200537242 w . 九、發明說明： 【發明所屬之技術領域】 本發明特別是關於一種做爲印刷電路板製造用之有用 的感光性轉印片。本發明也是關於一種使用上述之感光性轉 印片來製造印刷電路板之方法。 【先前技術】 在印刷電路板之製造領域中，電路圖案係藉由利用一種 使用一由支撐體（特別是可撓性透明薄膜支撐體）、和在該支 ^ 撐體上所形成的感光層所形成的感光性轉印片之光刻技術 來形成的。例如，在具有貫穿孔之印刷電路板的情況下，係 於印刷電路板形成用基板（例如，銅張積層板）上形成貫穿 孔，爲在貫穿孔內側壁部上形成金屬層後，再於基板表面上 疊合感光性轉印片，並將光照射在電路圖案形成區域和含有 貫穿孔開口部之區域上，並予以硬化形成預定圖案形狀之感 光層；接著剝取感光性轉印片之支撐體，並除去電路圖案形 成區域上之硬化層及貫穿孔開口部區域上之硬化層（稱爲帳 ® 篷（tent)膜）以外之未硬化感光層區域後，再對所露出之金屬 層部分進行蝕刻處理，然後除去硬化層而將電路圖案形成於 基板表面上。 爲了達成感光性轉印片之高解像度化，則使感光層之厚 度變薄是有效的方式。然而，使感光層之厚度變薄時’會有 在貫穿孔之邊緣部分中之硬化層產生變形，厚度變薄致使在 製造印刷電路板時硬化層容易破損之問題。因而’乃一直在 開發一種可形成高解像之圖案、且可以形成一帳篷膜難以發 200537242 ^ 生破損之硬化層之感光性轉印片。 例如，在專利文獻1中揭示一種具有於支撐體上設有驗 可溶、加熱所引起的流動性小、且感應活性能量線之第一感 光層，更且進一步地在其上設置支撐體上設有鹼可溶、加熱 所引起的流動性大、且感應活性能量線之第二感光層的感光 性轉印片。此專利文獻中，也說明藉由將該感光性轉印片之 第二感光層埋入貫穿孔內可以保護貫穿孔之金屬層。然而’ 由於在印刷電路板製造之最終步驟不得不將胲已埋入貫穿 孔內之硬化樹脂（第二感光之硬化物）予以除去，所以就會有 印刷電路板之製造步驟變爲複雜之問題。 近年來，電子機器已向小型、輕量化推進，印刷電路板 也要求微細化之電路，並且也要求光阻圖案細線化、感光性 轉印片之高解像度化。但是，習用的感光性轉印片卻無法滿 足此種要求。也就是說，上述之感光性轉印片由於係透過支 撐體來曝光，爲使得高解像度化則就應該使得該支撐體之厚 I 度變薄。然而，另一方面，支撐體係被要求具有用以擔任在 塗布感光性樹脂組成物時之支撐體的角色用之某種程度的 自身保持性，所以通常需要15〜25微米左右之厚度，而且就 使用習用等級的光穿透性支撐體薄膜而言，目前尙不能夠達 到符合高解像度化之要求。 對於此等要求而言，爲了達成高解像度化已進行過各式 各樣的嘗試。例如，在曝光之前先剝離支撐體，而直接將負 膜密接於感光層上之方法。通常，感光層係保持有與基材密 接用的某種程度之黏著性，直接適用此種方法時，一使負膜 200537242 . 和感光層密接時就難以剝離負膜，不僅會有降低作業性，又 且負膜會受到感光性樹脂之污染，以及會有空氣阻害而降低 感度等之問題。因此，嘗試著進行改良此種方法，以2層以 上之感光層，以及和負膜直接接觸之層使用非黏著性層等。 (參照專利文獻2、專利文獻3)。但是，此種方法由於將感 光層予以多層化的緣故，所以塗布手續費工之外，對於降低 感度也不具有效果。 又，其他的方法，則是嘗試著在感光性樹脂組成物上設 • 置中間層來解決此等缺點，如於專利文獻4、專利文獻5、 專利文獻6、專利文獻7、專利文獻8、專利文獻9、專利文 獻10等所示。但是，此等之中任一者，在支撐體和感光層 之間必須設置中間層，塗布就需要2次手續，又且就薄的 中間層而言處理也有困難。 使用透明薄膜來做爲支撐體，由於製造上之理由而含有 使薄膜表面形成凹凸.的骨材，就高解像度之圖案的形成而 言，該骨樣會造成曝光時之不良的影響，並會使得在光阻輪 ^ 廓上產生凹陷等之缺陷。在專利文獻11、專利文獻12、專 利文獻13、專利文獻14等之中，雖然揭示藉由改良支撐體 來解決高解像度圖案形成時之上述問題點的方法，然而尙無 法以習用的感光層之厚度而得到充分的解像力。 【專利文獻1】特開平8-54732號公報 【專利文獻2】特開平1-22 1 735號公報 【專利文獻3】特開平2-2301 49號公報 【專利文獻4】特開昭56-40824號公報 200537242 、 【專利文獻5】特開昭5 5 - 5 0 1 0 7 2號公報 【專利文獻6】特開昭5 4 -1 2 2 1 5號公報 【專利文獻7】特開昭4 7 - 4 6 9號公報 【專利文獻8】特開昭5 9 - 9 7 1 3 8號公報 【專利文獻9】特開昭5 9 - 2 1 6 1 4 1號公報 【專利文獻10】特開昭63-1 97942號公報 【專利文獻11】特開2001-13681號公報 【專利文獻12】特開2001 -921 23號公報 Φ 【專利文獻13】特開2001 -921 24號公報 【專利文獻14】特開2001 -921 25號公報 【發明內容】 【發明所欲解決之課題】 本發明之課題係在於：提供一種具備具有高的解像度， 而且可以形成高強度的硬化層（帳篷膜）之感光層的感光性 轉印片。又，本發.明之目的也在於：提供一種可以使用該感 光性轉印片，而有利於工業製造具有貫穿孔或通孔的印刷電 ®路板之方法。 【用以解決課題之手段】 本發明是一種感光性轉印片，其特徵在於：係在支撐體 上，依序積層一由黏合劑聚合物、乙烯性不飽和鍵含有單 體、及光聚合起始劑、感光性樹脂組成物所形成、並藉由光 之照射將乙烯性不飽和鍵含有單體予以聚合硬化而成的相 對低感度之第一感光層，然後積層一由黏合劑聚合物、乙烯 性不飽和鍵含有單體、及光聚合起始劑、感光性樹脂組成物 200537242 . 所形成、並藉由光之照射將乙烯性不飽和鍵含有單體予以@ 合硬化而成的相對高感度之第二感光層所積層而成；以及_ 種感光性轉印片，其特徵在於：在該支撐體之一側的表面 上，係使用已積層有含有微粒子之樹脂層的支撐體。 本發明之較佳的態樣係如以下所示。 (1) 第二感光層（高感度層）之厚度係在1〜10微米之範圍。 (2) 第一感光層（低感度層）之厚度係在50微米以下，而且 比第二感光層的厚度還厚。 Φ (3)用以將第二感光層予以硬化用所需要的光量A和用以 將第一感光層予以硬化用所需要的光量B間之比a / B 係在0.01〜0.5之範圍。 (4) 用以將第二感光層予以硬化用所需要的光量A和到第 一感光層之開始硬化前光量C間之差C - A係少於用以 將第二感光層予以硬化用所需要的光量A之1〇倍。 (5) 用以將第二感光層予以硬化用所需要的光量A和到第 一感光層之開始硬化前光量C間之差C - A係在 _ 100mJ/cm2 以下。 (6) 第一感光層及第二感光層係含有互爲相同的一由黏合 劑聚合物、乙烯性不飽和鍵含有單體、及光聚合起始 劑，而且第二感光層係含有比第一感光層還多的光聚合 起始劑。 (7) 第二感光層係進一步含有增感劑。 (8) 印刷電路板製造用。 又，本發明也是一種製造內壁表面爲以金屬層所覆蓋之 -10- 200537242 - 具有貫穿孔或通孔的印刷電路板之由下列步驟所構成的製 造方法： (1 )準備具有貫穿孔或通孔、且表面係經以金屬層所覆 蓋之印刷電路板形成用基板之步驟； (2) 在印刷電路板形成用基板之表面上，壓著上述本發 明之感光性轉印片，依照印刷電路板形成用基板、 第二感光層、第一感光層、然後爲支撐體之順序積 _ 層而形成積層體之積層步驟； (3) 在積層體之支撐體側到印刷電路板形成用基板之 電路圖案形成區域上，照射將第二感光層予以硬化 用所需要的光量之光使成爲預定之圖案形狀，而形 成預定圖案的硬化層區域之電路部曝光步驟； (4) 在積層體之支撐體側到印刷電路板形成用基板之 含有貫穿孔或通孔的開口部之區域上，照射同時將 第一感光層和第二感光層予以硬化用所需要的光 φ 量之光使成爲預定之圖案形狀，而形成被覆貫穿孔 或通孔之開口部區域的硬化層區域之孔部曝光步 驟； ί5)從積層體剝離支撐體之支撐體剝離步驟； (6)溶解除去印刷電路板形成用基板之第一感光層和 第二感光層之未硬化區域，以露出基板表面之該未 硬化區域的金屬層之顯像步驟； ί7)以蝕刻液溶解除去露出區域之金屬層之蝕刻步 -11- 200537242 - 驟；以及 (8)從印刷電路板形成用基板除去硬化層之硬化層除 去步驟。 更且，本發明也是一種積層體，其特徵爲：在具有貫穿 孔或通孔、表面爲金屬層所覆蓋之印刷電路板形成用基板 上，依序積層一由黏合劑聚合物、乙烯性不飽和鍵含有單 體、以及光聚合起始劑之感光性樹脂組成物所形成、並藉由 光之照射將乙烯性不飽和鍵含有單體予以聚合硬化而成的 ® 相對高感度之第二感光層，接著積層一由黏合劑聚合物、乙 烯性不飽和鍵含有單體、以及光聚合起始劑之感光性樹脂組 成物所形成、並藉由光之照射將乙烯性不飽和鍵含有單體予 以聚合硬化而成的相對低感度之第一感光層，然後在一側的 表面上，積層含有微粒子之樹脂層的支撐體，依照此順序積 層而成。 【發明·效果】 本發明之感光性轉印片，藉由改變光之照射量（曝光量） ^ 可以形成厚度不同的硬化層。從而，將本發明之感光性轉印 片使用於具有貫穿孔及通孔之印刷電路板之製造時，就可以 形成對於電路圖案形成區域而言爲相對的薄厚度之高解像 的硬化層，並可以形成相對於貫穿孔或通孔而言爲厚的厚度 之高強度的硬化層。 【實施方式】 【用以實施發明之最佳形態】 本發明之感光性轉印片的一例之斷面圖係示於第1圖 -12- 200537242 . 中。 在第1圖中，感光性轉印片1 〇係依照順序積層支撐體 11、第一感光層12、第二感光層13、其保護薄膜14而成。 第一感光層12和第二感光層13係分別由黏合劑聚合物、乙 烯性不飽和鍵含有單體、及含有光聚合起始劑之感光性樹脂 組成物所形成、並藉由光之照射將乙烯性不飽和鍵含有單體 予以聚合硬化而成。本發明之主要特徵點爲：第二感光層 1 3相對於第一感光層1 2係具有比較高的感度。此處所謂的 # 高感度係意謂著第二感光層13之硬化係以比第一感光層12 少之光照射量起始的。 一邊參照第2圖一邊說明關於本發明之感光性轉印片 中光照射量和感光層之硬化量間的關係。第2圖’係爲顯示 一表示從支撐體照射光於本發明之感光性轉印片時’光照射 量和所得到的硬化層之厚度間的關係之感度曲線的曲線 圖。.在第2圖中，橫軸係表示光之照射量，縱軸係表示因光 照射而硬化之感光層的厚度。縱軸之D係表示第二感光之厚 • 度，E係表示第一感光層之厚度和第二感光層之厚度的總和 之感光層總厚度。 如第2圖所示，在本發明之感光性轉印片中’儘管從支 撐體照射之光係以支撐體、第一感光層、然後第二感光層之 順序前進，然而第二感光層之硬化係先以比第一感光層少的 光量開始的。第二感光層之硬化開始光量S較宜是 0.01〜10mJ/cm2之範圍。第二感光層之硬化量係隨著光量之 增加而增加，沒多久第二感光層全體即硬化。使第二感光層 200537242 • 硬化用所需要的光量 A較宜是 20mJ/cm2以下（特別是 2〜1 5mJ/cm2之範圍內）。 全部之第二感光層硬化之後，當光量建漸增多時，則開 始第一感光層之硬化，當光量更進一步增多時，則第一感光 層就全部硬化。用以將第二感光層予以硬化所需要的光量 A、和用以將第一感光層予以硬化所需要的光量B之比B/A 較宜是在〇.〇1〜0.5之範圍。 第一感光層開始硬化前所需要之光量C可以是和用以 • 將第二感光層予以硬化所需要的光量A等量，然而較宜是比 光量大者。用以將第二感光層予以硬化所需要的光量A、和 第一感光層開始硬化前所需要的光量C間之差C-A，較宜是 比用以將第二感光層予以硬化所需要的光之照射量A的1 0 倍還少（特別是，1.1〜10倍之範圍內），較宜是1〇〇mJ/cm2 以下（特別是1~1〇〇mJ/cm2之範圍內）。 具有如上述之感度曲線之感光性轉印片，例如，可以藉 由使得第二感光層之光聚合起始劑之含量較第一感光層 ® 多，或者在第二感光層中添加增感劑而得到。 在本發明之感光性轉印片中所使用的黏合劑聚合物，較 宜是對鹼性水溶液爲可溶性、或者持有和鹼性水溶液接觸所 引起的膨脹最少之特性的共聚物。對於鹼性水溶液爲可溶性 或持有膨脹性之共聚物的例子，舉例來說，例如其可以是藉 由羧基含有乙烯基聚合物、及其他的可共聚合之乙烯基單體 間之共聚合所得到的羧基含有乙烯基共聚物。 羧基含有乙烯基單體的例子，舉例來說，例如其可以是 -14- 200537242 • (甲基）丙烯酸、乙烯基安息香酸、馬來酸、衣康酸、巴豆酸、 桂皮酸、丙烯酸二聚物、苯乙烯磺酸、2-丙烯醯胺-2-甲基丙 烷磺酸、及磷酸單（甲基）丙烯醯基乙酯等。又，也可以利用 2-羥乙基（甲基）丙烯酸酯等之具有羥基的單體和馬來酸酐或 如酞酸酐之環狀酐間的加成反應物。或者，也可以使用以馬 來酸酐、衣康酸酐等之酐含有單體做爲羧基之前驅物。另 外，從共聚合性、成本及溶解性等之觀點來看，此等之中以 (甲基）丙烯酸特別地理想。 P 其他的可共聚合的單體的例子，舉例來說，例如其可以 是不含有酸性基（特別是羧基）之乙烯不飽和單體。尤其，較 宜是不具有和酸性基間的化學反應性之物。例如，較宜是（甲 基）丙烯酸酯類、巴豆酸酯類、乙烯基酯類、馬來酸二酯類、 富馬酸二酯類、衣康酸二酯類、（甲基）丙烯醯胺類、苯乙烯 類及乙烯醚類。此等之單體，舉例來說，例如其可以是以下 之化合物。 (甲基）丙烯酸酯類的例子，舉例來說，例如其可以是甲 ® 基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、η-丙基（甲基）丙烯 酸酯、異丁基（甲基）丙烯酸酯、tert-丁基（甲基）丙烯酸酯、 η-己基（甲基）丙烯酸酯、2-乙基己基（甲基）丙烯酸酯、乙醯 基乙基（甲基）丙烯酸酯、苯基（甲基）丙烯酸酯、2-羥乙基（甲 基）丙烯酸酯、2-甲氧乙基（甲基）丙烯酸酯、2乙氧乙基（甲基） 丙烯酸酯、2-(2-甲氧乙氧）乙基（甲基）丙烯酸酯、環己基（甲 基）丙烯酸酯苄基（甲基）丙烯酸酯、二乙二醇單甲醚（甲基）丙 烯酸酯、二乙二醇單乙醚（甲基）丙烯酸酯、二乙二醇單苯醚 -15- 200537242 • (甲基）丙烯酸酯、三乙二醇單乙醚（甲基）丙烯酸酯等。 巴豆酸酯類的例子，舉例來說，例如其可以是巴豆酸丁 酯、及巴豆酸己酯等。乙烯基酯類的例子，舉例來說，例如 其可以是乙烯基乙酸酯、乙烯基丙酸酯、乙烯基丁酸酯、乙 烯基甲氧乙酸酯、及安息香酸乙烯酯等。 馬來酸二酯類的例子，舉例來說，例如可以是馬來酸二 甲酯、馬來酸二乙酯、馬來酸二丁酯等。富馬酸二酯類的例 子，舉例來說，例如可以是富馬酸二甲酯、富馬酸二乙酯、 • 富馬酸二丁酯等。衣康酸二酯類的例子，舉例來說，例如可 以是衣康酸二甲酯、衣康酸二乙酯、衣康酸二丁酯等。 (甲基）丙烯醯胺的例子，舉例來說，例如可以是（甲基） 丙烯醯胺、N -甲基（甲基）丙烯醯胺、N -乙基（甲基）丙烯醯胺、 N-丙基（甲基）丙烯醯胺、N-n-丁基丙烯酸基（甲基）醯胺、 N-tert-丁基（甲基）丙烯醯胺、η-環己基（甲基）丙烯醯胺、 Ν-(2-甲氧基乙基）（甲基）丙烯醯胺、Ν，Ν-二甲基（甲基）丙烯 醯胺、Ν,Ν-二乙基（甲基）丙烯醯胺、Ν-苯基（甲基）丙烯醯胺、 ® Ν-苄基（甲基）丙烯醯胺、及（甲基）丙烯醯基嗎啉等。 苯乙烯類的例子，舉例來說，例如其可以是苯乙烯、甲 基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異 丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁 氧基苯乙烯、乙醯氧基苯乙烯、氯化苯乙烯、二氯化苯乙烯、 溴化苯乙烯、氯化甲基苯乙烯、乙烯基安息香酸甲酯、及α -甲基苯乙烯等。乙烯基醚類的例子，舉例來說，例如其可 以是甲基乙烯基醚、丁基乙烯基醚、己基乙烯基醚、及甲氧 -16- 200537242 • 基乙基乙烯基醚等。 也可以使用其他的乙烯基吡啶、乙烯吡咯啶酮、乙儲基 咔唑、及（甲基）丙烯腈等。 此等化合物之中，可以僅使用其中的一種，或者也可以 倂用二種以上。特佳的可共聚合單體，係有甲基（甲基）丙條 酸酯、2-乙基己基（甲基）丙烯酸酯、苄基（甲基）丙烯酸酯、 苯乙烯、α -甲基苯乙烯、氯化苯乙烯、溴化苯乙烯、及羥 基苯乙烯等。 § 羧基含有乙烯共聚物之具有羧基之重複單位的含量，宜 是佔全體共聚物之重複單位中之1〜60莫耳。/。的範圍，較宜 是5〜50莫耳。/。之範圍，特佳爲1〇〜40莫耳％之範圍。羧基 含有乙燒共聚物之分子量，以平均分子量計較宜是在 1000〜200000之範圍，特佳爲在4000〜100000之範圍。 感光層中之黏合劑的含量在第一感光層和第二感光層 兩者之中較宜是佔5〜96質量％之範圍，特佳爲40〜80質量 %之範圍。 ® 合適的乙烯性不飽和鍵含有單體之例子，係爲具有至少 2個乙烯性不飽和雙鍵的化合物（以下，也稱爲多官能單 體）。舉例來說，例如可以在特公昭36-5093號公報、特公 昭35-1 471 9號公報、特公昭44-28727號公報等所記載的 化合物來做爲此種多官能單體的例子。上述公報上所記載的 化合物（（甲基）丙烯酸酯類、（甲基）丙烯醯胺類、烯丙基化合 物、乙烯基醚化合物、乙烯基酯類）的例子，可以是如以下 所列者。（甲基）丙烯酸酯及甲基丙烯酸酯類的例子，舉例來 -17- 200537242 • 說’例如其可以是多元醇之聚丙烯酸酯類及聚甲基丙烯酸酯 類（此處「聚」係指二（甲基）丙烯酸酯以上而言）；此等多元 醇的例子，舉例來說，例如聚乙二醇、聚丙二醇、聚丁二醇、 聚環氧己烷、聚環氧苯乙烯、聚氧雜環丁烷、四氫呋喃、環 己烷二醇、二甲苯二醇、二-(/3 -羥乙氧）苯、甘油、雙甘油、 新戊二醇、三羥甲基丙烷、三羥基乙烷、季戊四醇、雙季戊 四醇、縮水山梨糖醇、山梨糖醇、丁二醇、丁三醇、2-丁烷 -1,4-二醇、2-n-丁基-2-乙基-丙二醇、2-丁烷-1,4·二醇 3- ® 氯-1, 2-丙二醇、1,4-環己烷二甲醇、3-環己烷-1,1-二甲醇、 萘烷二醇、2,3-二溴-2-丁烯-1,4-二醇、2,2-二乙基-1,3-丙 二醇、1,5-二羥基-1,2,3,4-四氫萘、2,5-二甲基-2,5-己二 醇、2,2-二甲基-1,3-丙二醇、2,2-二苯基-1,3-丙二醇、十二 烷二醇、中赤藻糖醇、2-乙基-1 ,3-丙二醇、2-乙基-2-(羥甲 基）-1,3-丙二醇、2-乙基-2_甲基-1,3-丙二醇、庚二醇、己二 醇、3-己烷-2,5-二醇、羥苄基醇、羥乙基間苯二酚、2-甲基 -1,4-丁二醇、2-甲基-2,4-戊二醇、壬二醇、辛二醇、戊二 ® 醇、1-苯基-1,2-乙二醇、丙二醇、2,2,4,4-四甲基-1, 3-環丁 二醇、2,3,5,6-四甲基-P-二甲苯-α二醇、1,1,4,4-四苯 基-1,4-丁 二醇、1,1,4,4-四苯基 _2· 丁烷-4-二醇、1,2,6_ 三羥 基己烷、1,1’-雙-2-萘醇、雙羥基萘、1，Γ-亞甲基-二-2-萘酚、 1,2,4-苯三醇、聯酚、2,2’-雙（4_羥基苯基）丁烷、1,1·雙（4-羥基苯基）環己烷、雙（羥基苯基）甲烷、鄰苯二酚、4-氯間苯 二酚、3,4-二羥基氫肉桂酸、氫醌、羥苄基醇、甲基氫醌、 亞甲基-2,4,6-三羥基苯甲酸酯、氟化縮水甘油醇、苯三酚、 -18- 200537242 • 間苯二酚、葡萄糖、α - (1 -胺乙基）-p -羥苄基醇、2 -胺基-2 -乙基-1, 3 -丙二醇、2 -胺基-2-甲基-1, 3 -丙二醇、3 -胺基-1,2-丙二醇、N-(3-胺丙基卜二乙醇胺、ν,Ν，·雙- 2- (2 -羥乙基）哌 阱、2,2-雙（羥甲基卜2,2，，2，，-硝基三乙醇、2,2-雙（羥甲基）丙 酸、1,3·雙（羥甲基）脲、1,2 -雙（4-P比啶基）-1,2 -乙二醇、N-n-丁基二乙醇胺、二乙醇胺、N -伸乙基二乙醇胺、3 -氫硫基· 1，2 -丙二醇、3 -吡啶基-1 , 2 -丙二醇、2 - (2 -吡啶基）-1，3 -丙二醇、 三乙醇胺、α -(1-胺乙基卜p-羥苄基醇、3_胺基_4_羥苯基颯 •等。 