1267701 五、發明說明（Ο 發明背景 ⑴發明領域 本發明係關於一種正型光化射線分解及顯影性乾膜， 其由含具有胺基甲酸酯鍵聯之樹脂之光化射線分解及顯 影性樹脂組成物形成，其顯示高敏感性及良好之膜處理 性質，而且可形成在電子裝置中可用以形成電路之圖案， 用於印刷之材料。 ⑵背景技藝說明 在此技藝中已知一種形成光分解及顯影性光阻膜之方 法，其包括依照如噴塗、輥塗、絲網印刷等之塗覆或印 刷方法，將液態光分解及顯影性光阻組成物塗覆或印刷 在具有穿孔及/或非穿孔（以下可簡稱爲穿孔）之印刷 電路板上。然而，以上之方法具有將液態樹脂組成物直 接塗覆或印刷在印刷電路板上無法在穿孔內部形成令人 滿意之光阻膜之問題，如此生成穿孔內部如銅、銀等之 導電膜在蝕刻步驟時在蝕刻溶液中部份或完全溶解，而 造成產生如破裂等麻煩。 近年來，爲了保護穿孔免於蝕刻溶液之目的，已使用 將由將正型光分解及顯影性液態光阻組成物塗覆於基質 上而形成之正型膜光阻。至於正型光分解及顯影性液態 光阻組成物之實例，包括含羧基聚合物、聚乙烯醚化合 物及由於光化射線照射之分解製造酸之化合物之可見光 分解及顯影性組成物揭示於，例如，日本專利申請案公 1267701 五、發明說明（2) 開 313134/94、 313135/94、 313136/94、 308733/94、 295064/64 、 146552/95 等。 以上之組成物爲將由組成物形成之塗膜加熱，由於羧 基與乙烯醚基之間之加成反應而發生交聯而不溶於溶劑 與鹼性水溶液中，及在其上照射光化射線及加熱，然後 由於所製造之酸之催化作用而將交聯結構破碎，使得照 射區域再度溶於溶劑與鹼水溶液之光分解及顯影性組成 物。 然而，藉由包括將以上之正型光分解及顯影性組成物 塗覆於如聚對酞酸伸乙酯等之基質上繼而乾燥之方法形 成之正型乾膜產生問題：⑴因爲正型光分解及顯影性塗 覆之不令人滿意之機械性質，在捲繞如上乾燥及形成之 乾膜時發生塗膜裂開及與基質分離，⑵在印刷電路板表 面上使用乾膜形成正型光分解及顯影性塗膜之方法中 (此方法包括將正型光分解及顯影性塗膜面對印刷電路 板折疊，將乾膜加熱以層合及分離聚對酞酸伸乙酯基質 與正型光分解及顯影性塗膜），因爲正型光分解及顯影 性塗膜與基質間之不良黏附性質，在以上之分離步驟之 後，正型光分解及顯影性塗膜部份或完全殘留在聚對酞 酸伸乙酯基質表面上，及（3)因爲正型光分解及顯影性塗 膜之不令人滿意之機械性質，發生塗膜被蝕刻溶液腐蝕 而洗出，造成無法形成精細之光阻圖案。 至於正型光分解及顯影性乾膜之實例，日本專利申請 -4- 1267701 五、發明說明（3) 案公開506 1 06 / 93揭示一種藉由在撓性薄聚合物膜基質 上形成包括具有光-酸不安定基與光-酸產生劑之聚合物 之固態光分解及顯影性層而製備之乾膜光阻。即，以上 之乾膜使得聚合物中之光-酸不安定基因光-酸產生劑產 生之酸之作用或照射而分解，使得僅照射區域溶於顯影 溶液而提供正型影像，但是其具有因爲非照射塗膜區或 照射塗膜區之不溶解或溶解之不明確一致性而無法形成 精細影像之缺點。 發明槪沭： 本發明之目的爲提供一種正型光化射線分解及顯影性 乾膜，其顯示良好之機械性質以易於處理且可形成精細之 光阻圖案。 本發明之另一個目的爲提供一種形成圖案之方法，其可 使用以上之乾膜形成精細之光阻圖案。 即，本發明首先提供一種正型光化射線分解及顯影性 乾膜，其在非光化射線分解及顯影性基質之表面上具有 固態正型光化射線分解及顯影性胺基甲酸酯樹脂層，此 層由以下形成：⑴含以下作爲重要成分之樹脂組成物： (AJ至少一種選自包括含乙烯醚基化合物、含乙烯酯基化 合物及含丙烯酯基化合物之不飽和化合物，（Bi)具有 1，000至200,000之重量平均分子量及每公斤樹脂爲0.5 至10當量範圍之酸基含量之含酸基胺基甲酸酯樹脂，及 (C)光-酸產生劑；⑵含以下作爲重要成分之樹脂組成物： 1267701 五、發明說明（4) (八2)至少一種選自包括乙烯醚胺基甲酸酯爲主化合物、乙 烯酯胺基甲酸酯爲主化合物及丙烯酯胺基甲酸酯爲主化 合物之不飽和胺基甲酸酯爲主化合物，（b2)至少一種選自 包括以下之樹脂：（a)含羧基與羥苯基聚合物，（b)含 羧基聚合物，及（c)含羥苯基聚合物，及（C)光-酸產 生劑；或（3)含以下作爲重要成分之樹脂組成物：（A2)至 少一種選自包括乙烯醚胺基甲酸酯爲主化合物、乙烯酯 胺基甲酸酯爲主化合物及丙烯酯胺基甲酸酯爲主化合物 之不飽和胺基甲酸酯爲主化合物，（Bd具有1，000至 200,000之重量平均分子量及每公斤樹脂爲0.5至10 當量範圍之酸基含量之含酸基胺基甲酸酯樹脂，及（C)光 -酸產生劑。 其次，本發明提供一種形成圖案之方法，其包括以下 之步驟： ⑴將上述之正型光化射線分解及顯影性乾膜應用於塗層 基質表面上，使得塗層基質表面面對乾膜之胺基甲酸酯 樹脂層，⑵視情況地剝除乾膜之非光化射線分解及顯影性 基質， (3)經光罩或直接將光化射線照射在乾膜表面上以得到意 圖之圖案，視情況地熱處理， ⑷剝除在以上步驟⑵中未剝除之非光化射線分解及顯影 性基質， (5)使正型光化射線分解及顯影性胺基甲酸酯樹脂層接受 1267701 五、發明說明（5) 顯影處理，及 (6)去除胺基甲酸酯樹脂層之不必要區域以形成光阻圖案 膜，步驟⑴或⑵包括熱處理之步驟。 發明詳細說明 非光化射線分解及顯影性基質爲，例如，可將正型光 化射線分解及顯影性樹脂層固定於基質上，及易於對如 印刷電路板等之塗層基質表面進行應用之基質。基質之 實例可包括聚對酞酸伸乙酯、芳族醯胺、c a p t ο n e、聚甲 基戊烯、聚乙烯、聚丙烯等之膜。其中，由成本及提供 具有良好特徵之光分解及顯影性乾膜之觀點，聚對酞酸 伸乙酯膜特佳。爲了易於釋放之目的，以上之基質亦可 包括經如聚矽氧、蠟、氟烴樹脂等之釋放劑處理者。基 質具有1至100微米，特別是10至40微米範圍之膜 厚。在應用後，可釋放基質及移除。 正型光化射線分解及顯影性樹脂組成物可依照輥塗 法、噴塗法、絲網印刷法等塗覆或印刷在以上之基質上， 以製備光分解及顯影性正型乾膜。爲了增強光分解及顯 影性樹脂組成物膜自基質釋放之特徵之目的，基質可事 先塗覆如聚矽氧、蠟等之釋放劑。正型光化射線分解及 顯影性樹脂層具有通常爲1至100微米，特別是5至 40微米範圍之膜厚。 塗覆或印刷在基質表面上之樹脂組成物較佳爲在熱層 合於基質之前，在約50至150°C，較佳爲在約80至120 1267701 五、發明說明（6) °C加熱，使得塗料層可交聯，造成改良光分解及顯影性 正型乾膜之機械性質，如折疊性質等。 用於本發明之正型光化射線分解及顯影性樹脂組成物 爲使得光化射線照射可分解樹脂組成物，以溶於顯影溶 液中。 用於本發明乾膜之正型光化射線分解及顯影性胺基甲 酸酯樹脂層之各成分可解釋於下。 不飽和化合物（A ^ : 化合物（AJ爲至少一種選自包括含乙烯醚基化合物、含 乙烯酯基化合物及含丙烯酯基化合物之不飽和化合物。 含乙烯醚基化合物f低分子量或高分子量化合物，其 在一個分子中具有約1至4，較佳爲2至4個式： -；^-0-(：[1 = (：[12表示之乙烯醚基，其中R’表示具有1至6 個碳原子之直鏈或支鏈伸烷基，例如，伸乙基、伸丙 基、伸丁基等，而且可包括，例如，鹵化烷基乙烯醚 (如氯乙基乙烯醚等）與多酚化合物（如聯酚A 、聯酚 F、聯酚S 、酚樹脂等）；或與多元醇（如乙二醇、丙 二醇三羥甲基丙烷、異戊四醇等）之縮合產物。 含乙烯酯基化合物爲低分子量或高分子量化合物，其 在一個分子中具有約1 (一）至4，較佳爲2至4個乙 烯酯基，而且可包括，例如，乙酸乙烯酯、丙酸乙烯 酯、乳酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、己酸乙 烯酯、異己酸乙烯酯、三甲基乙酸乙烯酯、癸酸乙烯 1267701 五、發明說明（7) 酯、Veova單體（由Shell化學公司販售）等。 含丙烯酯基化合物爲低分子量或高分子量化合物，其 在一個分子中具有約1 (一）至4，較佳爲2至4個丙 烯酯基，而且可包括，例如，乙酸異丙烯酯、丙酸異丙 烯酯等。 不飽和化合物（Ai)中，使用含乙烯醚基化合物較佳， 因爲異於發生樹脂（B!)與化合物（Ai)中乙烯醚基之間之加 成反應。 不飽和聚胺基甲酸酯化合物（ 不飽和化合物（A2)爲至少一種選自包括乙烯醚胺基甲酸 酯爲主化合物、乙烯酯胺基甲酸酯爲主化合物及丙烯酯 胺基甲酸酯爲主化合物之不飽和胺基甲酸酯爲主化合 物。 乙烯醚胺基甲酸酯爲主化合物爲在一個分子中具有約 1至4，較佳爲2至4個不飽和醚基，如式：R'-〇-(：1{ = (^2表示之乙烯醚基，其中Rf表示具有1至6個碳原 子之直鏈或支鏈伸烷基，例如，伸乙基、伸丙基、伸丁 基等、1-丙烯醚基、丁烯醚基等，及具有至少一個胺基 甲酸酯鍵聯之不飽和化合物，而且更可包括，例如，以 下之聚異氰酸酯化合物（視情況地，在一個分子中含至 少兩個羥基之以上含羥基化合物）與羥烷基乙烯醚（如 羥乙基乙烯醚等）之反應產物；多酚化合物，如聯酚 A、聯酚F、聯酚S、酚樹脂等，多元醇，如乙二醇、丙 1267701 五、發明說明（8) 二醇、三羥甲基丙烷、異戊四醇等，及以下之聚異氰酸 酯化合物，與鹵化烷基乙烯醚（如氯乙基乙烯醚等）之 縮合產物。其中，由抗蝕刻性質、所形成圖案之精確性 等觀點，多酚化合物與鹵化烷基乙烯醚之縮合產物及具 有芳環之聚異氰酸酯化合物與羥烷基乙烯醚之反應產物 較佳。 乙烯酯胺基甲酸酯爲主化合物爲低分子量或高分子量 化合物，其在一個分子中具有約1 (一）至4，較佳爲2 至4個乙烯酯基，及至少一個胺基甲酸酯鍵聯，而且可 包括，例如，以下之聚異氰酸酯化合物（視情況地，在 一個分子中含至少兩個羥基之含羥基化合物）與羥基乙 烯酯（如乳酸乙烯酯等）之反應產物。 丙烯酯胺基甲酸酯爲主化合物爲低分子量或高分子量 化合物，其在一個分子中具有約1 (一）至4，較佳爲2 至4個丙烯酯基，及至少一個胺基甲酸酯鍵聯，而且可 包括，例如，以下之聚異氰酸酯化合物（視情況地，在 一個分子中含至少兩個羥基之含羥基化合物）、及羥基 丙烯酯。 不飽和化合物（A2)中，使用乙烯醚胺基甲酸酯爲主化 合物較佳，因爲可易於發生樹脂（Β,)或（B2)中羧基與化合 物（A2)中乙烯醚基之間之加成反應。 以上之聚異氰酸酯之實例可包括脂族二異氰酸酯化合 物，如六亞甲基二異氰酸酯、三亞甲基二異氰酸酯、 -10- 1267701 五、發明說明（9) 1，4 -四亞甲基一異氰酸酯、五亞甲基二異氰酸酯、丨，2_ 伸丙基一異氰酸酯、1，2、伸丁基二異氰酸酯、三甲基六 亞甲基一異氰酸酯、二元酸二異氰酸酯、離胺酸二異氰 酸酯、2，3 -伸丁基—異氰酸酯、丨，3 -伸丁基二異氰酸酯 等；脂環开異氰酸醋化合物，如異佛爾_二異氰酸 酯、4,4’-亞甲基貳（環己基異氰酸酯）、甲基環己烷_ 2,4-(或-2,6-) 一異氰酸酯、ι，3_(或丨〆）二（異氰酸酯甲 基）環己烷、1，4-環己烷二異氰酸酯、丨，％環戊烷二異氰 酸醋、1，2-環己焼二異氰酸酯等；芳族二異氰酸酯化合 物，如本一甲基一異氰酸酯、甲烷苯二甲基二異氰酸 酯、四甲基苯二甲基二異氰酸酯、甲伸苯基二異氰酸 酯、4,4·-一苯基甲烷二異氰酸酯、^弘萘二異氯酸酯、 1，4-萘二異氰酸酯、4,4、甲苯胺二異氰酸酯、4,4，·二 苯酸一異氰酸酯、（間-或對伸苯基二苯二甲基二異氰 酸酯、4，4 ’ -聯苯二異氰酸酯、3，3、二甲基_ 4，4、聯苯 二異氰酸醋、戴（4-異氰酸基苯基）楓、異亞丙基貳（4_苯 基異氰酸酯）等；其他之聚異氰酸酯，例如，具有三或 四個異氰酸基之聚異氰酸酯化合物，如三苯基甲烷_ 4,4'，4"-三異氰酸酯、1，3,5-三異氰酸苯、2,4,6-三異 氰酸甲苯、4，4\二甲基二苯基甲烷- 2,2:5,5^四異氰 酸酯等，藉由在相對多元醇之羥基爲過量異氰酸基下， 反應多元醇，如乙二醇、丙二醇、1,4 -丁二醇、聚伸烷 二醇、三羥甲基丙烷、己三醇等，與聚異氰酸酯化合物 -11- 1267701 五、發明說明（1〇) 而製備之加成物，六亞甲基二異氰酸酯、異佛爾酮二異 氰酸酯、伸甲苯基二異氰酸酯、苯二甲基二異氰酸酯、 4,4^二苯基甲烷二異氰酸酯、4,4^亞甲基貳（環己基異 氰酸酯）等之二脲型加成物，異氰酸環型加成物等。 其中，較佳實例可包括異佛爾酮二異氰酸酯、苯二甲 基二異氰酸酯、伸甲苯基二異氰酸酯、1，6 -六亞甲基二 異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等。 視情況使用且在一個分子中具有至少兩個羥基之化合 物之實例可包括二醇，如乙二醇、丙二醇、具有6000或 更低分子量之聚乙二醇、具有6000或更低分子量之聚丙 二醇、四亞甲二醇、1，4-丁二醇、1，3.-丁二醇、2,3-丁 二醇、1，2-丁二醇、3-甲基-1,2-丁二醇、1,2-戊二醇、 1，5 -戊二醇、1,4 -戊二醇、2,4 -戊二醇、2,3 -二甲基三 亞甲二醇、四亞甲二醇、3-甲基-3,4-戊二醇、3-曱基- 4.5- 戊二醇、2,2,4-三甲基-1，3-戊二醇、1,6-己二醇、 1.5- 己二醇、1,4-己二醇、2,5-己二醇、1，4-環己烷二 甲醇、新戊二醇、新戊二醇羥基三甲基乙酸酯、1，4-環 己烷二甲醇、三環癸烷二甲醇、聚己內酯、氫化聯酚A、 氫化聯酚F 、氫化聯酚A與氫化聯酚F之伸烷基氧化 物加成物等；聚酯二醇，如貳（羥乙基）對酞酸酯等，三 羥基或更高醇，如甘油、三羥甲基丙烷、三羥甲基乙 烷、二甘油、三甘油、1，2,6 -己三醇、異戊四醇、二異 -12- 1267701 五、發明說明（1 1 ) 戊四醇、花楸醇、甘露醇等，藉由內酯（如ε -己內酯）與 以上之二醇及/或三經基或更高醇之加成反應製備之聚 內酯多元醇等。其可單獨或組合使用。 其中，聚乙二醇、聚己內酯、聚丙二醇、四亞甲二 醇、三羥甲基丙烷等較佳。 化合物（AJ與（Α2)較佳爲包括在室溫爲液態者，或具有 150°C或更低，特別是130°C或更低之熔點或軟化點者， 因爲易於發生樹脂（BJ或（B2)中羧基或酚基與（AJ或（A2) 中乙烯醚基之加成反應。 含酸基胺基甲酸酯樹脂（BJ : 含酸基胺基甲酸酯樹脂（Bd爲藉由依照已知方法反應聚 異氰酸酯化合物、在一個分子中具有至少一個羥基與至 少一個酸基之羥基酸化合物、及視情況地在一個分子中 具有至少一個羥基之化合物，而且本質上不含自由異氰 酸基而製備之胺基甲酸酯樹脂。 以上之聚異氰酸酯化合物可包括與用於不飽和化合物 (A2)相同者。 以上羥基酸化合物之實例可包括二羥甲基丙酸、二羥 甲基丁酸、二羥甲基戊酸、酒石酸、1，2 -羥基硬脂酸、 對羥基苯甲酸、水楊酸、羥丁二酸、乳酸、羥乙酸、 2, 2 -二甲基-3-羥基丙酸等。 視情況地，可單獨或組合使用在一個分子中含一個羥 基之化合物，例如，甲醇、乙醇、丙醇、丁醇、己醇、 -13- 1267701 五、發明說明（12) 環己醇、苄醇等。 含酸基胺基甲酸酯樹脂（BJ具有約1，000至約200,000, 較佳爲約5,000至約1 50,000，更佳爲約20,000至約 1 00,000範圍之重量平均分子量，並且具有每公斤樹脂 爲約0 · 5至約1 0當量，較佳爲約〇 . 5至約8當量， 更佳爲約0 · 5至約5當量範圍之酸基含量。小於約 〇 · 5 /公斤之酸基含量造成在光化射線照射前加熱形成之 塗膜顯示不令人滿意之交聯程度，及光化射線照射區域 在鹼性顯影溶液中之低溶解度降低顯影性質。另一方面， 在超過約10當量時，組成物顯示不良之儲存安定力。 本發明之樹脂（B2)可包括（a)含羧基與羥苯基聚合物， (b )含羧基聚合物，（c )含羥苯基聚合物及其混合物。 含羧基與羥苯某聚合物（a 聚合物（a)爲在一個分子中具有至少一個羧基及至少 一個羥苯基之膜形成聚合物，而且可包括如對-羥基苯乙 烯等之羥基苯乙烯與含羧基可聚合不飽和單體之共聚物； 羥基苯乙烯、含羧基單體與其他可共聚合單體之共聚物 等。 含羧基可聚合不飽和單體之實例可包括丙烯酸、甲基 丙烯酸、巴豆酸、伊康酸等。其他可共聚合單體之實例 可包括（甲基）丙烯酸之（^.12烷酯，例如，（甲基）丙烯酸 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基） 丙烯酸丁酯、（甲基）丙烯酸己酯、（甲基）丙烯酸辛酯、 -14- 1267701 五、發明說明（13 ) (甲基）丙烯酸2 -乙基己酯、（甲基）丙烯酸壬酯、（甲基） 丙烯酸癸酯等；（甲基）丙烯酸之C2.6羥基烷酯，例如， (甲基）丙烯酸羥乙酯、（甲基）丙烯酸2 -羥基丙酯、（甲基） 丙烯酸3-羥基丙酯、（甲基）丙烯酸羥丁酯等，乙烯基芳 族化合物，如苯乙烯、α -甲基苯乙烯、對·第三丁基苯 乙烯等；乙酸乙烯酯、（甲基）丙烯腈、（甲基）丙烯醯 胺、乙烯基吡咯啶酮等。這些單體可單獨或組合使用。 聚合物U)亦可包括藉由酚羧酸（其具有酚、（^_18單-或二烷基酚或萘酚及選自間苯二酚、兒茶酚等之酚至少 之一），如羥基苯甲酸、五倍子酸、間苯二酸等，或其 混合物，與甲醛之縮合反應製備之聚合物。 聚合物（a)通常具有約1〇〇〇至約200,000，特別是約 20,000至約1 00,000範圍之重量平均分子量，通常每公 斤聚合物爲約0.5至約1 0當量，特別是約0.5至約 5 . 0當量範圍之羧基含量，及至少約1 . 0當量，特別是 約2.0至約8.0當量範圍之羥基苯基含量。 小於約0.5當量/公斤之羧基含量造成在光化射線照 射前加熱形成之塗膜顯示不令人滿意之交聯程度，及光 化射線照射區域在鹼性顯影溶液中之低溶解度降低顯影 性質。另一方面，在超過約1 0當量/公斤時，組成物顯 示不良之儲存安定力。另一方面，小於約1 · 〇當量/公 斤之羥基苯基含量在交聯時生成不令人滿意之交聯程 度。 -15- 1267701 五、發明說明（14) 聚合物較佳爲具有約〇°C或更高，特別是約5至約70 °C範圍之玻璃轉移溫度（Tg)。在Tg低於時，黏狀塗 膜生成外來顆粒、塵等之黏附，而難處理。 含羧基聚合物（b 1 : 聚合物（b)爲在一個分子中含至少一個羧基之膜形成 聚合物，而且可包括，例如，含羧基可聚合不飽和單體 之同元聚合物、含羧基單體與其他可共聚合單體之共聚 物；在一個分子中或在分子終端具有羧基，而且以聚 酯、聚胺基甲酸酯、聚醯胺等爲主之樹脂。 含竣基可聚合不飽和單體之實例可包括丙烯酸、甲基 丙烯酸、巴豆酸、伊康酸等。其他可與以上含羧基單體 共聚合之單體之實例可包括（甲基）丙烯酸之C2_6羥基烷 酯，例如，（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲 基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸己 酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸2 -乙基己酯、（甲 基）丙烯酸壬酯、（甲基）丙烯酸癸酯等；這些單體可單獨 或組合使用。由所形成影像圖案之精確性、抗蝕刻質等 之觀點，特佳之其他單體可包括乙烯基芳族化合物，如 苯乙烯、α-甲基苯乙烯，C2_6烷基取代苯乙烯，如對-第 三丁基苯乙烯等。 含羧基聚合物（b)具有通常爲約1，000至約200,000, 特別是約20,000至約100,000範圍之重量平均分子量， 並且具有通常每公斤聚合物爲約0.5至約10當量，特 -16- 1267701 五、發明說明（15) 別是約0 · 5至約5 · 0當量範圍之羧基含量。小於約1 . 〇 當量/公斤之羧基含量造成在可見光照射前加熱形成之 塗膜顯示不令人滿意之交聯程度，及照射區域在鹼性顯 影溶液中之低溶解度降低顯影性質。另一方面，在超過 約1 0當量時，組成物顯示不良之儲存安定力。 聚合物（b )較佳爲具有約〇 °C或更筒，特別是約5至 約7 0°C範圍之玻璃轉移溫度（Tg)。在Tg低於0°C時，黏 狀塗膜生成外來顆粒、塵等之黏附，而難處理。 聚合物（b )可組合以下之含羥苯基聚合物（c )使用。 含羥苯某聚合物（c ): 聚合物（c)爲在一個分子中含至少一個羥苯基之聚合 物，而且可包括，例如，單官能基或多官能基酚化合 物、烷基酚化合物或其混合物與如甲醛、丙酮等之羰基 化合物之縮合產物，如對-羥基苯乙烯之含經基乙烯基芳 族化合物之同元聚合物；含羥基乙烯基芳族化合物與可 共聚合單體之共聚物等。 單官能基或多官能基酚化合物之實例可包括在苯環上 具有1至3個羥基之化合物，例如，酚、鄰-甲苯酚、 間-甲苯酚、對-甲苯酚、3,5 -二甲苯酚、2,6 -二甲苯 酚、2,4-二甲苯酚、兒茶酚、間苯二酚、五倍子酚、聯 酚A等。烷基酚化合物之實例可包括L . 1()烷基酚，較佳 爲烷基酚，例如，對-異丙基酚、對-第三丁基酚、 對-第三戊基酚、對-第三辛基酚等。 -17- 1267701 五、發明說明（16) 可藉已知方法進行以上化合物與如甲醛、丙酮等之羰 基化合物之縮合反應，使得在鹼性觸媒之存在下之縮合 隨縮合反應進行而生成不溶性且不熔性酚醛樹脂型，及 在酸觸媒之存在下之縮合生成溶解性且熔化性酚醛淸漆 型。酚醛淸漆型樹脂爲其分子量隨縮合反應進行而增加 者，而且較佳爲包括藉由進行縮合反應1至3小時而 製備且具有500至2,000範圍之重量平均分子量者。 可與含羥基乙烯基芳族化合物共聚合之其他單體可包 括如以上聚合物（b )中共聚物之情形所例示之相同之其 他可共聚合單體。含羥苯基聚合物（c)較佳爲具有通常 爲約1，000至約200,000，特別是約1，〇〇〇至約30,000 範圍之重量平均分子量。 聚合物（c)較佳爲具有通常每公斤聚合物爲約1.〇至 約1 〇當量，特別是約2 · 0至約8.0當量範圍之羥苯基 含量。小於約1 . 〇當量/公斤之羥苯基含量造成在可見 光照射前加熱形成之塗膜顯示不令人滿意之交聯程度。 