的收縮或毛邊等的發生，亦未觀察到經時變化。 再者，實施例1中，除了使用氫醌單甲基醚取代吩噻 嗪作爲光聚合禁止劑以外，用同樣的成分組成調製光硬化 -39- 200935172 性熱硬化性樹脂組成物進行評估的結果，得到與實施 同樣的結果。 【圖式簡單說明】 [圖1]爲由使用含磷的光聚合起始劑（TPO )的 ，實施例1所得到的孔部的顯微鏡照片，a-1爲剛曝 、a-2爲曝光5分鐘後、a-3爲曝光10分鐘後、a-4 光15分鐘後各自剝離背面膜，進行顯影時的孔部的 鏡照片。 [圖2]爲由使用胺基苯乙酮系光聚合起始劑（ 907 )之乾膜，比較例1所得到的孔部的顯微鏡照片 爲剛曝光後、b-2爲曝光5分鐘後、b-3爲曝光1〇分 、b-4爲曝光1 5分鐘後各自剝離背面膜，進行顯影 孔部的顯微鏡照片。 [圖3]爲由使用α-胺基苯乙酮系光聚合起始劑（ 3 69 )之乾膜，比較例2所得到的孔部的顯微鏡照片 爲剛曝光後、c-2爲曝光5分鐘後、c-3爲曝光10分 、c-4爲曝光15分鐘後各自剝離背面膜，進行顯影時 部的顯微鏡照片。 例1 乾膜 光後 爲曝 顯微 Irg-，b-1 鐘後 時的 Irg-，c -1 鐘後 的孔 -40- 200935172(3) Evaluation results of the photopolymerization initiator containing phosphorus The evaluation substrates obtained by using the main component of Table 4 and the hardener of Table 2 were exposed by a step tablet of Kodak No. 2, and the back film was peeled off. Thereafter, the film was developed by spraying at a pressure of 0.2 MPa in a 1% by mass aqueous sodium carbonate solution at 30° C. for 60 seconds, and the pattern of the remaining step tablet was three stages as an optimum exposure amount. Next, a negative mask having a circular light-shielding portion having a diameter of 80 μm was formed on each of the evaluation substrates, and the back surface film was peeled off immediately after exposure for 1 minute, 30 minutes after the optimum exposure amount, by 30°. A 1% by mass aqueous solution of C sodium carbonate was developed at a spray pressure of 0.2 MPa for 60 seconds. The shape of the obtained resist pattern was evaluated by visual observation and microscopic photograph according to the following evaluation criteria. The results are shown in Table 7. 〇: Shrinkage of the opening diameter of the non-hole portion, occurrence of burrs, and the like. △: The opening diameter of the hole portion was only slightly contracted. -38- 200935172 X : Burr occurs in the hole. [Table 7] Example 7 8 9 Photopolymerization initiator ΤΡΟ TPO-L Irg-819 After peeling, the back film was peeled off after exposure for 15 minutes, and the back film was peeled off after exposure for 30 minutes. Peeling of the back film 〇〇〇 It is clear from Table 5 and Figs. 1 to 3 that Example 1 using a phosphorus-containing photopolymerization initiator, even after exposure, and after being exposed to the peeling back film for development At the time of the shape of the hole portion, the shrinkage of the opening diameter of the hole portion or the occurrence of burrs or the like was not observed as designed. On the other hand, in Comparative Example 1 and Comparative Example 2 using a liquid photo-resistance and an α-aminoacetophenone-based photopolymerization initiator generally used, shrinkage of the pores or occurrence of burrs were observed. Further, as is clear from Table 6, even if the photosensitive resin containing a carboxyl group was changed, a dry film of a photopolymerization initiator containing phosphorus (Examples 2 to 6) was used, and an α-amino group generally used was used. The dry film of the acetophenone-based photopolymerization initiator (Comparative Examples 3 to 7) had a stable pore shape. Further, as is clear from Table 7, even if the type of the photopolymerization initiator containing phosphorus was changed, the shape of the pore portion was designed so that the shrinkage of the opening diameter of the pore portion or the occurrence of burrs or the like was not observed, and no observation was observed. Change over time. Further, in Example 1, except that hydroquinone monomethyl ether was used in place of phenothiazine as a photopolymerization inhibiting agent, the same component composition was used to prepare a photocurable-39-200935172 thermosetting resin composition for evaluation. , get the same results as the implementation. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a micrograph of a hole obtained in Example 1 using a photopolymerization initiator (TPO) containing phosphorus, a-1 being just exposed and a-2 being exposed. After 5 minutes, a-3 was subjected to exposure for 10 minutes, and after a-4 light for 15 minutes, the back surface film was peeled off, and a mirror photograph of the hole portion at the time of development was performed. 2 is a dry film using an aminoacetophenone-based photopolymerization initiator (907), and the micrograph of the hole portion obtained in Comparative Example 1 is immediately after exposure, and b-2 is after exposure for 5 minutes. B-3 is an exposure of 1 minute, and b-4 is a micrograph of each of which the back surface film is peeled off after exposure for 15 minutes, and the development hole portion is performed. 3 is a dry film using an α-aminoacetophenone photopolymerization initiator (369), and a micrograph of the pore portion obtained in Comparative Example 2 is immediately after exposure, and c-2 is exposure 5 After a minute, c-3 was exposed for 10 minutes, and c-4 was exposed for 15 minutes, and then the back surface film was peeled off, and a microscope photograph of the developing portion was performed. Example 1 Dry film After light is exposed to the microscope Irg-, after Ir-1, after b-1, the hole after c -1 clock -40- 200935172