此等丙烯酸酯類、及甲基丙烯酸酯類之中，最佳的例 子’舉例來說，從容易取得的觀點來看，例如其可以是乙二 醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸 酯、四乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二 醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二 甲基丙烯酸酯、聚乙二醇二丙燦酸酯、四丙二醇二丙烯酸 酯、十二丙二醇二丙烯酸酯、三羥甲基烷三丙烯酸酯、三羥 ® 甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇 三丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇二甲基丙烯酸 酯、二季戊四醇五丙烯酸酯、甘油基三丙烯酸酯、二甘油基 二甲基丙烯酸酯、1,3_丙二醇二丙烯酸酯、1,2,4-丁三醇三 甲基丙烯酸酯、1 ,4-環己烷二醇二丙烯酸酯、1,5-戊二醇二 丙烯酸酯、新戊二醇二丙烯酸酯、環氧乙烷加成三羥甲基丙 烷之三丙烯酸酯等。 丙烯醯胺類及甲基丙烯醯胺類的例子，舉例來說’例如 -19- 200537242 . 其可以是亞甲基雙丙烯醯胺、亞甲基雙甲基 尙有伸乙二胺、二胺基丙烷、二胺基丁烷、 六亞甲基二胺、雙（2-胺丙基）胺、二伸乙基 亞甲基二胺、八亞甲基二胺及以異種原子中 環的聚胺（例如，伸苯二胺、伸二甲苯二胺、 乙基胺、二胺基苯甲酸、二胺基甲苯、二胺 等）等之聚丙烯醯胺及聚甲基丙烯醯胺。 烯丙基化合物的例子，舉例來說，例如 • 對酞酸、癸二酸、己二酸、戊二酸、及丙二 二烯丙酯，硝酸二烯丙酯、蒽醌二磺酸、萍 羥基-P-苯二磺酸、二羥基萘二磺酸及萘二 的二烯丙酯，以及二丙烯醯胺等。乙烯基酯 舉例來說，例如其可以是前述多元醇之聚Z 乙二醇二乙烯基醚、1,3,5_三- yS-乙烯氧基 二-/3 -乙烯氧基乙氧基苯、及甘油基三乙烯 的例子，舉例來說，例如其可以是二乙烯基 • 烯基己二酸酯、二乙烯基酞酸酯、二乙烯基 烯基苯-1, 3-二磺酸酯、二乙烯基丁烷-1,4-乙烯化合物的例子，舉例來說，例如其可β ρ-烯丙基苯乙烯及Ρ-異丙烷苯乙烯等。 上述化合物以外之化合物，舉例來說， 基(甲基丙烯醯胺）乙基丙烯酸酯、Ν，Ν_ 氧乙基）丙烯醯胺、烯丙基甲基丙烯酸酯等； 之不同的乙烯性不飽和雙鍵之化合物，更且 丙烯醯胺，之外 五亞甲基二胺、 三胺基二胺、七 斷的聚胺及具有 冷-(4-胺基苯基） 基蒽醌、二胺莽 I其可以是酞酸、 酸等之二羧酸之 :二磺酸、2,5-二 磺酸等之二磺酸 丨化合物之例子， 二烯基醚（例如， 乙氧基苯、1，3-基醚），乙烯酯類 琥珀酸酯、二乙 對酞酸酯、二乙 二磺酸酯等。苯 :是二乙烯基苯、 例如N-/S -羥乙 •雙（/3 -甲基丙烯 之具有2個以上 具有至少二個氫 -20- 200537242 . 氧基之多元醇化合物、和稍微過剩的具有至少二個的異氫酸 酯基的聚異氰酸酯化合物進行反應而得的反應生成物，與具 有至少一個的氫氧基和至少一個的乙烯性不飽和基之化合 物起反應所得到的具有至少二個乙烯性不飽和雙鍵之多官 能聚胺基甲酸酯化合物，也是適合於本發明使用的理想化合 物。 此等之多官能單體係可以單獨使用，也可以倂用二種以 上。感光層中之多官能單體之含量，在第一感光層和第二感 # 光層兩者之中較宜是5〜90重量。/。，特佳爲15〜60重量％。 光聚合起始劑，舉例來說，例如其可以是芳香族酮、美 國專利第2367660號說明書上所揭示之連位聚酮醛基化合 物、美國專利第2448828號說明書上所揭示之偶因醚化合 物、美國專利第272251 2號說明書上所揭示之以α -烴取代 之偶因化合物、美國專利第30461 27號說明書及美國專利 第295 1 758號說明書上所揭示之多核醌化合物、美國專利 第3549367號說明書上所揭示之三芳基咪唑化合物和Ρ-胺 •基酮之組合、特公昭51 -4851 6號公報上所記載的苯并噻唑 化合物和三鹵甲基-S-三畊化合物、美國專利第4239850號 說明書上所記載之三鹵甲基-S-三阱化合物、美國專利第 42 1 2976號說明書上所記載之三鹵甲基噻二唑化合物等。尤 其，特佳爲芳香族酮。 上述芳香族酮的較佳例子，舉例來說，例如其可以是二 苯甲酮、2-甲基二苯甲酮、3-甲基二苯甲酮、4-甲基二苯甲 酮、4-甲氧基二苯甲酮、2-氯二苯甲酮、4-氯二苯甲酮、4- -21 - 200537242 • 溴二苯甲酮、2·羧基二苯甲酮、2 -乙氧羰基二苯甲酮、二苯 甲酮四羧酸或其四甲酯、心甲氧- 4’-二甲基胺基二苯甲酮、 4,4，-二甲氧二苯甲酮、4 -二甲基胺基二苯甲酮、4 -二甲基胺 基苯乙酮、蒽醌、2-第三-丁基蒽醌、2-甲基蒽醌、菲醌、口山 酮、噻噸酮、2 -氯噻噸酮、2，4 -二甲基噻噸酮、2，4 -二乙基 噻噸酮、芴、吖啶酮及苯偶因、苯偶因醚類（例如，苯偶因 甲醚、苯偶因乙醚、苯偶因丙醚、苯偶因異丙醚、苯偶因苯 基醚、苄基二甲基縮酮）、4,4’-雙（二烷基胺）二苯甲酮類（例 # 如，4,4’-雙（二甲基胺）二苯甲酮、4,4、雙（二環己基胺）二苯 甲酮、4,4’-雙（二乙基胺）二苯甲酮、4,4’-雙（二羥乙基胺）二 苯甲酮）。特佳的例子，舉例來說，例如可以是二苯甲酮。 感光層中之光聚合起始劑的含量，一般在第一感光層及 第二感光層兩者中係爲0.1〜10重量％，較宜是〇_5〜5重量 %。在藉由光聚合起始劑之含量來調整第一感光層及第二感 光層間之感度差的情況下，第二感光層之光聚合起始劑的含 量，相對於第一感光層之光聚合起始劑的含量計較宜是 _ 1·5〜10倍的量，特佳爲2〜5倍之量。 就本發明之感光性轉印片而言，也可以在感光層中添加 增感劑。增感劑通常是只添加於第二感光層。 適合於做爲增感劑者，舉例來說，例如可以使用公知的 多核芳香族類（例如，ΪΕ、茈、三苯基乙院（triphenylene))、 咕噸類（例如，螢光素、伊紅、紅黴素、若丹明B、孟加拉玫 瑰紅）、酞菁類（例如，硫碳化酞菁、氧碳化酞菁）、部花菁類 (例如，部花菁、碳化部化菁）、噻畊類（例如，硫蓳、亞甲 -22 - 200537242 • 基藍、甲苯胺藍）、吖啶類（例如，吖啶橙、氯黃素、吖黃素、 烷基吖啶）、蒽醌類（例如，蒽醌）、角鯊鐵類（例如’角鯊鋤）、 以及香豆素類（例如，香豆素_1、香豆素-102、香豆素_152)。 增感劑之添加量，相對於感光層之總成分計宜是在 0.05〜30質量。/。之範圍，較宜是〇.1〜20質量。/。之範圍，特佳 爲0 · 2〜1 0質量％之範圍。 本發明之感光性轉印片之感光層也可以含有洛芬鹼二 聚物。洛芬鹼二聚物之例子，舉例來說’例如其可以是2-(2’_ • 氯苯基）-4,5-二苯基咪唑二聚物、2-(2’-氯苯基）-4,5-二（3’-甲氧苯基）咪唑二聚物、2-(2’·氟苯基）-4,5-二苯基咪唑二聚 物、2-(2’-甲氧苯基）-4,5-二苯基咪唑二聚物、2-(4’-甲氧苯 基）-4,5-二苯基咪唑二聚物。 又，本發明之感光性轉印片之感光層，例如，也可以含 有如J·可撒爾著「感光系統」第5章所記載之有機硫化合 物、過氧化物、乳膠系化合物、偶氮及重氮化合物、光還原 性色素、以及有機鹵素化合物等。有機硫化合物的例子，舉 • 例來說，例如其可以是二-η-丁基二硫化物、二苄基二硫化 物、2-氫硫基苯并噻唑、2-氫硫基苯并噚唑、噻酚、乙基三 氯甲烷硫酸酯、2-氫硫基苯并咪唑。過氧化物之例子，舉例 來說，例如其可以是過氧化二-t-丁基、過氧化苯甲醯、過氧 化甲乙酮等。乳膠化合物係由過氧化物和還原劑之組合所構 成之物’舉例來說，例如其可以是亞鐵離子和過硫酸離子、 鐵離子和過氧化物等。偶氮及重氮化合物，舉例來說，例如 其可以是α , α 偶氮雙丁腈、2-偶氮雙-2-甲基丁腈、p-胺 -23- 200537242 β 基二苯基胺之重氮鑰類。光還原性色素，舉例來說，例如其 可以是孟加拉玫瑰紅、紅黴素、伊紅、Ρ 丫黃素、核黃素、酉太 菁。有機鹵素化合物之例子，舉例來說，例如其可以是2 -三氯甲基-5 -苯基-1, 3，4-噚二唑、2 -三氯甲基-5-(氯苯 基）-1,3,4-噚二唑、2-三氯甲基- 5- (1-萘基）-1,3,4-噚二唑、 2 -三氯甲基- 5- (2 -萘基）-1,3,4-噚二唑、2-三溴甲基-5 -苯基 -1，3,4-曙二唑、2 -三溴甲基- 5- (2 -萘基）-1,3,4 -B萼二唑、2-三氯甲基-5-苯乙烯基-1,3,4-曙二唑、2-三氯甲基-5-(4-氯苯 Φ 乙烯基Μ，3,4-曙二唑、2 -三氯甲基-5-(4-甲氧苯乙烯 基）-1,3，4-曙二唑、2-三氯甲基-5-(1-萘基）-1,3,4-噚二唑、2-三氯甲基- 5-(4-η· 丁氧苯乙烯基）-1,3,4-曙二唑、2-三溴甲基 -5-苯乙烯基-1,3,4-曙二唑、苯基三溴甲基颯、ρ-硝基苯基三 溴甲基颯、P-氯苯基三溴甲基颯、2,4,6-三（三氯甲基）-s-三 阱、2-苯基-4,6·雙（三氯甲基）-s·三畊、2-(4-甲氧苯基）-4,6-雙（三氯甲基）-s-三阱、2-(4-氯苯基）-4,6-雙（三溴甲基）-s-三 畊。 ® 更且，也可以使用於本發明之有機鹵素化合物的例子， 舉例來說，例如其可以是鹵化烴、鹵化醇化合物、鹵化羰基 化合物、鹵化醚化合物、鹵化酯化合物、鹵化醯胺化合物。 鹵化烴的例子，舉例來說，例如其可以是四溴化碳、碘仿、 1，2-二溴乙烷、1,1,2,2-四溴乙烷、1,1_雙（ρ·氯苯基）_2,2,2-三氯乙烷、1，2-二溴·1，1 ,2-三氯乙烷、1,2,3-三溴丙烷、1· 溴-4-氯丁烷、1,2,3,4-四溴丁烷、四氯環丙烷、六氯環戊二 烯、二溴環己烷等。鹵化醇化合物的例子，舉例來說，例如 -24 - 200537242 • 其可以是2,2,2-三氯乙醇、三溴乙醇、1，3-二氯-2-丙醇、 1,1,1-三氯-2-丙醇、二（碘六亞甲基）胺異丙醇、三溴-第三_ 丁醇、2,2,3-三氯丁烷-1，4-二醇等。鹵化羰基化合物的例 子，舉例來說，例如其可以是1,1-二氯丙酮、1,3_二氯丙酮、 六氯丙酮、六溴丙酮、1,1,3,3-四氯丙酮、三氯丙酮、 3,4 -二溴-2-丁酮、1,4-二氯-2-丁酮-二溴環己酮等。鹵化醚 化合物的例子，舉例來說，例如其可以是2-溴乙基甲醚、2-二溴乙基乙醚、二（2-溴乙基）醚、2-二氯乙基乙醚等。鹵化 # 酯化合物的例子，舉例來說，例如其可以是鹵化羧酸之酯、 羧酸之鹵化酯、或鹵化羧酸之鹵化酯；此等之例子，舉例來 說，例如其可以是乙酸溴乙酯、三氯乙酸乙酯、三氯乙酸三 氯乙酯、2,3-二溴丙基丙烯酸酯之均聚物及共聚物、二溴丙 酸三氯乙酯、α，/3 -二氯丙烯酸乙酯等。鹵化醯胺化合物的 例子，舉例來說，例如其可以是氯乙醯胺、溴乙醯胺、二氯 乙醯胺、三氯乙醯胺、三溴乙醯胺、三氯乙基三氯乙醯胺.、 2-溴異丙醯胺、2,2,2-三氯丙醯胺、Ν-氯琥珀醯亞胺、Ν-溴 ® 琥珀醯亞胺等。在有機鹵素化合物中，較宜是持有二個以上 之鍵結於同一碳原子上的鹵素原子，特佳爲在一個碳原子上 持有三個鹵素原子。有機鹵素化合物可以單位獨使用，也可 以倂用二種以上。此等之中，特佳的有機鹵素化合物係爲五 溴甲基苯颯、2,4-雙（三氯甲基）6·苯基三唑。使用於本發明 的有機鹵素化合物之量，相對於感光層之總成分計一般係操 0.001〜5重量％之範圍，較宜是在〇·〇〇5〜1重量。/〇。 就本發明之感光性轉印片而言，在感光層中更進一步添 -25- 200537242 • 加熱聚合禁止劑。熱聚合禁止劑的例子，舉例來說，例如其 可以是P-甲氧酚、氫醌、烷基或芳基取代氫醌、卜丁基鄰苯 二酚、苯三酚、氯化亞酮、氯醌、萘胺、/3-萘酚、2,6 -二+ 丁基-P-甲酚、吡啶、硝基苯、二硝基苯、P-三啶、亞甲基藍、 有機銅、水楊酸甲酯等。所含有的此等熱聚合禁止劑，相對 於多官能單體計較宜是0.001〜5重量％。 就本發明之感光性轉印片而言，爲了控制膜物性（可撓 性），也可以在感光層中添加可塑性劑，其例子，舉例來說， • 例如其可以是二甲基酞酸酯、二丁基酞酸酯、二異丁基酞酸 酯、二辛基酞酸酯、辛基辛醯基酞酸酯、二環己基酞酸酯、 雙十三基酞酸酯、丁基苄基酞酸酯、雙十一基酞酸酯、二芳 基酞酸酯等之酞酸酯類，二甲基葡萄糖酞酸酯、乙基酞醯基 乙基乙醇酸酯、乙二醇甲基酞酸酯、丁二醇丁基酞酸酯、三 乙二醇二辛酸酯等之二醇酯，磷酸三甲苯酚酯、磷酸三苯基 酯等之磷酸酯類，二異丁基己二酸酯、二辛基己二酸酯、二 甲基癸二酸酯、二丁基癸二酸酯、二辛基癸二酸酯、二丁基 ® 馬來酸酯等之脂肪族二鹼基酯類，苯磺醯胺、p-甲苯磺醯 胺、N-n-丁基乙醯胺等之醯胺類，檸檬酸三酯、甘油三乙醯 酯、月桂酸丁酯等。較宜是P-甲苯磺醯胺。 就本發明之感光性轉印片而言，感光層可以含有無色顏 料（leuco-pigment) 〇 無色顏料的例子，舉例來說，例如其可 以是三（P-二甲基胺基苯基）甲烷（無色結晶紫）、三（ρ·二乙基 月女基苯基）甲院、三（ρ -二甲基胺基-〇-甲基苯基）甲院、三（ρ· 二乙基胺基-〇 -甲基苯基）甲烷、雙（Ρ -二丁基胺基苯基）- -26- 200537242 . 〔P-(2_氰乙基）甲基胺基苯基〕甲烷、雙（ρ·二甲基胺基苯 基）-2-喹啉基甲烷、三（ρ_二丙基胺基苯基）甲烷等之胺基三 芳基甲烷類，3,6 -雙（二甲基胺基）-9 -苯基咕噸、3 -胺基-6-一甲基胺基-2-甲基- 9- (o -氯苯基）咕噸等之胺基咕噸類，3,6-雙（二乙基胺基）-9-(0 -乙氧羰基苯基）噻噸、3,6 -雙（二甲基胺 基）噻噸等之胺基噻噸類，3,6-雙（二乙基胺基）-9,10-二氫- 9-苯基吖卩定、3，6 -雙（节基胺基）-9,1 0 -二氫-9 -甲基吖卩定等之胺 基-9,1 0-二氫吖啶類，3,7-雙（二乙基胺基）啡噻畊等之胺基 Φ 啡噻阱類，3,7-雙（乙基胺基）苯基噻阱等之胺基苯基噻阱 類，3,7-雙（二乙基胺基）-5-己基-5,10-二氫化啡阱等之二氫 化啡畊類，雙（P-二甲基胺基苯基）苯胺基甲烷等之胺基苯基 甲烷類，4-胺基-4’-二甲基胺基二苯基胺、4-胺基-α ,沒-二 氰基氫桂皮酸甲酯等之胺基氫桂皮酸類，1-(2-萘基）-2-苯基 肼等之肼類，1,4-雙（乙基胺基）-2,3-二氫蒽醌類之胺-2,3-二氫蒽醌類，N，N-二乙基-P-苯乙基苯胺等之苯乙基苯胺 類，含有1 〇_乙醯基-3,7_雙（二甲基胺基）啡噻阱等之鹼基性 • NH的無色顏料之醯基衍生物，三（4-二乙基胺基-〇-甲苯基） 乙氧羰基□烷等之不持有氧化所得到的氫但可經氧化發色 化合物所得到無色狀化合物，無色靛類顏料，如美國專利第 30425 1 5號及美國專利第30425 1 7號上所記載之氧化發色形 之有機胺類（例如，4,4’-伸乙二胺、二苯基胺、N，N-二甲基 苯胺、4,4’-亞甲基二胺三苯基胺、N·乙烯基咔唑）。特佳者 爲無色結晶紫。上述之無色顏料之量，相對於感光層之總成 分計，較宜是在〇·〇1〜1〇重量％之範圍，特佳爲0·05〜5重 -27- 200537242 . 量％之範圍。 在本發明之感光性轉印片中可使用以將感光層予以染 色、並賦與保存安定性爲目的之染料。合適的染料之例子， 舉例來說，例如其可以是艷綠硫酸鹽、乙基紫、伊紅、紅黴 素B、甲基綠、結晶紫、鹼性品紅、酚酞、1，3 -二苯基三吖 啶、土耳其紅S、百里香酞、甲基紫2 B、喹哪啶紅、孟加拉 玫瑰紅、米塔尼爾黃、百里香硫酞、二甲苯酚藍、甲基橙、 橙IV、二苯基酪卡巴胂、2，7 -二氯螢光素、對甲基紅、剛果 Φ 紅、本佐紅紫4 B、α -萘紅、尼羅藍A、迪吉納指示劑、甲 基紫、孔雀綠草酸鹽、副品紅、油藍-#603 (東方化學工業（股） 製）、若丹明B、若丹明6G等。特佳的染料爲孔雀綠草酸鹽。 就本發明而言，爲了提高第一感光層和第二感光層間之 密接性、或者第二感光層和印刷基板形成用基板間之密接 性，可以於感光層使用公知的所謂之密接促進劑。舉例來 說，例如其可以是苯并咪唑、苯并曙唑、苯并噻唑、2-甲毓 基苯并咪唑、2-甲锍基苯并噚唑、2-甲锍基苯并噻唑、3-嗎 Φ 啉甲基-1 -苯基-三唑-2-硫酮、3-嗎啉甲基-5-苯基-噚二唑- 2-硫酮、5-胺基-3-嗎啉甲基-噻二唑-2-硫酮' 2-氫硫基-5-甲硫 基-噻二唑等。較宜是3-嗎啉甲基-1 ·苯基-三唑·2-酮。 本發明之感光性轉印片’例如’係可以如下所述之做法 製造而得。 首先，將上述各種材料予以溶解或分散在溶劑中，分別 地調製第一感光層形成用之第一感光性樹脂組成物溶液和 第二感光層形成用之第二感光性樹脂組成物溶液。第一感光 -28- 200537242 〜 性樹脂組成物溶液和第二感光性樹脂組成物溶液之溶劑’舉 例來說，例如其可以是甲醇、乙醇、η-丙醇、異丙醇、η-丁 醇、第二-丁醇、η -己醇等之醇類，丙酮、甲乙酮、甲基異 丁酮、環己峒、二異丁酮等之酮類，乙酸乙酯、乙酸丁酯、 乙酸-η -戊酯、硫酸甲酯、丙酸乙酯、酞酸二甲酯、安息化 酸乙酯等之酯類，甲苯、二甲苯、苯、乙基苯等之芳香族羥 類，四氯化碳、三氯乙烷、氯仿、三氯乙烷、二氯甲 烷、一氯苯等之鹵化羥類，四氫呋喃、二乙醚、乙二醇一甲 # 醚、乙二醇一乙醚、1-甲氧-2-丙醇等之醚類，二甲基甲醯胺、 二甲亞硼等。在第一感光性樹脂組成物溶液和第二感光性樹 脂組成物溶液中也可以添加公知的界面活性劑。 其次，藉由將第一感光性樹脂組成物溶液塗布於支撐體 上並予以乾燥來形成第一感光層。藉由將第二感光性樹脂組 成物溶液塗布於支撐體上並予以乾燥來形成第二感光層。 可使用來做爲前述支撐體者，必須是一種光穿透性良好 之物。又，期望表面之平滑性是良好的。支撐體的例子，舉 • 例來說，例如其可以是聚對酞酸乙二醇酯、聚萘酸乙二醇 酯、聚丙烯、聚乙烯、三乙酸纖維素、二乙酸纖維素、聚（甲 基）丙烯酸烷酯、聚（甲基）丙烯酸酯共聚物、聚氯化乙烯、聚 乙烯基醇、聚碳酸酯、聚苯乙烯、賽洛芬、聚氯化亞乙烯共 聚物、聚醯胺、聚醯亞胺、氯化乙烯•乙酸乙燦共聚物、聚 四氟乙嫌、聚二乙嫌等之各種的塑膠薄膜。更且，也可以 使用由此等之二種上所形成的複合材料。上述之中，特佳爲 聚對酞酸乙二醇酯。支撐體的厚度，通常是5~彳50微米，較 -29- 200537242 、 宜是10〜50微米。 本發明中之支撐體，另一方面是一種含有微粒子的樹脂 層積層而得之物，上述之微粒子的平均粒徑較宜是0.01〜5.0 微米，更宜是〇.〇2〜4.0微米’特佳爲〇·〇3〜3.0微米。當此 平均粒徑小於〇 . 〇 1微米時’捲取等之作業性會有劣化的傾 向；當超過5.0微米時，就會有發生解像度及感度下降之傾 向。上述微粒子之摻混量，例如，雖然是隨著構成樹脂層的 基底樹脂、微粒子的種類及平均粒徑、預定的物性等而不 φ 同，然而相對於100質量份之樹脂計通常是〇·〇5〜5質量份 左右。 上述之微粒子，舉例來說，例如其可以是矽石、高嶺土、 滑石、礬土、磷酸鈣、二氧化鈦、碳酸鈣、硫酸鋇、氟化鈣、 氟化鋰、沸石、硫化鉬等之無機粒子，交聯高分子粒子、草 酸鈣原之有機粒子等；由透明性之觀點來看，較宜是矽石粒 子。此等係可以單獨使用，也可以組合.2種類以上來使用。 前述樹脂層之厚度較宜是 〇.〇1〜5.0微米，更宜是 Φ 0.05〜3_0微米，特佳爲0·1〜2.0微米，極佳爲0.1~1_0微米。 當此厚度小於〇 _ 〇 1微米時，就會有得不到本發明效果之傾 向；當超過5 _0微米時，就會有聚酯薄膜之透明變差、感度 及解像度惡化之傾向。另一方面，積層前述樹脂層之方法並 沒有特別地限定，例如，可以利用塗布等之公知方法來進行。 