另一方面，在超過約10當量/公斤時，光阻膜爲脆的。 如聚合物（a )與（b )，聚合物（c )較佳爲具有約〇°C 或更高，特別是約5至約70°C範圍之玻璃轉移溫度 (Tg) °在Tg低於〇。(：時，黏狀塗膜生成外來顆粒、塵等 之黏附，而難處理。 化合物（Μ )對含酸基胺基甲酸酯樹脂（B1 )，即，化合 •物樹脂（ΒΟ;化合物（Α2)對樹脂（β2)，即，化合物 -18- 1267701 五、發明說明（π) (Al) /樹脂（B2);或化合物（A2)對樹脂（Bi)，即化合物 U2)/樹脂（BJ之混合比例，基於化合物（Al)與樹脂 (B[)、化合物（A2)與樹脂（B2)、或化合物（A2)與樹脂（BJ 之總霆量，各爲0.5至50/ 99.5至50重量％，較佳爲 1至30/99至70重量％，更佳爲1至15/99重量％ 之範圍。小於〇·5重量％之化合物（Αι)或（A2)，或超過 99·5重量％之樹脂（Bd或（B2)之量，不欲地降低未照射 區域之顯影溶液抗性。另一方面，超過5 0重量％之化合 物（^)或（a2)，或小於50重量％之樹脂（BJ或（B2)之量， 不欲地降低敏感性及儲存安定力。 光-酸產牛劑f 產生劑（C )爲在光化射線照射時產生酸，使得樹脂在 產生之酸作爲觸媒之存在下分解之化合物，而且可包括 此技藝已知者。 作爲光-酸產生劑（C)之化合物及其混合物之實例可包 括重氮鹽、鳞、毓與碘鐵鹽；鹵化物；有機金屬與有機 鹵之組合；如甲苯磺酸等之強酸之安息香與鄰-硝基苄酯； 如美國專利43 7 1 605所揭示之N-羥基醯胺基與N-羥基 醯亞胺基磺酸酯等，亦可包括芳基萘醌重氮-4-磺酸酯。 較佳之光安定劑可包括二芳基碘鏺與三芳基錳。通常， 這些化合物以多合金金屬鹵化物離子之形式存在，如四 氟硼酸根、六氟銻酸根、六氟砷酸根、六氟亞磷酸根 等。 -19- 1267701 五、發明說明（彳8) 其他顯示光分解及顯影性性之有效酸產生劑包括加入 具有芳族鏺酸產生劑作爲正成對離子之陰離子基之低聚 物與聚合物。以上之聚合物亦包括在美國專利4，6 6 1 , 4 2 9 之第9欄，第卜68行，及第10欄，第1-14行揭示之 聚合物（如以下所述）。 爲了控制對可應用光化射線波長之光譜敏感性之目的， 較佳爲將增感劑加入以上之系統。以上加成之必要性可 視系統之需求及所使用之特定光分解及顯影性化合物而 定。 例如，在對應小於300nm之波長之碘鏺與毓鹽之情形， 使用二苯基酮及其衍生物，如二苯并蒽、辰與蒽之多環 芳族烴，其衍生物等，可在較長波長光固化。二芳基碘 鏺與三芳基毓鹽之分解亦可藉由使用貳（對- N，N-二甲胺 基亞戊基）-丙酮而光固化。鍵結在具有包括34個原子之 鏈長之蒽之毓鹽爲有效之光溶解劑。在MG. Til ley之博 士論文，北達可達州Fargo之北達可達州立大學（1988) [Diss, Abstr. Int. B, 49, 8791(1989): Chem. Abstr. 111，39942u]揭示之化合物爲較佳之光溶解劑。其他較 佳之酸產生劑可包括ATASS，即，二苯基毓六氟銻酸3-(9-蒽基）丙酯，其使得曹及毓鹽經包括3個碳原子之鏈 鍵結。在此使用之酸產生劑之額外實例可包括二苯基碘 鏺甲苯磺酸鹽、安息香甲苯磺酸鹽與三芳基毓六氟銻酸 鹽° -20- 1267701 五、發明說明（1 9 ) 酸產生劑之額外實例可包括鐵-丙二烯錯合物、釕-丙 二烯錯合物、矽烷-金屬鉗合劑錯合物、三畊化合物、二 疊氮基萘醒化合物、擴酸鹽、醯亞胺磺酸鹽、鹵化化合 物等，而且亦可包括日本專利申請案公開1 46552/95及 >曰本專利申請案2892 1 8 / 97所述之酸產生劑。 酸產生劑之混合量可爲每100重量份之化合物（八^與 樹脂（BO、化合物（A2)與樹脂（B2)、或化合物（A2)與樹脂 (BJ之總量爲約0.1至40重量份，特別是約0.2至20 重量之範圍。 用於本發明乾膜之正型光化射線分解及顯影性樹脂組 成物可包括藉由各將以上成分分散或溶解，或在使用顏 料作爲著色劑之情形將顏料顆粒均勻地分散於有機溶劑 中而製備之有機溶劑爲主樹脂組成物。 用以溶解或分散以上成分之有機溶劑之實例可包括酮， 如丙酮、甲乙酮、甲基異丁基酮等；酯，如乙酸乙酯、 乙酸丁酯、苯甲酸甲酯、丙酸甲酯等；醚，如四氫呋 喃、二噚烷、二甲氧基乙烷等；賽珞蘇，如甲基賽珞 蘇、乙基賽珞蘇二乙二醇單甲醚等；芳族烴，如苯、甲 苯、二甲苯、乙基苯等；鹵化烴，如氯仿、三氯乙烯、 二氯甲烷等；醇，如乙醇 '苄醇等；其他如二甲基甲醯 胺、二甲基亞楓等。 以上之樹脂組成物亦可包括藉由以鹼性化合物中和樹 脂組成物中之羧基，繼而將中和產物溶解或分散於水中 -21 - 1267701 五、發明說明（20) 而製備之水系樹脂組成物。 用於本發明乾膜之樹脂組成物在乾燥時在室溫爲固體 之形式。 在由用於本發明乾膜之樹脂組成物形成之塗膜暴露於 光化射線而產生之酸存在下，在暴露區域發生酸水解反 應。爲了順利進行酸水解反應之目的，水之存在爲希望 的，而如聚乙二醇、聚丙二醇、甲基纖維素、乙基纖維 素等之親水性樹脂對樹脂組成物之加成可易於對以上之 反應將所需之水引入生成之塗膜中。親水性樹脂之爲通 常每100重量份之樹脂成分爲20重量份或更少，較佳 爲0 . 1至1 0重量份之範圍。 除了以上之成分，用於本發明之樹脂組成物可視情況 地含在水中或有機溶劑中爲不溶性、溶解性或分散性， 而且可改良或損及在有機溶劑中或水性顯影溶液中之溶 解度之其他樹脂。其他樹脂之實例可包括酚系樹脂、聚 酯樹脂、丙烯樹脂、乙烯樹脂、乙酸乙烯酯樹脂、環氧 樹脂、聚砂氧樹脂、氟煙樹脂、其混合物、其修改產物 等。 爲了賦與生成乾膜適當之撓性、非膠黏性、膠黏性等， 用於本發明之樹脂組成物可含如酞酸酯等之塑性劑、聚 酯樹脂、丙烯樹脂等。 用於本發明之樹脂組成物可視情況地含流動力調節 劑、塑性劑、染料、如顏料等之著色劑等。 -22- 1267701 五、發明說明（21) 本發明之方法可應用於任何用途而無特別之限制，只 要包括以上之步驟。 用於本發明之塗層基質可包括用於以下用途之導體、 絕緣體、半導體、其組合之基質。 以上在各種工業領域之用途之實例可包括電領域，如 電零件、照明、電元件、半導體、印刷品、印刷電路、 電子通訊、電力等；物理領域，如儀器、光領域、指示 器、音領域、控制器、販賣領域、信號、資訊記錄領域 等；化學·冶金學•纖維領域，如無機化學、有機化 學、聚合物化學、冶金學、纖維等；處理•運輸領域， 如分離•混合、金屬處理、塑膠處理、印刷品、容器、 包裝等；生活物件，例如，農業與海洋領域、食品發 酵、家居物件、健康•娛樂領域等;機械工程等。 本發明之方法爲形成圖案之方法，其包括以下步驟： ⑴將上述之正型光化射線分解及顯影性乾膜應用於塗層 基質表面上，使得塗層基質表面面對乾膜之胺基甲酸酯 樹脂層， ⑵視情況地剝除乾膜之非光化射線分解及顯影性基質， ⑶經光罩或直接將光化射線照射在乾膜表面上以得到意 圖圖案，視情況地熱處理， ⑷剝除在以上步驟⑵中未剝除之非光化射線分解及顯影 性基質， ⑸使正型光化射線分解及顯影性胺基甲酸酯樹脂層接受 -23- 1267701 五、發明說明（22) 顯影處理，及 ⑥去除胺基甲酸酯樹脂層之不必要區域以形成光阻圖案 膜，步驟⑴或⑵包括熱處理之步驟。 乾膜可應用於塗層基質表面上，使得正型光化射線分 解及顯影性樹脂塗膜面對如具有非穿孔及/或穿孔之導 電性電路板之塗層基質表面，而且可層合於上，繼而熱 層合同時在乾膜之基質表面上加壓以將導電性基質黏結 在樹脂塗膜層表面。熱層一步驟可藉由將導電性基質加 熱，由乾膜之基質表面加熱，或兩者而進行。加熱溫度 爲通常60至150°C，特別是80至12(TC之範圍。 在將乾膜應用於塗層基質表面時，基質表面以液體處 理，例如，如Jone之美國專利3,645,772所述之黏著 性促進溶液，如Fi ekes所述用於光阻膜之溶劑，或膨脹 劑，可改良塗層基質表面與乾膜間之黏附性質。以上之 液體可具有光分解及顯影性性質，如jsaacsorl之美國專 利3,629,036所述之光阻溶液。使用真空層合裝置進行 乾膜對塗層基質之應用。 以上之熱處理可在實質上發生化合物（AO與含酸基胺 基甲酸酯樹脂（Bi)、化合物（A2)與樹脂（B2)、或化合物 (A2)與樹脂（)間之交聯反應之溫度條件進行，例如， 藉由在約60°C至約150°C加熱約1分鐘至約30分鐘。 光化射線照射可藉由，例如，經光罩照射光化射線之 方法、以雷射掃描直接繪製之方法等進行。 -24- 1267701 五、發明說明（23) 光化射線之實例可包括紫外光、可見光、雷射束（如 近紅外線、可見光雷射、紫外光雷射等）。照射劑量爲 通常0.5至2000毫焦耳/平方公分，較佳爲1至1〇00 毫;焦耳/平方公分之範圍。 光化射線之照射來源可包括此技藝已知者，例如，得 自超過壓录燈、局壓永燈、中壓录燈、低壓录燈、化學 燈、碳弧燈、氙燈、金屬鹵化物燈、螢光燈、鎢燈、日 光等之光源；以紫外光阻斷濾光器阻斷之可見光範圍， 各種具有可見光範圍之振盪期之雷射。高功率及安定之 雷射束來源可較佳地包括氬雷射及YAG-SHG雷射。 在乾膜應用於塗層基質表面之後，可視情況地自正型 光化射線分解及顯影性樹脂塗膜層剝除乾膜之基質。剝 除步驟可視情況地在以下光化射線照射步驟之後進行。 光化射線之照射後較佳爲熱處理，以在照射照產生之 酸之存在下將固化塗膜之交聯結構破碎之溫度條件下加 熱，例如，約60°C至約150°C約1分鐘至30分鐘。 顯影處理可藉由以鹼性水溶液、有機溶劑、水等洗出 暴露區域中之光阻膜而進行。鹼性水溶液可包括如苛性 鈉、碳酸鈉、苛性鉀、氨等之鹼之水溶液。溶解暴露區 域之有機溶劑可包括，例如，1，1，1 -三氯乙烷、三氯乙 烯、甲乙酮、二氯甲烷等。在顯影處理之後，以水淸洗 樹脂膜，繼而以熱風等乾燥以在導體上形成意圖之影 像。視情況地，可進行蝕刻以去除暴露區域中之導體及 -25- 1267701 五、發明說明（24) 製備印刷電路板。例如印刷電路板中導電膜爲銅之情形， 暴露區域中之導電膜可藉蝕刻去除，即，使用如氯化銅 溶液等之酸蝕刻溶液，及如氨水等之鹼蝕刻溶液。依照 本發明，穿孔內部之銅不發生溶解而不造成破裂。 蝕刻步驟之後，可視情況地去除殘留光阻膜。殘留光 阻膜之去除可使用剝除劑進行，例如，使用鹼或酸之水 溶液，及各種有機溶劑，其溶解光阻膜但是本質上不損 及基質及在基質表面上構成電路圖案之導電膜。 在使用具有導電電路圖案及穿孔及/或非穿孔之基質 作爲具有穿孔之導電性基質之情形，光阻膜在穿孔、非 穿孔及經細電路圖案上令人滿意之覆蓋可易於形成熔焊 光阻及對電絕緣性質、化學抗性等具高可靠度之中間絕 緣層。 依照本發明，使用由含胺基甲酸酯鍵聯光化射線分解 及顯影性樹脂組成物形成之正型乾膜提供在乾膜彎曲時 光化射線分解及顯影性塗膜不發生裂開或剝離而易於處 理，及顯影與蝕刻處理可形成精細圖案之效果。 實例 本發明由以下之實例及比較例詳細解釋，其中”份”及 〃 ％ "各表示"重量份〃及"重量vf。 製備例1 含乙烯醚基例化合物（Ay Π之製備 250毫升燒瓶裝有45.6克之聯酚A、80毫升之2-氯乙 -26- 1267701 五、發明說明（25) 基乙烯醚及100毫升之甲苯，繼而引入氮，裝以20克 之氫氧化鈉，在80°C加熱30分鐘，裝以藉由將4.56克 之四丁銨溴鹽溶於20毫升之2-氯化乙基乙烯醚中而製備 之溶液，在95°C加熱及反應5小時，以去離子水淸洗 反應產物三次，分離油層，及蒸發且去除2 -氯乙基乙燃 醚與甲苯，而得到具有368之重量平均分子量且在一個 分子中含2個乙儲醚基之乙烯醚化合物（Ai-1)。 製備例2 乙烯醚胺基甲酸酯爲主化合物f A2 - 1 )之製備 210份三甲基六亞甲基二異氰酸酯、232份之羥丁基 乙烯醚與5滴之吡咯之混合物在90°C反應6小時而得 到二乙烯醚化合物（A2-l)。 製備例3 乙烯醚胺基甲酸酯爲主化合物（Α γ 2 )之製備 在1份之二乙酸二丁錫之存在下，875份藉由反應1 莫耳之三羥甲基丙烷與3莫耳之伸二甲苯基二異氰酸酯 而製備之聚異氰酸酯之75%乙二醇二甲醚溶液、及264 份之2-羥乙基乙烯醚之混合物在35°C反應3小時，而 得到在一個分子中含3個乙烯醚基且具有約81%之固體 含量之乙烯醚化合物（A2-2)。 製備例4 含酸基胺基甲酸酯樹脂（B1 -1)夕製備 275份之甲乙酮、23 3份之三甲基六亞甲基二異氰酸 -27- 1267701 五、發明說明（26) 酯、1 08份之三丙二醇與73份之二羥甲基丁酸之混合物 在80°C反應10小時而得到反應產物，繼而在75°C以上 之反應產物反應24份之羥基乙酸1 1小時，而得到具有 約47,000之重量平均分子量及1.4莫耳/公斤之羧基 含量（即，79毫克KOH/克之酸値）之樹脂（B「l)。 製備例5 含酸基胺基甲酸酯樹脂（B1-2)之製備 596份之甲乙酮、576份之異氟爾酮二異氰酸酯、81 份之三丙二醇與70份之二羥甲基丁酸之混合物在80°C反 應10小時，而得到具有約40,000之重量平均分子量及 1.6莫耳/公斤之羧基含量（即，88毫克KOH/克之酸 値）之樹脂（B「2)。 製備例6 含羧基樹脂（Βγ 1 )之製備 將216份之丙烯酸、500份之苯乙烯、284份之甲基 丙烯酸正丁酯、與50份之偶氮貳異丁腈之混合物滴入 600份在80°C加熱之甲基異丁基酮中且攪拌2小時， 繼而在此溫度保持2小時，而得到具有約62.5%之固 體含量及3莫耳/公斤之羧基含量之聚合物（b2-1)。 製備例7 含殘基樹脂（Βγ 3 )之製備 將288份之丙烯酸、300份之苯乙烯、255份之丙烯 酸正丁酯、157份之丙烯酸2-羥乙酯與100份之第三丁 -28- 1267701 五、發明說明（27) 基過氧基苯甲酸酯之混合物滴入1 000份在ll〇°C加熱之 2 - 丁氧基乙醇中且攪拌2小時，繼而在此溫度保持2 小時，而得到具有約5 0 %之固體含量及4莫耳/公斤 之殘基含量之聚合物（B2 - 2 )。 製備例8 含羧基與羥苯基樹脂（B2-3)之製備 200份之四氫呋喃、65份之對-羥基苯乙烯、28份之 丙烯酸正丁酯、11份之丙烯酸與3份之偶氮貳異丁腈之 混合物在1 00°C反應2小時，而得到反應產物，繼而將 反應產物注射至1 500毫升之甲苯溶劑中，沈澱且分離反 應產物，及在60°C乾燥沈澱物，而得到具有約5200之 重量平均分子量及4.6莫耳/公斤之羥苯基含量之光分 解及顯影性樹脂（B2-3)。 製備例9 盒羥苯基樹脂（B2-4)夕製備 燒瓶裝有1 490份之鄰-甲苯酚、1145份之30%福馬 林、1 30份之去離子水與6 . 5份之草酸，繼而在回流下 加熱60分鐘，加入1 3 . 5份之1 5%氯酸，在回流下加熱 40分鐘，加入400份約15°C之去離子水，生成混合物 保持在約75°C以沈澱樹脂，加入35%氫氧化鈉水溶液， 中和，去除去水，加入400份之去離子水，在75°C淸 洗樹脂，去除去水，重複相同之淸洗步驟2次，及在真 空下在約120°C乾燥，而得到具有600之重量平均分子 -29- 1267701 五、發明說明（28) 量之酚醛淸漆酚樹脂（B2-4)。 實例1 〜 90份之含酸基胺基甲酸酯（B1-1)、10份之含乙烯醚基 化合物（A1-1)、5份之光-酸產生劑ΝΑΙ·105(商標名稱， Midori Kagamku有限公司上市）與2份之1，2,3-苯并三 唑之混合物溶於環己酮，而得到具有28%之固體含量之 光分解及顯影性溶液。 以棒塗器將光分解及顯影性溶液塗覆於聚對酞酸伸乙 酯膜上成爲10微米之乾燥膜厚，繼而在120°C加熱10 分鐘而得到乾膜。乾膜之性能示於表1 。使用乾膜層合 器將乾膜層合於兩側鍍有覆銅層合物之穿孔上，繼而剝 除聚對酞酸伸乙酯膜而得到具光阻膜之塗層基質。使用 汞燈經正型光罩將具有50毫焦耳/平方公分強度之紫外 光照射在基質上，繼而在120°C加熱1〇分鐘，並且以 0 · 75%碳酸鈉水溶液顯影。結果示於表1 。然而，以40 °C之氯化銅水溶液進行蝕刻，繼而以3%苛性鈉水溶液去 除殘留之光阻膜而得到印刷電路板。結果示於表1 。 實例2 - 4 及比較例1 - 2 各依照表1所示之配方製備光分解及顯影性溶液，繼 而以如實例1之相同方式製備乾膜，及使各乾膜接受如 實例1之相同試驗。結果示於表1 。 -30- 1267701 五、發明說明（29) 表1 實 例 比較例 1 2 3 4 1 2 10 10 30 10 10 30 配方 B1 - 1 90 70 •(份） B^2 90 70 B2-l 90 70 光-酸產生劑 5 5 5 5 5 5 1，2,3-苯并二唑 2 2 2 2 2 2 乾膜性能 應用作業力 2 2 2 2 2 2 帳篷形成性質 2 2 2 2 1 1 顯影性質 2 2 2 2 2 2 抗蝕刻性質 2 2 2 2 1 1 -31 - 1267701 五、發明說明（3〇) 實例5 重複實例1 ，除了使用含酸基樹脂（B2-1)及乙烯醚胺 基甲酸酯爲主化合物（A2 - 1 )。結果示於表2 。 實例6 - 1 4及比較例3 - 各依照表2所示之配方製備光分解及顯影性溶液，繼 而以如實例5之相同方式製備乾膜，及使各乾膜接受如 實例5之相同試驗。結果示於表2 。 -32- 1267701 五、發明說明（31) 抗蝕刻性質 顯影性質 乾膜性能 ' 齙方 (份） 帳篷形成I 性質 應用Ί乍業力i 1,2,3- j 苯并二唑 1 光-酸產生劑 > 1 ω ω ω ω Μ·. Μ· A CO.tO Ρ > > to to t?0 二 to to to tsD to Of g I—1 o Ol i 實例 to to to to to CJI o 1—A • o CJi to tsD to to to OX g h-1 o to to to to to Ol g 1-^ o 00 to to to to to αχ g s CD to to K) to to Ol g s s to to to to Ol g Η-1 to to to to to cn g g to to to to to to Oi g to to to to to cn — to h-1 to to cn s CO cr l·-» tSD f—* to to CTf s A i-* to — to to cn o cn μα to h-* to to cn s ① h-* to to to αχ <ϊ -33- 1267701 五、發明說明（32) 實例15 重複實例1 ，除了使用含酸基胺基甲酸酯樹脂（B, - 1 ) 及乙烯醚胺基甲酸酯爲主化合物（A2 - 1 )。結果示於表3。 實例1 5 - 2 2及比較例8 - 9各依照表3所示之配備光分解及顯影性溶液，繼而以 如實例1 5之相同方式製備乾膜，及使各乾膜接受如實例 1 5之相同試驗。結果示於表3 。 -34 1267701 五、發明說明（33)1267701 V. OBJECTS OF THE INVENTION (1) Field of the Invention The present invention relates to a positive-type actinic ray-decomposing and developing dry film which is characterized by photochemical ray decomposition and developability of a resin having a urethane-bonded bond. The resin composition is formed, which exhibits high sensitivity and good film processing properties, and can be formed into a pattern which can be used in an electronic device to form a circuit for printing. (2) Background Art Description A light is known in the art. A method of decomposing and developing a photoresist film comprising coating or printing a liquid photodecomposition and developable photoresist composition in a perforation and/or according to a coating or printing method such as spray coating, roll coating, screen printing or the like. Or a non-perforated (hereinafter may be referred to simply as a perforated) printed circuit board. However, the above method has a method of directly coating or printing a liquid resin composition on a printed circuit board, and a satisfactory photoresist film cannot be formed inside the perforation. The problem is that the conductive film such as copper, silver or the like which is formed inside the perforation is partially or completely dissolved in the etching solution during the etching step, causing generation of cracks. In recent years, in order to protect the perforation from the etching solution, a positive film photoresist which is formed by applying a positive photodecomposition and a developable liquid photoresist composition to a substrate has been used. Examples of the decomposition and developability liquid photoresist composition, including a carboxyl group-containing polymer, a polyvinyl ether compound, and a visible light decomposition and developability composition of a compound which produces an acid due to decomposition by actinic radiation, are disclosed, for example, in Japanese Patent Application. Case 1267701 5, invention description (2) open 313134/94, 313135/94, 313136/94, 308733/94, 295064/64, 146552/95, etc. The above composition is to heat the coating film formed by the composition, Crosslinking due to the addition reaction between the carboxyl group and the vinyl ether group, insoluble in the solvent and the alkaline aqueous solution, and irradiation with actinic rays and heating thereon, and then crosslinking due to the catalytic action of the produced acid The structure is broken, so that the irradiated region is again dissolved in the photodegradation and developability composition of the solvent and the aqueous alkali solution. However, by including the above positive photodecomposition and developability group The positive dry film formed by the method of coating on a substrate such as polyethylene terephthalate and then drying causes problems: (1) because of the unsatisfactory mechanical properties of positive photodegradation and developability coating, (W) a method of forming a positive photodecomposition and a developable coating film by using a dry film on a surface of a printed circuit board when winding a dry film formed as described above and forming a dry film (this method includes a positive type) The photodecomposition and developing coating film is folded toward the printed circuit board, and the dry film is heated to laminate and separate the poly(p-benzoic acid ethyl ester matrix and the positive photodegradable and developable coating film) because of positive photodecomposition and development. The poor adhesion property between the coating film and the substrate, after the above separation step, the positive photodegradation and development coating film partially or completely remains on the surface of the poly(p-ethyl phthalate) substrate, and (3) because The undesired mechanical properties of the photodegradable and developable coating film cause the coating film to be etched away by the etching solution, resulting in the inability to form a fine photoresist pattern. As an example of a positive type photodecomposition and a developable dry film, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 506 1 06/93 discloses a form comprising a flexible thin polymer film substrate comprising Dry film photoresist prepared by solid photodegradation and developability of a photo-acid restless base and a photo-acid generator polymer. That is, the above dry film decomposes by the action or irradiation of an acid generated by the photo-acid labile gene photo-acid generator in the polymer, so that only the irradiation region is dissolved in the developing solution to provide a positive image, but it has The disadvantage that the non-illuminated coating film area or the irradiation coating film area is insoluble or dissolved with unclear consistency and cannot form a fine image. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive-type actinic ray-decomposing and developable dry film which exhibits good mechanical properties for easy handling and can form a fine photoresist pattern. Another object of the present invention is to provide a method of forming a pattern which can form a fine photoresist pattern using the above dry film. That is, the present invention firstly provides a positive-type actinic ray-decomposing and developing dry film having solid positive-type actinic ray decomposition and developable urethane resin on the surface of the non-actinic ray-decomposing and developing substrate. a layer formed of the following: (1) a resin composition containing the following as an important component: (AJ at least one selected from the group consisting of a vinyl ether group-containing compound, a vinyl ester group-containing compound, and an acrylate-containing compound-containing unsaturated compound, (Bi ) having a weight average molecular weight of 1,000 to 200,000 and a resin per kg of the resin. An acid group-containing urethane resin having an acid group content of 5 to 10 equivalents, and (C) a photo-acid generator; (2) a resin composition containing the following as an important component: 1267701 V. Description of invention (4) ( VIII) at least one selected from the group consisting of a vinyl ether urethane-based compound, a vinyl ester urethane-based compound, and an acryl ester urethane-based compound as an unsaturated urethane-based compound. The compound, (b2) at least one selected from the group consisting of: (a) a carboxyl group-containing and hydroxyphenyl polymer, (b) a carboxyl group-containing polymer, and (c) a hydroxyphenyl group-containing polymer, and (C) light. - an acid generator; or (3) a resin composition containing as an important component: (A2) at least one selected from the group consisting of vinyl ether urethane-based compounds, vinyl ester urethane-based compounds, and propylene The ester urethane-based compound is an unsaturated urethane-based compound, (Bd has a weight average molecular weight of 1,000 to 200,000 and a resin per kg of the resin. An acid group-containing urethane resin having an acid group content of 5 to 10 equivalents, and (C) a photo-acid generator. Next, the present invention provides a method of forming a pattern comprising the steps of: (1) applying the above-mentioned positive-type actinic ray decomposition and developable dry film to the surface of a coating substrate such that the surface of the coating substrate faces the dry film. a urethane resin layer, (2) optionally removing a non-actinic ray-decomposing and developing substrate of the dry film, (3) irradiating the actinic ray on the surface of the dry film via a photomask or directly to obtain an intended pattern (4) Stripping the non-actinic ray decomposing and developing substrate which is not stripped in the above step (2), (5) Decomposing the positive actinic ray and the developing urethane resin layer accepting 12677701 5. Description of the Invention (5) Developing treatment, and (6) removing unnecessary regions of the urethane resin layer to form a photoresist pattern film, and the step (1) or (2) includes a heat treatment step. DETAILED DESCRIPTION OF THE INVENTION The non-actinic ray-decomposing and developing substrate is, for example, a positive-type actinic ray-decomposing and developing resin layer fixed on a substrate, and is easy to apply to a surface of a coated substrate such as a printed circuit board. Matrix. Examples of the substrate may include a film of polyethylene terephthalate, an aromatic amide, c a p t ο n e, polymethylpentene, polyethylene, polypropylene or the like. Among them, a poly(p-citric acid) ethyl ester film is particularly preferable from the viewpoint of cost and providing a photodegradable and developable dry film having good characteristics. For ease of release, the above substrates may also be treated by a release agent such as polyoxymethylene, wax, fluorocarbon resin or the like. The matrix has a film thickness in the range of 1 to 100 μm, particularly 10 to 40 μm. After application, the matrix can be released and removed. The positive-type actinic ray-decomposing and developing resin composition can be coated or printed on the above substrate in accordance with a roll coating method, a spray coating method, a screen printing method, or the like to prepare a photodegradable and developable positive dry film. In order to enhance the characteristics of photodegradation and release of the film of the photosensitive resin composition from the substrate, the substrate may be previously coated with a releasing agent such as polyfluorene oxide, wax or the like. The positive actinic ray decomposing and developing resin layer has a film thickness of usually from 1 to 100 μm, particularly from 5 to 40 μm. The resin composition coated or printed on the surface of the substrate is preferably heated at about 50 to 150 ° C, preferably at about 80 to 120 1267701, before the thermal layer is laminated to the substrate. The coating layer can be crosslinked, resulting in improved photodegradation and development of the positive dry film mechanical properties, such as folding properties. The positive-type actinic ray-decomposing and developing resin composition used in the present invention is such that the actinic ray is irradiated to decompose the resin composition to be dissolved in the developing solution. The components of the positive actinic ray decomposing and developing urethane resin layer used in the dry film of the present invention can be explained