已積層含有微粒子的樹脂層之聚對酞酸乙二醇酯的市 售品的例子，舉例來說，例如其可以是東洋紡績（股）公司製 之可斯莫塞茵Α1517、Κ1531(厚度：16微米、25微米）、帝 -30- 200537242 • 人杜邦薄膜（股）公司製之Χ91(厚度：15.5 18微米）、三菱化學聚酯薄膜（股）公司製二 16微米）。此等中之任一者均可以使用來 感光性轉印片之感光性層雖然可以？ 體的微粒子之面，也可以形成於未塗布面 之凹凸、及感光性樹脂組成物塗布後的捲 較宜是將感光層形成於未塗布微粒子之面 本發明之感光性轉印片，可以在第二 • 置如前述之保護薄膜。上述之保護薄膜的 例如其可以是使用於前述支撐體之物、以 乙烯、聚丙烯的紙等。特佳爲聚乙烯薄膜 護薄膜之厚度通常是5〜100微米，較宜| 時，感光性樹脂層和支撐體的拉著力A、 保護薄膜的接著力B，必須是成爲A>B ^ 護薄膜之組合的例子，舉例來說，例.如其 二醇酯/聚丙烯、聚對酞酸乙二醇酯/聚乙 • 賽洛芬、聚醯亞胺/聚丙烯等。除了如以_ 保護薄膜相互不同種類物質的選取方法以 和保護薄膜之至少一者進行表面，可使接 係。一般而言，支撐體之表面處理係爲了 脂層間之接著力，舉例來說，例如可以塗 電處理、火焰處理、紫外線照射處理、高 光放電照射處理、活性電漿照射處理、雷 來實施。又，支撐體和保護薄膜間之靜電 微米、17.5微米、 R340G 1 6(厚度： 做爲支撐體。 衫成於塗布有支持 ，然而從光阻表面 取之安定性來看， 上。 感光層上進一步設 例子，舉例來說， 及紙、或積層有聚 、聚丙烯薄膜。保 I 1 0〜50微米。此 與感光性樹脂層和 L關係。支撐體/保 可以是聚對酞酸乙 i烯、聚氯化乙烯/ 上所述之支撐體和 外，藉由對支撐體 著力滿足前述之關 達成提高感光性樹 設底塗層、電暈放 周照射波處理、輝 射光線照射處理等 摩擦係數也是很重 200537242 « - 要的。此等靜電摩擦係數較宜是0.3〜1·4,特佳爲0.5〜1.2。 當小於0 · 3時，由於過於滑溜而於捲成圓筒時會發生捲縫。 又，當超過1 · 4的情況下，則於捲成良好的圓筒狀。 又，保護薄膜也可以進行表面處理。表面處理之進行係 爲了降低和感光性樹脂層間之接著性。例如，可以在保護薄 膜的表面上設置聚有機矽氧烷、氟化聚烯烴、聚氟乙烯、聚 乙烯醇等之底塗層。底塗層之形成，一般係藉由在保護薄膜 表面上塗布上述之聚合物的塗布液後，再於3 0〜1 5 0 °C (特別 • 是5〇〜12〇°C )下乾燥1〜3〇分鐘來進行的。 本發明之感光性轉印片係可以非常適用於製造具有貫 穿孔或通孔之印刷電路板。 一邊參附圖之第3圖，一邊說明使用本發明之感光性轉 印片製造具有貫穿孔之印刷電路板之方法。 準備如第3(A)圖所示之具有貫穿孔22，且表面爲金屬 層23所覆蓋之印刷電路板製造用基板2 1。可以使用銅張積 層基板及在玻璃-環氧樹脂等之絕緣基材上形成銅被覆層之 • 基板來做爲印刷電路板製造用基板2 1。 其次，如第3(B)圖所示使用加壓輥31將本發明之感光 性轉印片1 〇之第二感光層1 3壓貼在印刷電路板形成用基板 21之表面上。藉此將印刷電路板形成用基板2 1、第二感光 層1 3、第一感光層1 2、然後支撐體1 1，依照此順序予以積 層而得到積層體。感光性轉印片之積層係可以在室溫（15〜30 °C )或加熱下（30〜180°C )下進行。特別理想是於60~140°C下 進行。 -32- 200537242 . 又，也可以改變所使用的感光性轉印片，在印刷電路板 形成用基板之表面上依照順序直接塗布感光性轉印片製造 用之第二感光性樹脂組成物溶液和第一感光性樹脂組成物 溶液，並藉由乾燥而得依照印刷電路板形成用基板、第二感 光層、然後第一感光層之順序積層而得的積層體。 其次，如第3(C)圖所示，從積層體之支撐體1 1側之面 進行光照射將感光層予以硬化。在印刷電路板形成用基板 21之電路圖案形成區域上照射預定之圖案狀的用以使第二 # 感光層13硬化所需的光量之光，而形成電路圖案形成用的 硬化層1 5之區域（電路部曝光工程）。在印刷電路板形成用 基板之貫穿孔22的開口部及其周圍上，分別照射用以使第 一感光層12和第二感光層13硬化所需要的光量之光，而形 成貫穿孔之金屬層保護用之硬化層16的區域（孔部曝光工 程）。電路部曝光工程和孔部曝光工程可以分別獨立地進 行，較宜是並行地進行。曝光可以藉由照射透過光罩之光來 進行，或者使用雷射曝光裝置照射雷射光來進行。曝光所使 ® 用的光源，可以使用透過支撐體11，並可以產生對於所使 用的光聚合起始劑而言爲活性之電磁波，且波長爲3 1 0〜7 0 0 奈米（較宜是3 5 0〜5 0 0奈米）之範圍的紫外線到可見光線之 光源。例如，可以使用（超）高壓水銀燈、氙燈、碳弧燈、鹵 素燈、複印用之螢光燈管、半導體雷射等之公知的光源。 其次，如第3(D)圖所示，從積層體剝離支撐體11。 接著，如第3 ( E )圖所示，於適當的顯像液中將印刷電路 板形成用基板21上之第一感光層12和第二感光層13之未 -33 - 200537242 f . 硬化區域予以溶解除去，並將電路圖案形成用之硬化層15 和貫穿孔之金屬層保護用之硬化層1 6予以顯像，露出基板 表面之金屬層23(顯像工程）。就顯像液而言，舉例來說，例 如其可以是鹼性水溶液（例如，碳酸鈉溶液）、含有機溶劑之 鹼性水溶液、及有機溶劑。 其次，如第3(F)圖所示，以蝕刻液將基板表面之已露出 的金屬層23予以溶解除去（蝕刻工程）。藉此在印刷電路板 形成用基板21上形成電路圖案24。在以銅形成金屬層23 # 之情況下，蝕刻液可以使用氯化亞鐵水溶液、氯化銅水溶 液、及氯化亞銅水溶液。 接著，如第3(G)圖所示於氫氧化鈉或氫氧化鉀等之強鹼 性水溶液中，將硬化層1 5、1 6從印刷電路板形成用基板予 以除去做成剝離片17(硬化層除去工程）。 【實施例】 在支撐薄膜（K1531(具有含平均粒徑爲0_06微米之矽的 樹脂層）：東洋紡績（股）公司製、25微米厚之聚對酞酸乙二 ® 醇酯薄膜）的微粒子層未塗布面上，塗布由下述之組成所構 成的第一感光性樹脂組成物溶液，並予以乾燥而形成25微 米厚之感光層（第一感光層）。 -34- 200537242 m - 〔第一感光性樹脂組成物溶液之組成〕 甲基丙烯酸甲基酯/2 -乙基己基丙烯酸酯/苄15質量份 基甲基丙烯酸酯/甲基丙烯酸共聚物（共聚物 組成（莫耳比：55/1 1.7/4.5/28.8、質量平均分 子量：90000、Tg : 7(TC)) 6.5質量份 1 . 5質量份 0.0 4質量份 1.0質量份 0.5質量份 0.0 2質量份 0.0 1質量份 0.2質量份 0.1質量份 30質量份 十二聚丙二醇二丙烯酸酯 四乙二醇二甲基丙烯酸酯 4-4’-雙（二乙胺基）二苯甲酮 B二苯甲酮 P -甲苯磺醯胺 孔雀綠草酸鹽 3-嗎啉甲基-1 -苯三唑-2-硫酮 無色結晶紫 三溴甲基苯基颯 甲乙酮 接著，在第一感光層之上塗布由下述之組成所構成的第 二感光性樹脂組成物溶液，並予以乾燥而形成5微米厚之感 光層（第二感光層）。 -35 - 200537242 〔第二感光性樹脂組成物溶液之組成〕 甲基丙烯酸甲基酯/2-乙基己基丙烯酸酯/苄 基甲基丙烯酸酯/甲基丙烯酸共聚物（共聚物 組成（莫耳比：55/1 1 .7/4.5/28.8、質量平均分 子量：90000、Tg: 50°C)) 1 5質量份 十二聚丙二醇二丙烯酸酯 6.5質量份 四乙二醇二甲基丙烯酸酯 1·5質量份 4-4’·雙（二乙胺基）二苯甲酮 〇 · 4質量份 二苯甲酮 3 _ 〇質量份 p -甲苯擴醯胺 〇 · 5質量份 孔雀綠草酸鹽 〇·〇2質量份 3 -嗎啉甲基-1 -苯三唑-2 -硫酮 〇 · 〇 1質量份 無色結晶紫 0 _ 2質量份 三溴甲基苯基颯 〇 _ 1質量份 甲乙酮 30質量份 最後在第二感光層之上積層20微米厚之聚乙烯薄膜而 得到感光性轉印片。藉由下述之方法來測定此種做法所得到 的感光性轉印片之感度，結果用以將第二感光層予以硬化所 需要的光量A係爲4 mJ/cm2，用以將第一感光層予以硬化 所需要的光量B係爲40 mJ/cm2，到第一感光層開始硬化所 需要的光量C係爲14 mJ/cm2(光量C和光量A之差爲1〇 mJ/cm2)。 〔感度之測定方法〕 - 36- 200537242 、 在感光性轉印片之感光層上，使用高壓水銀燈，從聚對 酞酸乙二醇酯薄膜側，以21/2倍之間隔照射自0_1 mJ/cm2 到1 00 mJ/cm2的不同光量之光。接著，剝取聚對酞酸乙二 醇酯薄膜，以碳酸鈉水溶液溶解除去感光層之未曝光部，將 硬化層予以顯像，並測定該硬化層之厚度。其次’繪製而得 到光之照射量和硬化層之厚度間之關係的感度曲線。由此種 做法所得到的感度曲線讀取硬化層之厚度成爲5微米時之 光量（光量A)、硬化層之厚度成爲30微米時之光量（光量 # B)、硬化層之厚度超過5微米時之光量（光量C)。 〔印刷版電路板之製造〕 在內壁上備有銅被覆層、具有直徑爲3毫米之貫穿孔、 表面爲以經硏磨、乾燥之銅層所覆蓋，將經剝離聚對酞酸乙 二醇酯薄膜之感光性轉印片的第二感光層予以重疊，使用熱 輥積層機以不使氣泡跑入地壓接，並以銅張積層板、第二感 光層、第一感光層、然後聚對酞酸乙二醇酯薄膜之順序進行 積層而得到積層體。從所得到的積層體之聚對酞酸乙二醇酯 • 薄膜之上方，使用具有405奈米之藍色雷射光源之曝光裝 置，以預定圖案狀的4 mJ/cm2之光照射銅張積層板的電路 圖案形成區域；另一方面，銅張積層板之貫穿孔的開口部及 其周圍區域上照射40 mJ/cm2之光而將感光層予以曝光。曝 光後，從積層體剝取聚對酞酸乙二醇酯薄膜，接著將濃度爲 1質量。/。之烹酸鈉水溶液噴灑在第二感光層表面上，將第一 感光層和第二感光層之未硬化區域予以溶解除去而得到硬 化層浮雕。 -37 - 200537242 、 觀察銅張積層板之硬化層圖案時，在電路圖案形成區域 上之硬化層、及貫穿孔開口部上之硬化層上見不到剝痕及破 損等之缺陷。又，測定硬化層之厚度時，電路圖案形成區域 上之硬化層的厚度爲5微米，而貫穿孔開口部上之硬化層的 厚度爲30微米。更且，在圖案上觀察不到缺損等之缺陷。 其次，在銅張積層板之表面上，噴灑塗布氯化鐵鈾刻劑 (含有氯化鐵之蝕刻溶液），溶解除去不爲硬化層所覆蓋而顯 露的區域之銅層，接著噴灑濃度爲2質量。/。之氫氧化鈉水溶 • 液而除去硬化層浮雕，進而得到具有貫穿孔、在表面上備有 電路圖案狀之銅層的印刷電路板。以目視觀察所得到的印刷 電路板之貫穿孔時，在貫穿孔內壁的銅被覆層上見不到異常 現象。 【圖式簡單說明】 第1圖爲依照本發明的感光性轉印片之一例的斷面圖。 第2 ·圖係顯示表明從支撐體側照射光於本發明之感光 性轉印片時之光照射量和硬化層之厚度間的關係感度曲線 1之圖。 第3圖係爲顯示具有依照本發明之貫穿孔的印刷電路 板的製造程序之圖。 【元件符號 說 明 ] 10 感 光 性 轉 印片 11 支 撐 體 12 第 一 感 光 層 13 第 二 感 光 層 -38- 200537242 14 保 護 薄 膜 15 電 路 圖 案 形 16 貫 穿 孔 之 金 17 剝 離 片 2 1 印 刷 電 路 板 22 貫 穿 孔 23 金 屬 層 24 電 路 圖 案 31 加 壓 輥200537242 w. 9. Description of the invention: [Technical field to which the invention belongs] The present invention relates in particular to a photosensitive transfer sheet useful for the manufacture of printed circuit boards. The present invention also relates to a method for manufacturing a printed circuit board using the above-mentioned photosensitive transfer sheet. [Prior art] In the manufacturing field of printed circuit boards, circuit patterns are obtained by using a photosensitive layer formed on a support (particularly a flexible transparent film support) and the support. The formed photosensitive transfer sheet is formed by a photolithography technique. For example, in the case of a printed circuit board having a through hole, a through hole is formed on a substrate for forming a printed circuit board (for example, a copper laminate), and a metal layer is formed on the inner side wall portion of the through hole. A photosensitive transfer sheet is laminated on the surface of the substrate, and light is irradiated onto the circuit pattern forming area and the area containing the opening portion of the through hole, and is cured to form a photosensitive layer having a predetermined pattern shape. Then, the photosensitive transfer sheet is peeled off. The support body, after removing the hardened layer on the circuit pattern formation area and the hardened layer (called the tent film) on the through hole opening area, then the exposed metal layer A part is subjected to an etching treatment, and then a hardened layer is removed to form a circuit pattern on the surface of the substrate. In order to increase the resolution of the photosensitive transfer sheet, it is effective to reduce the thickness of the photosensitive layer. However, when the thickness of the photosensitive layer is made thinner, there is a problem that the hardened layer is deformed in the edge portion of the through hole, and the thinned thickness makes the hardened layer easily broken when the printed circuit board is manufactured. Therefore, ′ has been developing a photosensitive transfer sheet that can form a high-resolution pattern and can form a hardened layer that is difficult to be damaged. For example, Patent Document 1 discloses a support having a first photosensitive layer provided with a first photosensitive layer which is soluble in solution, has low mobility due to heating, and senses active energy rays, and further includes a support provided thereon. A photosensitive transfer sheet provided with a second photosensitive layer that is alkali-soluble, has high fluidity due to heating, and senses active energy rays. This patent document also describes that the metal layer of the through hole can be protected by burying the second photosensitive layer of the photosensitive transfer sheet in the through hole. However, since the hardened resin (the second photosensitive hardened material) that has been buried in the through hole has to be removed in the final step of the printed circuit board manufacturing, there is a problem that the manufacturing process of the printed circuit board becomes complicated . In recent years, electronic devices have been promoted to be smaller and lighter, and printed circuit boards have been required to be miniaturized circuits, and thinner photoresist patterns have been required, and high-resolution photographic transfer sheets have been required. However, the conventional photosensitive transfer sheet cannot meet this requirement. That is, since the above-mentioned photosensitive transfer sheet is exposed through a support, in order to increase the resolution, the thickness I