below. Unsaturated compound (A ^ : compound (AJ is at least one selected from the group consisting of a vinyl ether group-containing compound, a vinyl ester group-containing compound, and an acrylate group-containing compound-containing unsaturated compound. A vinyl ether group-containing compound f low molecular weight or high molecular weight compound) It has about 1 to 4, preferably 2 to 4 in one molecule: -; ^-0-(:[1 = (:[12 represents a vinyl ether group, wherein R' represents 1 to 6 a straight or branched alkyl group of a carbon atom, for example, an ethyl group, a propyl group, a butyl group, etc., and may include, for example, a halogenated alkyl vinyl ether (such as chloroethyl vinyl ether) and the like. a phenolic compound (such as biphenol A, biphenol F, biphenol S, phenolic resin, etc.); or a condensation product with a polyhydric alcohol (such as ethylene glycol, propylene glycol trimethylolpropane, isoamyl alcohol, etc.). The ester group compound is a low molecular weight or high molecular weight compound having about 1 (one) to 4, preferably 2 to 4 vinyl ester groups in one molecule, and may include, for example, vinyl acetate or vinyl propionate. , vinyl lactate, vinyl butyrate, vinyl isobutyrate, ethylene hexanoate , vinyl isopropionate, trimethyl vinyl acetate, ethylene niobate 12678701 5. invention description (7) ester, Veova monomer (sold by Shell Chemical Company), etc. The propylene ester-containing compound is low molecular weight or high molecular weight. A compound having about 1 (one) to 4, preferably 2 to 4 acrylate groups in one molecule, and may include, for example, isopropenyl acetate, isopropenyl propionate, etc. Unsaturated compound (Ai) Among them, the use of a vinyl ether-containing compound is preferred because it is different from the addition reaction between the resin (B!) and the vinyl ether group in the compound (Ai). Unsaturated polyurethane compound (unsaturated compound) (A2) is at least one selected from the group consisting of a vinyl ether urethane-based compound, a vinyl ester urethane-based compound, and an acryl ester urethane-based compound as an unsaturated urethane. The main compound is a vinyl ether urethane-based compound having about 1 to 4, preferably 2 to 4, unsaturated ether groups in one molecule, such as: R'-〇-(:1{ = ( ^2 represents a vinyl ether group, wherein Rf represents 1 to 6 carbon atoms a straight or branched alkyl group, for example, an ethyl group, a propyl group, a butyl group, a 1-propenyl ether group, a butenyl group, etc., and an unsaturated group having at least one urethane linkage a compound, and more preferably, for example, a polyisocyanate compound (optionally, a hydroxyl group-containing compound having at least two hydroxyl groups in one molecule) and a hydroxyalkyl vinyl ether (such as hydroxyethyl vinyl ether) Reaction product; polyphenol compound, such as biphenol A, biphenol F, biphenol S, phenol resin, etc., polyhydric alcohol, such as ethylene glycol, C1267771 5. Invention description (8) diol, trimethylolpropane, A condensation product of pentaerythritol or the like and a polyisocyanate compound below with a halogenated alkyl vinyl ether (e.g., chloroethyl vinyl ether). Among them, a condensation product of a polyphenol compound with a halogenated alkyl vinyl ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl vinyl ether are preferred from the viewpoints of etching resistance, accuracy of a formed pattern, and the like. The vinyl ester urethane-based compound is a low molecular weight or high molecular weight compound having about 1 (one) to 4, preferably 2 to 4 vinyl ester groups in one molecule, and at least one urethane group. The ester linkage may include, for example, a reaction product of a polyisocyanate compound (optionally, a hydroxyl group-containing compound having at least two hydroxyl groups in one molecule) and a hydroxyvinyl ester (e.g., vinyl lactate or the like). The acrylate urethane-based compound is a low molecular weight or high molecular weight compound having about 1 (one) to 4, preferably 2 to 4 acrylate groups in one molecule, and at least one amide formic acid. The ester linkage may include, for example, the following polyisocyanate compound (optionally, a hydroxyl group-containing compound having at least two hydroxyl groups in one molecule), and a hydroxypropenyl ester. In the unsaturated compound (A2), a vinyl ether urethane-based compound is preferably used because it is liable to occur between the carboxyl group in the resin (Β,) or (B2) and the vinyl ether group in the compound (A2). Into a reaction. Examples of the above polyisocyanate may include an aliphatic diisocyanate compound such as hexamethylene diisocyanate, trimethylene diisocyanate, -10- 1267701 V, invention description (9) 1,4 -tetramethylene monoisocyanate, Pentamethylene diisocyanate, hydrazine, 2_ propyl monoisocyanate, 1, 2, butyl diisocyanate, trimethyl hexamethylene monoisocyanate, dibasic acid diisocyanate, leucine diisocyanate, 2, 3-butylene-isocyanate, hydrazine, 3-tert-butyl diisocyanate, etc.; alicyclic open isocyanate compound, such as isophoric-diisocyanate, 4,4'-methylene fluorene (cyclohexyl isocyanate) , methylcyclohexane _ 2,4-(or-2,6-) monoisocyanate, iota, 3_(or hydrazine) bis(isocyanate methyl)cyclohexane, 1,4-cyclohexane diisocyanate,丨,% cyclopentane diisocyanate, 1,2-cyclohexyl diisocyanate, etc.; aromatic diisocyanate compounds, such as the monomethyl monoisocyanate, methane benzene diisocyanate, tetramethyl benzene Methyl diisocyanate, methylphenyl diisocyanate, 4,4·-benzene Methane diisocyanate, phthalocyanine diisochlorite, 1,4-naphthalene diisocyanate, 4,4, toluidine diisocyanate, 4,4, dibenzoic acid monoisocyanate, (meta- or para-phenylene) Diphenyldimethyl diisocyanate, 4,4 '-biphenyl diisocyanate, 3,3, dimethyl-4,4, biphenyl diisocyanate, Dai (4-isocyanatophenyl) maple , isopropylidene oxime (4-phenylisocyanate), etc.; other polyisocyanates, for example, polyisocyanate compounds having three or four isocyanato groups, such as triphenylmethane _ 4,4', 4"- Triisocyanate, benzene 1,3,5-triisocyanate, toluene 2,4,6-triisocyanate, 4,4\-dimethyldiphenylmethane-2,2:5,5^tetraisocyanate, etc. Reactive polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, polyalkylene glycol, trimethylolpropane, and trisole by reacting the hydroxyl group of the relative polyol with an excess of isocyanate groups. An alcohol or the like, an adduct prepared by the polyisocyanate compound-11-1267701, invention description (1〇), hexamethylene diisocyanate, isophorone diisocyanate, tolyl diisocyanate Diurea-type adducts such as benzodimethyl diisocyanate, 4,4 diphenylmethane diisocyanate, 4,4 methylene sulfonium (cyclohexyl isocyanate), isocyanate cyclic adducts, and the like. Among them, preferred examples may include isophorone diisocyanate, benzodimethyl diisocyanate, tolyl diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Examples of the compound used as the case and having at least two hydroxyl groups in one molecule may include a glycol such as ethylene glycol or propylene glycol. Polyethylene glycol having a molecular weight of 6000 or less, polypropylene glycol having a molecular weight of 6000 or less, tetramethylene glycol, 1,4-butanediol, 1, 3. -butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-3,4-pentanediol, 3-anthracene Base - 4. 5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1. 5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, neopentyl glycol hydroxytrimethyl acetate, 1 , 4-cyclohexanedimethanol, tricyclodecane dimethanol, polycaprolactone, hydrogenated phenol A, hydrogenated phenol P, hydrogenated hydrazine A and hydrogenated hydrazine F alkylene oxide adduct a polyester diol such as hydrazine (hydroxyethyl) phthalate or the like, a trihydric or higher alcohol such as glycerol, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1, 2,6-hexanetriol, pentaerythritol, diiso-12- 1267701 V. Description of the invention (1 1 ) pentaerythritol, phytosterol, mannitol, etc., by lactone (such as ε-caprolactone) a polylactone polyol prepared by an addition reaction with the above diol and/or a tri- or higher alcohol. They can be used singly or in combination. Among them, polyethylene glycol, polycaprolactone, polypropylene glycol, tetramethylene glycol, trimethylolpropane, and the like are preferred. The compound (AJ and (Α2) preferably includes those which are liquid at room temperature or have a melting point or softening point of 150 ° C or lower, particularly 130 ° C or lower, because of the tendency to occur (BJ or ( B2) Addition reaction of a carboxyl group or a phenol group with a vinyl ether group in (AJ or (A2). An acid group-containing urethane resin (BJ: an acid group-containing urethane resin (Bd is The known method comprises reacting a polyisocyanate compound, a hydroxy acid compound having at least one hydroxyl group and at least one acid group in one molecule, and optionally a compound having at least one hydroxyl group in one molecule, and is substantially free of free isocyanic acid. The urethane resin prepared by the above. The above polyisocyanate compound may include the same as used for the unsaturated compound (A2). Examples of the above hydroxy acid compound may include dimethylolpropionic acid, dimethyloldine Acid, dimethylol valeric acid, tartaric acid, 1,2-hydroxystearic acid, p-hydroxybenzoic acid, salicylic acid, hydroxysuccinic acid, lactic acid, glycolic acid, 2,2-dimethyl-3-hydroxyl Propionic acid, etc., as appropriate, can be used alone or in combination a compound containing a hydroxyl group in one molecule, for example, methanol, ethanol, propanol, butanol, hexanol, -13-1267701 5. Description of the invention (12) Cyclohexanol, benzyl alcohol, etc. Acid-containing amine group A The acid ester resin (BJ has a weight average molecular weight ranging from about 1,000 to about 200,000, preferably from about 5,000 to about 1 50,000, more preferably from about 20,000 to about 10,000,000, and having from about 0.5 to about 5 per kg of resin. About 10 equivalents, preferably about 〇. From 5 to about 8 equivalents, more preferably from about 0.5 to about 5 equivalents of acid group content. The acid group content of less than about 〇·5 /kg causes the coating film formed by heating before the actinic ray irradiation to show an unsatisfactory degree of crosslinking, and the low solubility of the actinic ray irradiation region in the alkaline developing solution is lowered. nature. On the other hand, at more than about 10 equivalents, the composition showed poor storage stability. The resin (B2) of the present invention may comprise (a) a carboxyl group-containing and hydroxyphenyl polymer, (b) a carboxyl group-containing polymer, (c) a hydroxyphenyl group-containing polymer, and a mixture thereof. a polymer containing a carboxyl group and a hydroxybenzene (a polymer (a) is a film-forming polymer having at least one carboxyl group and at least one hydroxyphenyl group in one molecule, and may include hydroxystyrene such as p-hydroxystyrene a copolymer with a carboxyl group-containing polymerizable unsaturated monomer; a hydroxystyrene, a copolymer of a carboxyl group-containing monomer and another copolymerizable monomer, etc. Examples of the carboxyl group-containing polymerizable unsaturated monomer may include acrylic acid, methacrylic acid. , crotonic acid, itaconic acid, etc. Examples of other copolymerizable monomers may include (meth)acrylic acid (^. 12 alkyl ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, (methyl) Octyl acrylate, -14-1267701 V. Description of the invention (13) 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, etc.; (meth)acrylic acid C2. a 6-hydroxyalkyl ester, for example, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc., vinyl An aromatic compound such as styrene, α-methylstyrene, p-tert-butylstyrene, etc.; vinyl acetate, (meth)acrylonitrile, (meth)acrylamide, vinyl pyrrolidone, etc. . These monomers may be used singly or in combination. The polymer U) may also include a phenolic carboxylic acid having at least one of a phenol, (^-18 mono- or dialkylphenol or naphthol, and a phenol selected from the group consisting of resorcinol, catechol, etc.), such as a polymer prepared by the condensation reaction of hydroxybenzoic acid, gallic acid, isophthalic acid, etc., or a mixture thereof with formaldehyde. The polymer (a) usually has from about 1 Torr to about 200,000, particularly from about 20,000 to about 1, The weight average molecular weight in the range of 00,000, usually about 0 per kg of polymer. 5 to about 10 equivalents, especially about 0. 5 to about 5 . a carboxyl group content in the range of 0 equivalents, and at least about 1. 0 equivalents, especially about 2. 0 to about 8. Hydroxyphenyl content in the range of 0 equivalents. Less than about 0. The carboxyl group content of 5 equivalents/kg causes the coating film formed by heating before the actinic ray irradiation to exhibit an unsatisfactory degree of crosslinking, and the low solubility of the actinic ray irradiation region in the alkaline developing solution reduces the developing property. On the other hand, at more than about 10 equivalents/kg, the composition showed poor storage stability. On the other hand, a hydroxyphenyl group content of less than about 1 · 〇 equivalent / kg produces an unsatisfactory degree of crosslinking at the time of crosslinking. -15- 1267701 V. INSTRUCTION DESCRIPTION (14) The polymer preferably has a glass transition temperature (Tg) in the range of about 〇 ° C or higher, particularly from about 5 to about 70 ° C. When the Tg is lower, the adhesive coating forms adhesion of foreign particles, dust, etc., and is difficult to handle. a carboxyl group-containing polymer (b 1 : polymer (b) is a film-forming polymer containing at least one carboxyl group in one molecule, and may include, for example, a homopolymer of a carboxyl group-containing polymerizable unsaturated monomer, a carboxyl group a copolymer of a monomer and another copolymerizable monomer; a resin having a carboxyl group in one molecule or at a molecular terminal, and mainly a polyester, a polyurethane, a polyamide, etc. Examples of the unsaturated monomer may include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, etc. Examples of other monomers copolymerizable with the above carboxyl group-containing monomer may include C2_6 hydroxyalkyl (meth)acrylate, For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, etc.; these monomers can be used singly or in combination. The accuracy and etch resistance of the formed image pattern Etc. The other monomer may include a vinyl aromatic compound such as styrene, α-methylstyrene, C2-6 alkyl-substituted styrene, such as p-tert-butylstyrene, etc. The carboxyl group-containing polymer (b) has a usual It is a weight average molecular weight in the range of from about 1,000 to about 200,000, especially from about 20,000 to about 100,000, and has typically about 0 per kg of polymer. 5 to about 10 equivalents, especially -16-1267701 V. Description of the invention (15) is a carboxyl group content in the range of from about 0.5 to about 0.5 equivalent. Less than about 1. 羧基 Equivalent/kg of carboxyl group causes the coating film formed by heating before visible light irradiation to exhibit an unsatisfactory degree of crosslinking, and the low solubility of the irradiated region in the alkaline developing solution reduces the developing property. On the other hand, when it exceeds about 10 equivalents, the composition exhibits poor storage stability. The polymer (b) is preferably a glass transition temperature (Tg) having a range of about 〇 ° C or more, particularly from about 5 to about 70 ° C. When the Tg is lower than 0 °C, the adhesive coating film forms adhesion of foreign particles, dust, and the like, and is difficult to handle. The polymer (b) can be used in combination with the following hydroxyphenyl group-containing polymer (c). Hydroxybenzene-containing polymer (c): The polymer (c) is a polymer containing at least one hydroxyphenyl group in one molecule, and may include, for example, a monofunctional or polyfunctional phenol compound, an alkylphenol compound a condensation product of a mixture thereof with a carbonyl compound such as formaldehyde, acetone or the like, such as a homopolymer of a vinyl-containing aromatic compound containing p-hydroxystyrene; a hydroxyl group-containing vinyl aromatic compound and a copolymerizable monomer Copolymer and the like. Examples of the monofunctional or polyfunctional phenol compound may include a compound having 1 to 3 hydroxyl groups on a benzene ring, for example, phenol, o-cresol, m-cresol, p-cresol, 3,5-di Methyl phenol, 2,6-xylenol, 2,4-xylenol, catechol, resorcinol, gallic phenol, biphenol A, and the like. Examples of the alkylphenol compound may include L. The alkylphenol (1) is preferably an alkylphenol such as p-isopropylphenol, p-tert-butylphenol, p-third amyl phenol, p-t-octyl phenol or the like. -17- 1267701 V. INSTRUCTION DESCRIPTION (16) The condensation reaction of the above compound with a carbonyl compound such as formaldehyde, acetone or the like can be carried out by a known method, so that condensation in the presence of a basic catalyst is insoluble as the condensation reaction proceeds. The non-fusible phenolic resin type and the condensation in the presence of an acid catalyst form a soluble and fusible phenolic lacquer type. The phenolic enamel type resin is an increase in molecular weight as the condensation reaction proceeds, and preferably includes a weight average molecular weight prepared by carrying out a condensation reaction for 1 to 3 hours and having a range of from 500 to 2,000. Other monomers which may be copolymerized with the hydroxyl group-containing vinyl aromatic compound may include the same other copolymerizable monomers as exemplified in the case of the copolymer in the above polymer (b). The hydroxyphenyl-containing polymer (c) preferably has a weight average molecular weight in the range of usually from about 1,000 to about 200,000, particularly from about 1, from about 30,000 to about 30,000. The polymer (c) preferably has a weight of about 1. 