of the support should be made thin. However, on the other hand, the support system is required to have a certain degree of self-retainability to play the role of a support when coating the photosensitive resin composition, so a thickness of about 15 to 25 microns is generally required, and For conventional light-transmitting support films, it is currently not possible to meet the requirements for high resolution. For these requirements, various attempts have been made to achieve high resolution. For example, a method in which the support is peeled off prior to exposure and the negative film is directly adhered to the photosensitive layer. Generally, the photosensitive layer maintains a certain degree of adhesion to the substrate. When this method is directly applied, the negative film 200537242 is used. When it is in close contact with the photosensitive layer, it is difficult to peel off the negative film, which not only reduces workability, but also contaminates the negative film with the photosensitive resin, and reduces the sensitivity due to air blocking. Therefore, attempts have been made to improve this method by using a non-adhesive layer for two or more photosensitive layers and a layer in direct contact with the negative film. (Refer to Patent Document 2 and Patent Document 3). However, this method has multiple layers of the light-sensitive layer, so it has no effect on reducing sensitivity in addition to the coating process. In other methods, attempts have been made to provide an intermediate layer on the photosensitive resin composition to solve these disadvantages, such as Patent Document 4, Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8, These are shown in Patent Document 9, Patent Document 10, and the like. However, in any of these, an intermediate layer must be provided between the support and the photosensitive layer, the application requires two procedures, and the thin intermediate layer is difficult to handle. The transparent film is used as a support, and it contains irregularities on the surface of the film due to manufacturing reasons. In terms of the formation of high-resolution patterns, the bone-like material will cause adverse effects during exposure and cause defects such as depressions on the photoresist wheel. In Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14, etc., although a method for solving the above-mentioned problems in the formation of a high-resolution pattern by improving the support is disclosed, it is not possible to use a conventional photosensitive layer. Thickness to obtain sufficient resolution. [Patent Document 1] JP 8-54732 [Patent Document 2] JP 1-22 1 735 [Patent Document 3] JP 2-2301 49 [Patent Document 4] JP 56-40824 JP 200537242, [Patent Document 5] JP 5 5-5 0 1 0 7 2 [Patent Document 6] JP 5 4 -1 2 2 1 5 [Patent Document 7] JP 4 7-4 6 9 [Patent Document 8] JP 5 9-9 7 1 3 8 [Patent Document 9] JP 5 9-2 1 6 1 4 1 [Patent Document 10] Special Kai Sho 63-1 97942 [Patent Document 11] Japanese Patent Laid-Open Publication No. 2001-13681 [Patent Literature 12] Japanese Patent Laid-Open Publication No. 2001-921 23 [Patent Literature 13] Japanese Patent Laid-Open Publication No. 2001-921 24 [Patent Literature] 14] Japanese Unexamined Patent Publication No. 2001-921 25 [Summary of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to provide a hardened layer (tent film) which has a high resolution and can form a high strength. Photosensitive transfer sheet of a photosensitive layer. Again, the hair. The purpose of Ming is also to provide a method for using the photosensitive transfer sheet to facilitate the industrial manufacture of printed circuit boards with through holes or through holes. [Means to solve the problem] The present invention is a photosensitive transfer sheet, which is characterized in that it is tied to a support, and is sequentially laminated with a binder polymer, an ethylenically unsaturated bond containing a monomer, and photopolymerization. A relatively low-sensitivity first photosensitive layer formed from an initiator and a photosensitive resin composition, and polymerized and hardened by the irradiation of light with an ethylenically unsaturated bond-containing monomer, and then laminated with a binder polymer 5, ethylenic unsaturated bond contains monomer, photopolymerization initiator, and photosensitive resin composition 200537242. A relatively high-sensitivity second photosensitive layer formed by laminating and curing the ethylenically unsaturated bond-containing monomer by irradiation with light; and _ kinds of photosensitive transfer sheets, characterized by : On the surface on one side of the support, a support in which a resin layer containing fine particles has been laminated is used. A preferred aspect of the present invention is shown below. (1) The thickness of the second photosensitive layer (high-sensitivity layer) is in the range of 1 to 10 microns. (2) The thickness of the first photosensitive layer (low-sensitivity layer) is less than 50 microns, and it is thicker than the thickness of the second photosensitive layer. Φ (3) The ratio a / B between the amount of light A required to harden the second photosensitive layer and the amount of light B required to harden the first photosensitive layer is 0. 01 ~ 0. 5 range. (4) The difference C-A between the amount of light A required to harden the second photosensitive layer and the amount of light C before the first curing of the first photosensitive layer is less than that used to harden the second photosensitive layer The required amount of light A is 10 times. (5) The difference C-A between the amount of light A required to harden the second photosensitive layer and the amount of light C before the first hardening of the first photosensitive layer is _ 100mJ / cm2 or less. (6) The first photosensitive layer and the second photosensitive layer contain a binder polymer, an ethylenically unsaturated bond containing monomer, and a photopolymerization initiator, and the second photosensitive layer contains A photosensitive layer also has many photopolymerization initiators. (7) The second photosensitive layer further contains a sensitizer. (8) For printed circuit board manufacturing. In addition, the present invention is also a manufacturing method for manufacturing a printed circuit board having a through-hole or a through-hole by covering the inner wall surface with a metal layer-10-200537242-(1) preparing a through-hole or The through-holes and the surface are subjected to the step of forming a printed circuit board-forming substrate covered with a metal layer; (2) pressing the photosensitive transfer sheet of the present invention on the surface of the printed circuit-board-forming substrate in accordance with printing The step of forming a laminated body by sequentially laminating layers of a substrate for forming a circuit board, a second photosensitive layer, a first photosensitive layer, and a support; (3) From the support side of the laminated body to the substrate for forming a printed circuit board The circuit pattern forming area is irradiated with a light amount required to harden the second photosensitive layer to a predetermined pattern shape, and a circuit portion exposure step is performed to form a predetermined pattern of the hardened layer area; (4) In the laminated body It is necessary to harden the first photosensitive layer and the second photosensitive layer while irradiating the area of the support body to the area of the printed circuit board-forming substrate containing the through hole or through hole. A light amount of light φ is formed into a predetermined pattern shape to form a hole exposing step of the hardened layer region covering the opening region of the through-hole or through-hole; 5) a support peeling step of peeling the support from the laminate; 6) a step of dissolving and removing the uncured area of the first photosensitive layer and the second photosensitive layer of the substrate for forming a printed circuit board to expose the metal layer of the uncured area on the substrate surface; 7) dissolving and removing the exposure with an etching solution Area metal layer etching step-11- 200537242-step; and (8) a hardened layer removing step of removing a hardened layer from a printed circuit board formation substrate. Furthermore, the present invention is