〇 to about 1 〇 equivalent, especially about 2 · 0 to about 8. A hydroxyphenyl group content in the range of 0 equivalents. Less than about 1. The hydroxyphenyl group content of 〇 equivalent/kg causes the coating film formed by heating before visible light irradiation to exhibit an unsatisfactory degree of crosslinking. On the other hand, at more than about 10 equivalents/kg, the photoresist film is brittle. For polymers (a) and (b), the polymer (c) preferably has a glass transition temperature (Tg) ° of less than about 〇 ° C or higher, particularly from about 5 to about 70 ° C. Hey. (: When the adhesive coating film forms adhesion of foreign particles, dust, etc., it is difficult to handle. The compound (Μ) is an acid group-containing urethane resin (B1), that is, a compound resin (ΒΟ; compound ( Α 2) p-resin (β2), ie, compound-18-1267701 5. Invention (π) (Al) / Resin (B2); or Compound (A2) to Resin (Bi), Compound U2) / Resin (BJ) The mixing ratio is based on the total amount of the compound (Al) and the resin (B[), the compound (A2) and the resin (B2), or the compound (A2) and the resin (BJ, each of which is 0. 5 to 50/ 99. It is 5 to 50% by weight, preferably 1 to 30/99 to 70% by weight, more preferably 1 to 15/99% by weight. Less than 〇·5% by weight of the compound (Αι) or (A2), or more than 99.5% by weight of the resin (Bd or (B2), undesirably reducing the development solution resistance of the unirradiated area. , more than 50% by weight of the compound (^) or (a2), or less than 50% by weight of the resin (BJ or (B2), undesirably reduce sensitivity and storage stability. Light-acid bovine f The generating agent (C) is a compound which generates an acid upon irradiation with actinic rays, so that the resin is decomposed in the presence of the generated acid as a catalyst, and may include those known in the art. As a photo-acid generator (C) Examples of the compound and the mixture thereof may include a diazonium salt, a scale, an anthracene and an iron iodide salt; a halide; a combination of an organic metal and an organic halogen; a strong acid benzoin and an o-nitrobenzyl ester such as toluenesulfonic acid; The N-hydroxy guanamine group and the N-hydroxy quinone sulfonate disclosed in Patent No. 43 7 605, and the like, may also include an arylnaphthoquinonediazide-4-sulfonate. Preferred light stabilizers may include Diaryl iodonium and triaryl manganese. Usually, these compounds are in the form of multi-alloy metal halide ions. For example, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphite, etc. -19- 1267701 V. Description of the invention (彳8) Other effective acid generators exhibiting photolysis and developability Including the addition of an oligomer having an aromatic tannin generator as an anion group of a positive pair of ions and a polymer. The above polymers are also included in column 9 of U.S. Patent 4,6 6 1 , 4 2 9 , And the polymer disclosed in column 10, lines 1-14 (as described below). For the purpose of controlling the spectral sensitivity to the wavelength of actinic radiation, it is preferred to add the sensitizer to the above system. The necessity of the above addition depends on the requirements of the system and the specific photolysis and developability compounds used. For example, in the case of iodonium and phosphonium salts corresponding to wavelengths less than 300 nm, diphenyl ketone and its derivatives are used. The polycyclic aromatic hydrocarbons such as dibenzopyrene, hen and oxime, derivatives thereof, etc., can be photocured at a longer wavelength. Decomposition of the diaryl iodonium and the triaryl sulfonium salt can also be achieved by using hydrazine ( Photocuring with p-N,N-dimethylaminopentylene)-acetone. The bond is an effective photosolvent in the bismuth salt having a chain length of 34 atoms. In MG. Tilley's blog, North Da Tat State University, Fargo, North Dato (1988) [Diss, Abstr. Int. B, 49, 8791 (1989): Chem. Abstr. 111,39942u] The disclosed compound is a preferred photolytic agent. Other preferred acid generators may include ATASS, i.e., 3-(9-mercapto)propyl diphenylphosphonium hexafluoroantimonate, which allows the coca and sulfonium salts to be bonded via a chain comprising three carbon atoms. Additional examples of the acid generator used herein may include diphenyliodonium tosylate, benzoin tosylate, and triarylsulfonium hexafluoroantimonate -20 - 1267701. V. Description (1 9 ) Acid Additional examples of the generating agent may include iron-propadiene complex, hydrazine-propadiene complex, decane-metal chelating agent complex, three-till compound, diazide naphthol compound, acid salt, The yttrium sulfonate, the halogenated compound, and the like, and may also include the acid generator described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. The acid generator may be compounded in an amount of about 100 parts by weight of the compound (B, compound (A2) and resin (B2), or compound (A2) and resin (the total amount of BJ is about 0. 1 to 40 parts by weight, especially about 0. 2 to 20 weight range. The positive-type actinic ray-decomposing and developing resin composition used for the dry film of the present invention may include uniformly dispersing or dissolving the above-mentioned components by dispersing or dissolving the above components, or uniformly dispersing the pigment particles in an organic solvent in the case of using a pigment as a coloring agent. The prepared organic solvent is a main resin composition. Examples of the organic solvent used to dissolve or disperse the above components may include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc. Ether, such as tetrahydrofuran, dioxane, dimethoxyethane, etc.; celluloid, such as methyl cyproterone, ethyl cyproterone, diethylene glycol monomethyl ether, etc.; aromatic hydrocarbons, such as benzene, Toluene, xylene, ethylbenzene, etc.; halogenated hydrocarbons such as chloroform, trichloroethylene, dichloromethane, etc.; alcohols such as ethanol 'benzyl alcohol, etc.; others such as dimethylformamide, dimethyl sulfoxide and the like. The above resin composition may further comprise a water-based resin composition prepared by neutralizing a carboxyl group in a resin composition with a basic compound, and then dissolving or dispersing the neutralized product in water - 21 - 1267701 V. Inventive Note (20) Things. The resin composition used in the dry film of the present invention is in the form of a solid at room temperature upon drying. An acid hydrolysis reaction occurs in the exposed region in the presence of an acid produced by exposure of the coating film formed of the resin composition for the dry film of the present invention to actinic rays. For the purpose of smooth acid hydrolysis reaction, the presence of water is desirable, and the addition of a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methyl cellulose, ethyl cellulose or the like to the resin composition can be easily performed. The above reaction introduces the desired water into the resulting coating film. The hydrophilic resin is usually 20 parts by weight or less per 100 parts by weight of the resin component, preferably 0. A range of from 1 to 10 parts by weight. In addition to the above components, the resin composition used in the present invention may optionally be insoluble, soluble or dispersible in water or an organic solvent, and may improve or impair the solubility in an organic solvent or an aqueous developing solution. Other resins. Examples of the other resin may include a phenol resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, a polyoxyn resin, a fluorine smoke resin, a mixture thereof, a modified product thereof, and the like. The resin composition used in the present invention may contain a plasticizer such as phthalic acid ester, a polyester resin, an acrylic resin or the like in order to impart appropriate flexibility, non-adhesiveness, adhesiveness and the like to form a dry film. The resin composition used in the present invention may optionally contain a fluidity regulator, a plasticizer, a dye, a coloring agent such as a pigment, or the like. -22- 1267701 V. DESCRIPTION OF THE INVENTION (21) The method of the present invention can be applied to any use without particular limitation, and only includes the above steps. The coating substrate used in the present invention may comprise a substrate for conductors, insulators, semiconductors, combinations thereof for the following purposes. Examples of the above uses in various industrial fields may include electrical fields such as electrical parts, lighting, electrical components, semiconductors, printed matter, printed circuits, electronic communications, electric power, etc.; physical fields such as instruments, optical fields, indicators, sound fields , controllers, sales, signals, information recording, etc.; chemistry, metallurgy, fiber, such as inorganic chemistry, organic chemistry, polymer chemistry, metallurgy, fiber, etc.; processing and transportation, such as separation, mixing, metal Processing, plastic processing, printed matter, containers, packaging, etc.; living objects, for example, agriculture and marine areas, food fermentation, household items, health and entertainment, etc.; mechanical engineering. The method of the present invention is a method for forming a pattern, comprising the steps of: (1) applying the above-mentioned positive-type actinic ray decomposing and developing dry film to the surface of the coating substrate such that the surface of the coating substrate faces the amino group of the dry film; a formate resin layer, (2) optionally removing the non-actinic ray decomposition and developability matrix of the dry film, (3) irradiating the actinic film on the surface of the dry film by a photomask or directly to obtain an intended pattern, optionally heat-treating (4) Stripping the non-actinic ray decomposing and developing substrate which has not been removed in the above step (2), (5) Decomposing the positive actinic ray and accepting the urethane resin layer -23- 1267701 V. Description of the invention (22) developing treatment, and 6 removing unnecessary regions of the urethane resin layer to form a photoresist pattern film, and the step (1) or (2) includes a heat treatment step. The dry film can be applied to the surface of the coating substrate such that the positive-type actinic ray decomposition and the developable resin coating film face the surface of the coating substrate such as a conductive circuit board having non-perforation and/or perforation, and can be laminated on Then, the hot layer is contracted to pressurize the surface of the substrate of the dry film to bond the conductive substrate to the surface of the resin coating layer. The hot layer step can be carried out by heating the conductive substrate, heating the surface of the substrate of the dry film, or both. The heating temperature is usually from 60 to 150 ° C, especially from 80 to 12 (the range of TC. When the dry film is applied to the surface of the coated substrate, the surface of the substrate is treated with a liquid, for example, as described in U.S. Patent No. 3,645,772 to Jone. A sexually-promoting solution, such as a solvent for a photoresist film as described by Fiekes, or a swelling agent, which improves the adhesion between the surface of the coating substrate and the dry film. The above liquid may have photodecomposition and developability properties, such as jsaacsorl A photoresist solution as described in U.S. Patent No. 3,629,036. The application of a dry film to a coating substrate using a vacuum lamination apparatus. The above heat treatment can occur substantially in the compound (AO and acid group urethane resin (Bi), The temperature condition of the crosslinking reaction between the compound (A2) and the resin (B2) or the compound (A2) and the resin () is carried out, for example, by heating at about 60 ° C to about 150 ° C for about 1 minute to about 30 The actinic ray irradiation can be performed by, for example, a method of irradiating an actinic ray through a reticle, a method of directly drawing by laser scanning, etc. -24- 1267701 V. Description of the invention (23) An example of actinic ray can be Including ultraviolet light, See light, laser beam (such as near infrared, visible laser, ultraviolet laser, etc.). The dose is usually 0. 5 to 2000 mJ/cm 2 , preferably 1 to 1 00 m; Joules per square centimeter. Sources of illumination of actinic radiation may include those known to the art, for example, from over-recording lamps, local pressure permanent lamps, medium voltage recording lamps, low voltage recording lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps. Light source such as fluorescent lamp, tungsten lamp, daylight, etc.; visible light range blocked by ultraviolet light blocking filter, and various lasers having an oscillation period in the visible light range. High power and stabilized laser beam sources may preferably include argon lasers and YAG-SHG lasers. After the dry film is applied to the surface of the coated substrate, the substrate of the dry film is optionally peeled off from the positive actinic ray decomposition and the developable resin coating layer. The stripping step can optionally be carried out after the following actinic ray irradiation step. After the irradiation of the actinic ray, it is preferably heat-treated to heat the temperature at which the crosslinked structure of the cured coating film is broken in the presence of an acid generated by irradiation, for example, about 60 ° C to about 150 ° C for about 1 minute. Up to 30 minutes. The development treatment can be carried out by washing out the photoresist film in the exposed region with an alkaline aqueous solution, an organic solvent, water or the like. The aqueous alkaline solution may include an aqueous solution of a base such as caustic soda, sodium carbonate, caustic potash, ammonia or the like. The organic solvent which dissolves the exposed region may include, for example, 1,1,1-trichloroethane, trichloroethylene, methyl ethyl ketone, dichloromethane or the like. After the development treatment, the resin film is rinsed with water, followed by drying with hot air or the like to form an intended image on the conductor. Optionally, etching can be performed to remove conductors in the exposed areas and -25-1267701. V. Invention (24) Preparation of printed circuit boards. For example, in the case where the conductive film in the printed circuit board is copper, the conductive film in the exposed region can be removed by etching, that is, using an acid etching solution such as a copper chloride solution, and an alkali etching solution such as ammonia water. According to the present invention, the copper inside the perforations does not dissolve without causing cracking. After the etching step, the residual photoresist film can be removed as appropriate. The removal of the residual photoresist film can be carried out using a stripping agent, for example, using an aqueous solution of a base or an acid, and various organic solvents which dissolve the photoresist film but do not substantially impair the substrate and the conductive film constituting the circuit pattern on the surface of the substrate. . In the case of using a conductive circuit pattern and a perforated and/or non-perforated substrate as the conductive substrate having perforations, the photoresist film can be easily formed into a weld light by satisfactorily covering the perforated, non-perforated and fine circuit patterns. It has an intermediate insulation layer with high reliability, such as electrical insulation properties and chemical resistance. According to the present invention, the positive dry film formed by the actinic group-containing actinic ray decomposition and the developable resin composition is used to provide actinic ray decomposition and development of the developed film without cracking or peeling when the dry film is bent. The ease of handling, and development and etching processes can form a fine pattern. EXAMPLES The present invention is explained in detail by the following examples and comparative examples, in which "parts" and 〃 % " each represent "parts by weight" and "weight vf. Preparation Example 1 Compound containing vinyl ether (Preparation of Ay® 250 ml flask was charged 45. 6 grams of biphenol A, 80 ml of 2-chloroethane-26-1267701 V. Description of the invention (25) vinyl ether and 100 ml of toluene, followed by introduction of nitrogen, 20 g of sodium hydroxide, heated at 80 ° C 30 minutes, with 4 by means of a solution prepared by dissolving 56 g of tetrabutylammonium bromide in 20 ml of 2-ethyl chloride ether, heating and reacting at 95 ° C for 5 hours, washing the reaction product three times with deionized water, separating the oil layer, and Evaporation and removal of 2-chloroethyl ethane ether and toluene gave a vinyl ether compound (Ai-1) having a weight average molecular weight of 368 and containing two ethyl ether ether groups in one molecule. Preparation 2 Preparation of vinyl ether urethane-based compound f A2 - 1 ) Preparation of 210 parts of trimethylhexamethylene diisocyanate, a mixture of 232 parts of hydroxybutyl vinyl ether and 5 drops of pyrrole at 90° C was reacted for 6 hours to obtain a divinyl ether compound (A2-l). Preparation Example 3 Preparation of vinyl ether urethane-based compound (Α γ 2 ) In the presence of 1 part of dibutyltin diacetate, 875 parts by reaction of 1 molar trimethylolpropane and 3 moles a mixture of a polyisocyanate 75% ethylene glycol dimethyl ether solution prepared by stretching xylylene diisocyanate and 264 parts of 2-hydroxyethyl vinyl ether is reacted at 35 ° C for 3 hours to obtain 3 molecules in one molecule. A vinyl ether compound (A2-2) having a vinyl ether group and having a solid content of about 81%. Preparation Example 4 An acid group urethane resin (B1 -1) was prepared by preparing 275 parts of methyl ethyl ketone and 23 parts of trimethyl hexamethylene diisocyanate -27 - 1267701. V. Invention (26) A mixture of ester, 10 parts by weight of tripropylene glycol and 73 parts of dimethylolbutanoic acid is reacted at 80 ° C for 10 hours to obtain a reaction product, and then a reaction product of 75 parts or more is reacted with 24 parts of glycolic acid for 1 hour. And obtained a weight average molecular weight of about 47,000 and 1. a resin having a carboxyl group content of 4 mol/kg (i.e., 79 mg KOH/g of yttrium acid) (B "l). Preparation 5 Preparation of acid-containing urethane resin (B1-2) 596 parts of methyl ethyl ketone And a mixture of 576 parts of isophorone diisocyanate, 81 parts of tripropylene glycol and 70 parts of dimethylolbutanoic acid was reacted at 80 ° C for 10 hours to obtain a weight average molecular weight of about 40,000 and 1. Resin of 6 mol/kg carboxyl group (ie, 88 mg KOH/g acid bismuth) (B "2). Preparation Example 6 Preparation of carboxyl group-containing resin (Βγ 1 ) 216 parts of acrylic acid, 500 parts of styrene , a mixture of 284 parts of n-butyl methacrylate and 50 parts of azobisisobutyronitrile was added dropwise to 600 parts of methyl isobutyl ketone heated at 80 ° C and stirred for 2 hours, and then maintained at this temperature. 