also a laminated body, which is characterized in that a printed circuit board forming substrate having a through-hole or a through-hole and whose surface is covered by a metal layer is sequentially laminated with an adhesive polymer, an ethylenic polymer, and the like. A relatively high-sensitivity second photosensitivity formed from a photosensitive resin composition containing a saturated bond containing a monomer and a photopolymerization initiator and polymerizing and hardening the ethylenically unsaturated bond-containing monomer by irradiation with light Layer, and then a layer is formed of a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated bond-containing monomer, and a photopolymerization initiator, and the ethylenically unsaturated bond-containing monomer is irradiated by light. A relatively low-sensitivity first photosensitive layer is polymerized and hardened, and then a support body containing a resin layer containing fine particles is laminated on one surface and laminated in this order. [Invention and Effects] The photosensitive transfer sheet of the present invention can form hardened layers having different thicknesses by changing the amount of light exposure (exposure amount) ^. Therefore, when the photosensitive transfer sheet of the present invention is used in the manufacture of a printed circuit board having a through-hole and a through-hole, a hardened layer with a relatively high resolution and a relatively thin thickness can be formed for the circuit pattern formation area. It is possible to form a hardened layer with a high strength, which is thicker than a through-hole or a through-hole. [Embodiment] [The best form for implementing the invention] A cross-sectional view of an example of the photosensitive transfer sheet of the present invention is shown in Fig. 1 -12-200537242. in. In Fig. 1, a photosensitive transfer sheet 10 is formed by laminating a support 11, a first photosensitive layer 12, a second photosensitive layer 13, and a protective film 14 thereof in this order. The first photosensitive layer 12 and the second photosensitive layer 13 are respectively formed of a binder polymer, a monomer containing an ethylenically unsaturated bond, and a photosensitive resin composition containing a photopolymerization initiator, and are irradiated with light. The ethylenically unsaturated bond-containing monomer is polymerized and hardened. The main feature of the present invention is that the second photosensitive layer 13 has a higher sensitivity than the first photosensitive layer 12. The “high sensitivity” here means that the hardening of the second photosensitive layer 13 is initiated with less light exposure than the first photosensitive layer 12. The relationship between the amount of light irradiation and the amount of curing of the photosensitive layer in the photosensitive transfer sheet of the present invention will be described with reference to Fig. 2. Fig. 2 'is a graph showing a sensitivity curve showing the relationship between the amount of light irradiation and the thickness of the obtained hardened layer when the photosensitive transfer sheet of the present invention is irradiated with light from a support. . In Fig. 2, the horizontal axis represents the amount of light irradiated, and the vertical axis represents the thickness of the photosensitive layer that is hardened by light irradiation. D on the vertical axis represents the thickness of the second photosensitive layer, and E is the total thickness of the photosensitive layer, which is the sum of the thickness of the first photosensitive layer and the thickness of the second photosensitive layer. As shown in FIG. 2, in the photosensitive transfer sheet of the present invention, although the light irradiated from the support is advanced in the order of the support, the first photosensitive layer, and then the second photosensitive layer, The hardening process starts with a lower amount of light than the first photosensitive layer. The light amount S of the hardening start of the second photosensitive layer is preferably 0. The range is from 01 to 10 mJ / cm2. The amount of hardening of the second photosensitive layer increases as the amount of light increases, and it does not take long for the entire second photosensitive layer to harden. Make the second photosensitive layer 200537242 • The amount of light A required for curing is preferably 20 mJ / cm2 or less (especially in the range of 2 to 15 mJ / cm2). After all the second photosensitive layers are hardened, when the amount of light gradually increases, the hardening of the first photosensitive layer starts, and when the amount of light further increases, the first photosensitive layer is completely hardened. The ratio B / A of the amount of light A required to harden the second photosensitive layer and the amount of light B required to harden the first photosensitive layer is preferably 0. 〇1 ~ 0. 5 range. The amount of light C required before the first photosensitive layer starts to harden may be the same as the amount of light A required to harden the second photosensitive layer, but it is more preferable than the amount of light. The difference CA between the amount of light A required to harden the second photosensitive layer and the amount of light C required before the first photosensitive layer starts to harden is more than the light required to harden the second photosensitive layer. 10 times the exposure A (especially, 1. 1 to 10 times), more preferably 100 mJ / cm2 or less (especially 1 to 100 mJ / cm2). For a photosensitive transfer sheet having a sensitivity curve as described above, for example, the content of the photopolymerization initiator in the second photosensitive layer may be greater than that in the first photosensitive layer®, or a sensitizer may be added to the second photosensitive layer. And get. The adhesive polymer used in the photosensitive transfer sheet of the present invention is preferably a copolymer that is soluble in an alkaline aqueous solution or has characteristics that minimize swelling due to contact with the alkaline aqueous solution. Examples of copolymers in which the aqueous alkaline solution is soluble or swellable are, for example, copolymers containing vinyl polymers containing carboxyl groups and other copolymerizable vinyl monomers. The obtained carboxyl group contains a vinyl copolymer. Examples of carboxyl-containing vinyl monomers, for example, it may be -14-200537242 • (meth) acrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimerization Compounds, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and mono (meth) acrylamidoethyl phosphate. Further, an addition reaction product between a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a maleic anhydride or a cyclic anhydride such as phthalic anhydride may be used. Alternatively, an anhydride-containing monomer such as maleic anhydride or itaconic anhydride may be used as the carboxyl precursor. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Examples of other copolymerizable monomers are, for example, ethylene unsaturated monomers which do not contain an acidic group (especially a carboxyl group). In particular, those having no chemical reactivity with acidic groups are preferred. For example, (meth) acrylates, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and (meth) acrylic acid are preferred. Amine, styrene and vinyl ether. These monomers may be, for example, the following compounds. Examples of (meth) acrylates, which may be, for example, methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isobutyl (Meth) acrylate, tert-butyl (meth) acrylate, η-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethynylethyl (meth) Acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2 ethoxyethyl (meth) acrylate, 2 -(2-methoxyethoxy) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, di Ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether-15-200537242 • (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, etc. Examples of crotonic acid esters include, for example, butyl crotonic acid and hexyl crotonic acid. Examples of vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of the maleic acid diesters include, for example, dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of fumaric acid diesters include, for example, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include, for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like. Examples of (meth) acrylamide are, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N -Propyl (meth) acrylamide, Nn-butylacryl (meth) amidine, N-tert-butyl (meth) acrylamide, η-cyclohexyl (meth) acrylamide, Ν- (2-methoxyethyl) (meth) acrylamide, Ν, Ν-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Ν -Phenyl (meth) acrylamidoxamine, N-benzyl (meth) acrylamidoxamine, and (meth) acrylamidomorpholine. Examples of styrenes are, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, Hydroxystyrene, methoxystyrene, butoxystyrene, ethoxylated styrene, chlorinated styrene, dichlorinated styrene, brominated styrene, methyl chloride, vinyl benzoic acid Methyl ester, and α-methylstyrene. Examples of the vinyl ethers include, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxy-16-200537242 methyl ethyl ether. Other vinylpyridines, vinylpyrrolidone, ethyl carbazole, and (meth) acrylonitrile can also be used. Among these compounds, only one kind may be used, or two or more kinds may be used in combination. Particularly good copolymerizable monomers are methyl (meth) propionate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, styrene, α-methyl Styrene, chlorinated styrene, brominated styrene, and hydroxystyrene. § The carboxyl group contains repeating units with a carboxyl group in the ethylene copolymer, and it is preferably 1 to 60 moles of the repeating units of the entire copolymer. /. The range is preferably 5 to 50 moles. /. A particularly preferred range is from 10 to 40 mole%. The carboxyl group contains the molecular weight of the ethylenic copolymer. The average molecular weight is preferably in the range of 1,000 to 200,000, and particularly preferably in the range of 4,000 to 100,000. The content of the binder in the photosensitive layer is preferably in the range of 5 to 96% by mass, and particularly preferably in the range of 40 to 80% by mass in both the first photosensitive layer and the second photosensitive layer. ® Examples of suitable ethylenically unsaturated bond-containing monomers are compounds having at least two ethylenically unsaturated double bonds (hereinafter, also referred to as polyfunctional monomers). For example, compounds described in, for example, Japanese Patent Publication No. 36-5093, Japanese Patent Publication No. 35-1 471, Japanese Patent Publication No. 44-28727, and the like can be exemplified as such polyfunctional monomers. Examples of the compounds ((meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ether compounds, vinyl esters) described in the above-mentioned publications) may be as follows . Examples of (meth) acrylates and methacrylates are -17-200537242 • Say 'for example, they can be polyacrylates and polymethacrylates of polyols (here "poly" refers to Di (meth) acrylates above); examples of such polyols are, for example, polyethylene glycol, polypropylene glycol, polybutanediol, polyhexane, polystyrene, polystyrene Oxetane, tetrahydrofuran, cyclohexanediol, xylene glycol, di-(/ 3-hydroxyethoxy) benzene, glycerol, diglycerol, neopentyl glycol, trimethylolpropane, trihydroxyethyl Alkane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, butanediol, butanetriol, 2-butane-1,4-diol, 2-n-butyl-2-ethyl-propanediol, 2-butane-1,4 · diol 3- ® chloro-1,2-propanediol, 1,4-cyclohexanedimethanol, 3-cyclohexane-1,1-dimethanol, decalindiol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3,4-tetrahydro Naphthalene, 2,5-dimethyl-2,5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol , Dodecanediol, erythritol, 2-ethyl-1,3-propanediol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-2_ Methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexane-2,5-diol, hydroxybenzyl alcohol, hydroxyethylresorcinol, 2-methyl-1,4 -Butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, glutarol®, 1-phenyl-1,2-ethylene glycol, propylene glycol, 2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-P-xylene-αdiol, 1,1,4,4-tetraphenyl- 1,4-butanediol, 1,1,4,4-tetraphenyl-2-butane-4-diol, 1,2,6-trihydroxyhexane, 1,1'-bis-2-naphthalene Alcohol, dihydroxynaphthalene, 1, Γ-methylene-di-2-naphthol, 1,2,4-benzenetriol, biphenol, 2,2'-bis (4-hydroxyphenyl) butane, 1,1 · bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, Hydroxybenzyl alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, fluorinated glycidyl alcohol, pyroglycerol, -18- 200537242 • resorcinol, glucose, α -(1-aminoethyl) -p- Benzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1, 3-propanediol, 3-amino-1,2-propanediol, N- ( 3-aminopropyl diethanolamine, ν, N, · bis-2- (2-hydroxyethyl) piperin, 2,2-bis (hydroxymethylbuth 2,2,2 ,,-nitrotri Ethanol, 2,2-bis (hydroxymethyl) propionic acid, 1,3 · bis (hydroxymethyl) urea, 1,2-bis (4-P than pyridyl) -1,2-ethylene glycol, Nn -Butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-hydrothio · 1,2-propanediol, 3-pyridyl-1, 2-propanediol, 2- (2-pyridyl) -1 , 3-propanediol, triethanolamine, α- (1-aminoethyl p-hydroxybenzyl alcohol, 3-amino-4_hydroxyphenylfluorene, etc. Among these acrylates and methacrylates, the best example is' for example, from the viewpoint of easy availability, for example, it may be ethylene glycol diacrylate, diethylene glycol diacrylate , Triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Dimethacrylate, polyethylene glycol dipropionate, tetrapropylene glycol diacrylate, dodecanepropylene glycol diacrylate, trimethylolane triacrylate, trimethylolmethylpropane trimethacrylate, Pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glyceryl triacrylate, diglyceryl dimethacrylate, 1,3-propanediol diacrylate Ester, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, cyclic Trimethylol Triacrylate and the like. Examples of acrylamide and methacrylamide, for example, ‘for example -19- 200537242. It can be methylene bisacrylamide, methylene bismethylamine with ethylenediamine, diaminopropane, diaminobutane, hexamethylenediamine, bis (2-aminopropyl) Amines, diethylidenemethylenediamine, octamethylenediamine, and polyamines ringed with heteroatoms (e.g., phenylenediamine, dimethylenediamine, ethylamine, diaminobenzoic acid, diamine Amine toluene, diamine, etc.) and other polyacrylamide and polymethacrylamide. Examples of allyl compounds, such as, for example • terephthalic acid, sebacic acid, adipic acid, glutaric acid, and allyl diallyl, diallyl nitrate, anthraquinone disulfonic acid, pyrene Hydroxy-P-benzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid and diallyl esters of naphthalene, and dipropenamide. By way of example, the vinyl ester may be, for example, the aforementioned polyethylene glycol ethylene glycol divinyl ether, 1,3,5_tri-yS-vinyloxydi / 3 / 3-vinyloxyethoxybenzene And glyceryl triethylene, for example, for example, it may be divinyl alkenyl adipate, divinyl phthalate, divinyl benzene-1, 3-disulfonate Examples of divinyl butane-1,4-ethylene compounds include, for example, βρ-allylstyrene and P-isopropylstyrene. Compounds other than the above compounds, for example, (methacrylamide) ethyl acrylate, N, N_oxyethyl) acrylamine, allyl methacrylate, etc .; different ethylenically unsaturated Compounds with double bonds, in addition to acrylamide, in addition to pentamethylene diamine, triamine diamine, heptamine polyamine, and cold- (4-aminophenyl) anthraquinone, diamine I It may be a dicarboxylic acid such as phthalic acid, an acid, etc .: Examples of disulfonic acids such as disulfonic acid, 2,5-disulfonic acid, and the like, dienyl ethers (for example, ethoxybenzene, 1, 3-yl ether), vinyl ester succinate, diethyl terephthalate, diethylene disulfonate, etc. Benzene: is divinylbenzene, such as N- / S-hydroxyethyl • bis (/ 3-methacrylic acid), which has 2 or more, and has at least two hydrogens -20- 200537242. A reaction product obtained by reacting a polyhydric alcohol compound having an oxy group and a slightly excess polyisocyanate compound having at least two isohydrogen groups, and having ethylenic unsaturation having at least one hydroxyl group and at least one A polyfunctional polyurethane compound having at least two ethylenically unsaturated double bonds obtained by reacting a basic compound is also an ideal compound suitable for use in the present invention. These polyfunctional monosystems can be used alone or in combination of two or more. The content of the polyfunctional monomer in the photosensitive layer is preferably 5 to 90 weights in both the first photosensitive layer and the second photosensitive layer. /. Particularly preferred is 15 to 60% by weight. The photopolymerization initiator may be, for example, an aromatic ketone, a vicinal polyketoaldehyde compound disclosed in the specification of US Patent No. 2367660, or a ketone ether compound disclosed in the specification of US Patent No. 2448828. 