2 hours, and got about 62. a polymer having a solid content of 5% and a carboxyl group content of 3 mol/kg (b2-1). Preparation Example 7 Preparation of residue-containing resin (Βγ 3 ) 288 parts of acrylic acid, 300 parts of styrene, 255 parts of n-butyl acrylate, 157 parts of 2-hydroxyethyl acrylate and 100 parts of third butyl group - 28- 1267701 V. INSTRUCTION DESCRIPTION (27) A mixture of a base peroxybenzoate is added dropwise to 1 000 parts of 2-butoxyethanol heated at ll ° C and stirred for 2 hours, and then maintained at this temperature 2 The polymer (B2-2) having a solid content of about 50% and a residue content of 4 mol/kg was obtained in an hour. Preparation Example 8 Preparation of Carboxyl Group and Hydroxyphenyl Resin (B2-3) 200 parts of tetrahydrofuran, 65 parts of p-hydroxystyrene, 28 parts of n-butyl acrylate, 11 parts of acrylic acid and 3 parts of arsenazo The mixture of isobutyronitrile was reacted at 100 ° C for 2 hours to obtain a reaction product, and then the reaction product was injected into a solvent of 1 500 ml of toluene, and the reaction product was precipitated and separated, and the precipitate was dried at 60 ° C to obtain Has a weight average molecular weight of about 5200 and 4. Light decomposition of 6 mol/kg hydroxyphenyl group and developable resin (B2-3). Preparation Example 9 Preparation of a box of hydroxyphenyl resin (B2-4) The flask was charged with 1 490 parts of o-cresol, 1145 parts of 30% formalin, 1 30 parts of deionized water and 6. 5 parts of oxalic acid, followed by heating under reflux for 60 minutes, adding 1 3 . 5 parts of 5% chloric acid, heated under reflux for 40 minutes, 400 parts of deionized water at about 15 ° C was added, the resulting mixture was kept at about 75 ° C to precipitate the resin, and 35% aqueous sodium hydroxide solution was added to neutralize Remove the deionized water, add 400 parts of deionized water, rinse the resin at 75 ° C, remove the dewatered water, repeat the same washing step twice, and dry at about 120 ° C under vacuum to obtain 600 Weight average molecular -29- 1267701 V. Description of the invention (28) Amount of phenolic enamel phenol resin (B2-4). Example 1 to 90 parts of acid group-containing urethane (B1-1), 10 parts of vinyl ether-containing compound (A1-1), and 5 parts of photo-acid generator ΝΑΙ·105 (trade name, Midori) A mixture of 2 parts of 1,2,3-benzotriazole in 2 parts of Kagamku Co., Ltd. was dissolved in cyclohexanone to obtain a photodecomposition and developability solution having a solid content of 28%. The photodecomposition and developability solution was applied to a polyethylene terephthalate film by a bar coater to a dry film thickness of 10 μm, followed by heating at 120 ° C for 10 minutes to obtain a dry film. The properties of the dry film are shown in Table 1. The dry film was laminated on the perforations coated with the copper clad laminate on both sides using a dry film laminate, and then the polyethylene terephthalate film was peeled off to obtain a coating substrate having a photoresist film. Ultraviolet light having a intensity of 50 mJ/cm 2 was irradiated onto the substrate through a positive illuminator using a mercury lamp, followed by heating at 120 ° C for 1 Torr and development with a 0.77 % aqueous solution of sodium carbonate. The results are shown in Table 1. However, etching was carried out with an aqueous solution of copper chloride at 40 ° C, and then the residual photoresist film was removed with a 3% aqueous solution of caustic soda to obtain a printed circuit board. The results are shown in Table 1. Examples 2 - 4 and Comparative Examples 1 - 2 Each of the photodecomposition and developability solutions was prepared according to the formulation shown in Table 1, and then a dry film was prepared in the same manner as in Example 1, and each dry film was subjected to the same test as in Example 1. . The results are shown in Table 1. -30- 1267701 V. INSTRUCTIONS (29) Table 1 Example Comparative Example 1 2 3 4 1 2 10 10 30 10 10 30 Formulation B1 - 1 90 70 • (Parts) B^2 90 70 B2-l 90 70 Light - Acid generator 5 5 5 5 5 5 1,2,3-benzobisazole 2 2 2 2 2 2 Dry film properties Application work force 2 2 2 2 2 2 Tent formation properties 2 2 2 2 1 1 Development properties 2 2 2 2 2 2 Anti-etching properties 2 2 2 2 1 1 -31 - 1267701 V. Description of the invention (3〇) Example 5 Example 1 was repeated except that the acid-containing resin (B2-1) and vinyl ether urethane were used. The main compound (A2 - 1 ). The results are shown in Table 2. Examples 6 - 14 and Comparative Example 3 - Each of the photodecomposition and developability solutions was prepared according to the formulation shown in Table 2, followed by preparing dry films in the same manner as in Example 5, and subjecting each dry film to the same test as in Example 5. . The results are shown in Table 2. -32- 1267701 V. INSTRUCTIONS (31) Anti-etching properties Developing properties Dry film properties '龅方(份) Tent formation I Nature application i 力 i 1,2,3- j benzobisazole 1 photo-acid Producer > 1 ω ω ω ω Μ·. Μ· A CO. tO Ρ >> to to t?0 two to to to tsD to Of g I-1 o Ol i example to to to to CJI o 1—A • o CJi to tsD to to OX g h-1 o To to to to Ol g 1-^ o 00 to to to to αχ gs CD to to K) to to Ol gss to to to Ol g Η-1 to to to to cn gg to to to to to Oi g to to to to cn — to h-1 to to cn s CO cr l·-» tSD f—* to to CTf s A i-* to — to to cn o cn μα to h-* to to cn s 1 h-* to to to αχ <ϊ -33- 1267701 V. INSTRUCTION DESCRIPTION (32) Example 15 Example 1 was repeated except that an acid group-containing urethane resin (B, -1 ) and a vinyl ether urethane-based compound (A2) were used. - 1 ). The results are shown in Table 3. Example 1 5 - 2 2 and Comparative Examples 8 - 9 Each was equipped with a photodecomposition and developability solution as shown in Table 3, followed by preparing a dry film in the same manner as in Example 15 and subjecting each dry film to Example 15 The same test. The results are shown in Table 3. -34 1267701 V. Description of invention (33)
抗蝕刻性質 _ .. 翳 漭 β 国 1 乾膜性能 配方 .(份） ^ _J 帳篷形成 性質 應用作業力 1,2,3- 苯并二唑 光-酸產生劑 bd ίΟ « Η > 1 Η ω ω t t tN〇 — > > to to tsD tSD N) to to to at g — _實例 •. to to to to to οι g I—1 to to to to bO οι to to to to to αι s to to to to to αι g I—4 s to to to to to 〇τ g g to to to to to cn CO 〇 to CnO to bO to to αι tND to I—* to M to to οχ g κ* Ο 00 比較例 h-* tsO — to bO ΟΙ CD -35- 1267701 五、發明說明（34) 在表1 - 3中，配方均以π份"表示。各使用如實例1 之相同光-酸產生劑。 乾膜性能試驗方法· 應用作業力 使用層合器將乾膜壓黏在磨面覆銅層合物上，繼而剝 除基質。如下進行評估。 2:樹脂層完全轉移至覆銅層合物上（良好）。 1 :樹脂層部份或完全殘留在基質上（失敗）。 帳篷形成件質： 使用層合器將乾膜壓黏在具有穿孔之磨面覆銅層合物 上，繼而剝除基質。 如下進行評估。 2 :穿孔上之樹脂層拉伸而形成中空（良好）。 1 :穿孔上之樹脂層破裂（失敗）。 顯影件質 2 :顯影後：無光阻殘渣殘留在塗層基質上（良好）。 1 :顯影後：光阻殘渣殘留在塗層基質上（失敗）。 抗蝕件質： 2 :顯影後之蝕刻處理顯示非照射區域（包括穿孔上之中空 樹脂膜）中之光阻無變化（良好）。 1 .光阻顯示如膨脹、溶解、剝離等之缺點（失敗）。 -36-Anti-etching properties _ .. 翳漭β 国1 Dry film performance formula. (Parts) ^ _J Tent forming properties Application work force 1,2,3- benzobisazole photo-acid generator bd Ο Ο « Η > 1 Η ω ω tt tN〇— >> to to tsD tSD N) to to to g — _ instance •. to to to to οι g I-1 to to to bO οι to to to to αι s to To to to to αι g I—4 s to to to to 〇τ gg to to to to cn CO 〇to CnO to bO to to αι tND to I—* to M to to οχ g κ* Ο 00 Comparative Example H-* tsO — to bO ΟΙ CD -35- 1267701 V. INSTRUCTIONS (34) In Table 1-3, the formulations are expressed in terms of π parts ". The same photo-acid generator as in Example 1 was used. Dry film performance test method · Application work force The laminate is pressed onto the ground copper clad laminate using a laminate, and then the substrate is peeled off. The evaluation is as follows. 2: The resin layer was completely transferred to the copper clad laminate (good). 1 : The resin layer partially or completely remains on the substrate (failure). Tent forming quality: The laminate is pressed onto the ground copper clad laminate with perforations using a laminate, which in turn is stripped. The evaluation is as follows. 2: The resin layer on the perforation was stretched to form a hollow (good). 1: The resin layer on the perforation is broken (failure). Developing material 2: After development: no photoresist residue remains on the coating substrate (good). 1 : After development: the photoresist residue remains on the coating substrate (failure). Resist material: 2: The etching treatment after development showed no change (good) in the photoresist in the non-irradiated area (including the hollow resin film on the perforation). 1. Photoresist shows defects such as expansion, dissolution, and peeling (failure). -36-