2. United States Patent No. 272251 No. 2 Specification for Alpha-Hydrocarbon Substituted Compounds; U.S. Patent No. 30461 No. 27 and U.S. Patent No. 295 1 758; Polynuclear Quinone Compounds; No. 3549367 A combination of a triarylimidazole compound and a P-amine • ketone disclosed in the specification, a benzothiazole compound and a trihalomethyl-S-sanken compound described in Japanese Patent Publication No. 51-4851 6, and a U.S. patent The trihalomethyl-S-triple compound described in the specification No. 4239850, the trihalomethylthiadiazole compound described in the specification No. 42 1 2976, and the like. In particular, aromatic ketones are particularly preferred. Preferred examples of the above-mentioned aromatic ketones include, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4 -Methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4--21-200537242 • bromobenzophenone, 2.carboxybenzophenone, 2-ethoxy Carbonyl benzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, cardiac methoxy-4'-dimethylaminobenzophenone, 4,4, -dimethoxybenzophenone, 4 -Dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, xanthonone, thiophene Tonone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, amidine, acridone and benzoin, benzoin ethers (for example, Benzoin methyl ether, Benzoin ether, Benzoin propyl ether, Benzoin isopropyl ether, Benzoin phenyl ether, Benzyl dimethyl ketal), 4,4'-bis (dialkyl Amines) benzophenones (eg #, 4,4'-bis (dimethylamine) benzophenone, 4,4, bis (dicyclohexylamine) benzophenone, 4,4'- double( Ethyl amine) benzophenone, 4,4'-bis (diethanolamine) benzophenone). A particularly preferred example is, for example, benzophenone. The content of the photopolymerization initiator in the photosensitive layer is generally 0 in both the first photosensitive layer and the second photosensitive layer. 1 to 10% by weight, more preferably 0 to 5 to 5% by weight. In the case where the sensitivity difference between the first photosensitive layer and the second photosensitive layer is adjusted by the content of the photopolymerization initiator, the content of the photopolymerization initiator of the second photosensitive layer is relative to the photopolymerization of the first photosensitive layer. The content of the initiator is more preferably _1.5 to 10 times, and particularly preferably 2 to 5 times. In the photosensitive transfer sheet of the present invention, a sensitizer may be added to the photosensitive layer. The sensitizer is usually added only to the second photosensitive layer. Suitable as a sensitizer, for example, known polynuclear aromatics (for example, Ϊ, 茈, triphenylene), glutenoids (for example, fluorescein, Red, erythromycin, rhodamine B, Bengal rose red), phthalocyanines (for example, thiocarbonated phthalocyanine, oxycarbonated phthalocyanine), merocyanines (for example, merocyanine, carbonized merocyanine), Thienol (for example, thizone, methylene-22-200537242 • radical blue, toluidine blue), acridine (for example, acridine orange, chloroflavin, acrylflavin, alkylacridine), anthraquinone Class (for example, anthraquinone), squid iron (for example, 'squalin'), and coumarins (for example, coumarin_1, coumarin-102, coumarin_152). The addition amount of the sensitizer should be 0. relative to the total composition of the photosensitive layer. 05 ~ 30 quality. /. The range is more preferably 0. 1 ~ 20 quality. /. The range is particularly preferably in the range of 0.2 to 10% by mass. The photosensitive layer of the photosensitive transfer sheet of the present invention may contain a luffin base dimer. Examples of dimethoprim bases, for example 'may be 2- (2'_ • chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl ) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2 '· fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (4'-methoxyphenyl) -4,5-diphenylimidazole dimer. The photosensitive layer of the photosensitive transfer sheet of the present invention may contain, for example, an organic sulfur compound, a peroxide, a latex compound, and an azo as described in Chapter 5 of "Photosensitive System" by J. Korsal. And diazo compounds, photoreducible pigments, and organic halogen compounds. Examples of organic sulfur compounds are, for example, di-η-butyl disulfide, dibenzyl disulfide, 2-hydrothiobenzothiazole, 2-hydrothiobenzopyrene Azole, thiophenol, ethyltrichloromethane sulfate, 2-hydrothiobenzimidazole. Examples of the peroxide include, for example, di-t-butyl peroxide, benzophenone peroxide, methyl ethyl ketone peroxide, and the like. The latex compound is a substance composed of a combination of a peroxide and a reducing agent '. For example, it can be a ferrous ion and a persulfate ion, an iron ion and a peroxide. Azo and diazo compounds, for example, which may be, for example, α, α-azobisbutyronitrile, 2-azobis-2-methylbutyronitrile, p-amine-23- 200537242 β-based diphenylamine Diazo key class. Photoreducible pigments can be, for example, bengal rosin, erythromycin, eosin, p-flavin, riboflavin, and phytocyanine. Examples of organic halogen compounds, which may be, for example, 2-trichloromethyl-5 -phenyl-1,3,4-fluorenediazole, 2-trichloromethyl-5- (chlorophenyl) -1,3,4-fluorenediazole, 2-trichloromethyl- 5- (1-naphthyl) -1,3,4-fluorenediazole, 2-trichloromethyl- 5- (2-naphthalene Group) -1,3,4-fluorenediazole, 2-tribromomethyl-5 -phenyl-1,3,4-esoxadiazole, 2-tribromomethyl-5 (2-naphthyl) -1,3,4-Boxadiazole, 2-trichloromethyl-5-styryl-1,3,4-aradiazole, 2-trichloromethyl-5- (4-chlorobenzeneΦ Vinyl M, 3,4-esoxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-esoxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-fluorenediazole, 2-trichloromethyl- 5- (4-η · butoxystyryl) -1,3,4-aradiazole, 2- Tribromomethyl-5-styryl-1,3,4-dioxadiazole, phenyltribromomethylphosphonium, p-nitrophenyltribromomethylphosphonium, P-chlorophenyltribromomethyl Samarium, 2,4,6-tris (trichloromethyl) -s-triple, 2-phenyl-4,6 · bis (trichloromethyl) -s · sangen, 2- (4-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triple, 2- (4-chlorophenyl) -4,6-bis (tribromomethyl) -s-trigen. ® MORE Examples of organic halogen compounds that can be used in the present invention, for example, they can be halogenated hydrocarbons, halogenated alcohol compounds, halogenated carbonyl compounds, halogenated ether compounds, halogenated ester compounds, halogenated ammonium compounds. Examples of halogenated hydrocarbons For example, it may be carbon tetrabromide, iodoform, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,1-bis (ρ · chlorophenyl ) _2,2,2-trichloroethane, 1,2-dibromo · 1,1,2-trichloroethane, 1,2,3-tribromopropane, 1 · bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropane, hexachlorocyclopentadiene, dibromocyclohexane, etc. Examples of halogenated alcohol compounds, for example, -24-200537242 • It can Yes 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, bis (iodohexamethylene) amine Isopropanol, tribromo-tertiary-butanol, 2,2,3-trichlorobutane-1,4-diol, etc. Examples of halogenated carbonyl compounds, for example, which may be 1,1- Dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, trichloropropane , 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc. Examples of halogenated ether compounds, for example, which can be 2-bromoethyl Methyl ether, 2-dibromoethyl ether, bis (2-bromoethyl) ether, 2-dichloroethyl ether and the like. Examples of halogenated # ester compounds, for example, they may be halogenated carboxylic acid esters, carboxylic acid halogenated esters, or halogenated carboxylic acid halogenated esters; for example, they may be, for example, bromine acetate Ethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropylacrylate, trichloroethyl dibromopropionate, α, / 3 -di Ethyl chloroacrylate and the like. Examples of halogenated halogen compounds, which may be, for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroethyl Lamine. , 2-bromoisopropylamine, 2,2,2-trichloropropanamine, N-chlorosuccinimide, N-bromo ® succinimine, etc. Among the organic halogen compounds, it is preferable to hold two or more halogen atoms bonded to the same carbon atom, and it is particularly preferable to hold three halogen atoms on one carbon atom. The organic halogen compound may be used singly or in combination of two or more kinds. Among these, particularly preferred organic halogen compounds are pentabromomethylphenylhydrazone and 2,4-bis (trichloromethyl) 6-phenyltriazole. The amount of the organic halogen compound used in the present invention is generally 0. relative to the total composition of the photosensitive layer. The range is from 001 to 5% by weight, preferably from 0.05 to 1% by weight. / 〇. As for the photosensitive transfer sheet of the present invention, the photosensitive layer is further added with -25- 200537242. • Heat polymerization inhibitor. Examples of thermal polymerization inhibitors, for example, which may be, for example, P-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, butylcatechol, pyrogallol, methylene chloride, chloroquinone , Naphthylamine, / 3-naphthol, 2,6-di + butyl-P-cresol, pyridine, nitrobenzene, dinitrobenzene, P-triidine, methylene blue, organic copper, methyl salicylate Wait. The thermal polymerization inhibitor contained is preferably 0. relative to the polyfunctional monomer. 001 ~ 5% by weight. For the photosensitive transfer sheet of the present invention, in order to control the film physical properties (flexibility), a plasticizer may be added to the photosensitive layer. Examples thereof include, for example, dimethyl phthalate , Dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl octyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate Phthalates, such as esters, diundecyl phthalates, diaryl phthalates, dimethyl glucose phthalates, ethyl phthaloethyl ethyl glycolates, ethylene glycol methyl phthalates Esters, butylene glycol butyl phthalates, triethylene glycol dicaprylates and other glycol esters, trimethylphenol phosphates, triphenyl phosphates and other phosphate esters, diisobutyl adipate, Dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dibutyl® maleate, etc. Sulfonamide, p-tolusulfamide, Nn-butylacetamide and other amines, citric acid triester, triethylglyceride, butyl laurate and the like. More preferred is P-toluenesulfonamide. In the photosensitive transfer sheet of the present invention, the photosensitive layer may contain a leuco-pigment. 0 An example of a leuco-pigment, for example, it may be tris (P-dimethylaminophenyl) methane. (Colorless crystal violet), tris (ρ · diethylmonthlylphenyl), Ayumi, tris (ρ-dimethylamino-o-methylphenyl) a, Tris (ρ · diethylamine) -O-methylphenyl) methane, bis (P-dibutylaminophenyl)-26-200537242. [P- (2-cyanoethyl) methylaminophenyl] methane, bis (ρ · dimethylaminophenyl) -2-quinolinylmethane, tris (ρ_dipropylaminophenyl) ) Amino triarylmethanes such as methane, 3,6-bis (dimethylamino) -9-phenylgluttonium, 3-amino-6-monomethylamino-2-methyl-9 -(o-Chlorophenyl) glutathiones, 3,6-bis (diethylamino) -9- (0-ethoxycarbonylphenyl) thioxanthan, 3,6-bis (Dimethylamino) thiothione, etc., 3,6-bis (diethylamino) -9,10-dihydro-9-phenylazidine, 3,6-bis (Benylamino) -9,1 0-dihydro-9-methyl acridinium, etc. amines-9,1 0-dihydroacridines, 3,7-bis (diethylamino) Amino groups such as phanthiene Φ phenyithiones, 3,7-bis (ethylamino) phenyl thiophenes, etc. amine phenylthiones, 3,7-bis (diethylamine) -5-hexyl-5,10-dihydrophenorphine and other dihydrogenamines, bis (P-dimethylaminophenyl) aniline methane and other aminophenylmethanes, 4-amino- Amines of 4'-dimethylaminodiphenylamine, 4-amino-α, meso-dicyanohydrocinnamate Hydrocinnamic acids, hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine, 1,4-bis (ethylamino) -2,3-dihydroanthraquinone amines-2,3 -Dihydroanthraquinones, phenethylanilines such as N, N-diethyl-P-phenethylaniline, etc., containing 10-acetamido-3,7_bis (dimethylamino) morphine Basicity of thionium etc. • The fluorenyl derivative of NH colorless pigment, tris (4-diethylamino-0-tolyl) ethoxycarbonyl, etc. does not hold the hydrogen obtained by oxidation but can Colorless compounds obtained by oxidizing chromogenic compounds, colorless indigo pigments, such as the organic amines in the oxidative color form described in US Pat. No. 30425 15 and US Pat. No. 30425 17 (for example, 4,4 '-Ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4'-methylenediamine triphenylamine, N · vinylcarbazole). Particularly preferred is colorless crystal violet. The amount of the above-mentioned colorless pigment is preferably in the range of 0.001 to 10% by weight relative to the total composition of the photosensitive layer, and particularly preferably 0.05 to 5 weights -27 to 200537242. Amount% range. In the photosensitive transfer sheet of the present invention, a dye for the purpose of coloring the photosensitive layer and imparting stability to storage can be used. Examples of suitable dyes can be, for example, brilliant green sulfate, ethyl violet, eosin, erythromycin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-bis Phenyltriacridine, Turkish Red S, Thymephthalein, Methyl Violet 2 B, Quinalidin Red, Bengal Rose Red, Mittenil Yellow, Thyme Thiophthalate, Xylenol Blue, Methyl Orange, Orange IV, Diphenyl casein, 2,7-dichlorofluorescein, p-methyl red, Congo Φ red, Benzo red violet 4 B, α-naphthalene red, Nile Blue A, Digina indicator, methyl Purple, peacock green grass acid salt, paramagenta, oil blue- # 603 (made by Dongfang Chemical Industry Co., Ltd.), rhodamine B, rhodamine 6G, etc. A particularly preferred dye is malachite greenate. In the present invention, in order to improve the adhesion between the first photosensitive layer and the second photosensitive layer, or the adhesion between the second photosensitive layer and the substrate for forming a printed substrate, a known so-called adhesion promoter can be used for the photosensitive layer. For example, it may be benzimidazole, benzisole, benzothiazole, 2-methylbenzimidazole, 2-methylfluorenylbenzoxazole, 2-methylfluorenylbenzothiazole, 3 -Morpholinylmethyl-1 -phenyl-triazol-2-thione, 3-morpholinyl-5-phenyl-pyridadiazole- 2-thione, 5-amino-3-morpholine Methyl-thiadiazole-2-thione '2-hydrothio-5-methylthio-thiadiazole and the like. More preferred is 3-morpholinomethyl-1.phenyl-triazol-2-one. The photosensitive transfer sheet "for example" of the present invention can be produced as described below. First, the above-mentioned various materials are dissolved or dispersed in a solvent, and a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition solution for forming a second photosensitive layer are separately prepared. The first photosensitive-28-200537242 ~ solvent of the second photosensitive resin composition solution and the second photosensitive resin composition solution, for example, it may be methanol, ethanol, η-propanol, isopropanol, η-butanol , Second-butanol, η-hexanol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, diisobutanone and other ketones, ethyl acetate, butyl acetate, acetic acid-η -Esters of amyl ester, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc., aromatic hydroxyls such as toluene, xylene, benzene, ethylbenzene, etc , Trichloroethane, chloroform, trichloroethane, dichloromethane, monochlorobenzene, etc., halogenated hydroxyls, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl # ether, ethylene glycol monoethyl ether, 1-methoxy- Ethers such as 2-propanol, dimethylformamide, dimethylboron, etc. A known surfactant may be added to the first photosensitive resin composition solution and the second photosensitive resin composition solution. Next, the first photosensitive resin composition solution is coated on a support and dried to form a first photosensitive layer. The second photosensitive resin composition solution is coated on a support and dried to form a second photosensitive layer. It can be used as the aforementioned support, and it must be a light-transmitting material. In addition, the smoothness of the surface is desired. Examples of support bodies, for example, can be polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly ( Alkyl (meth) acrylate, poly (meth) acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, xylofen, polyvinyl chloride copolymer, polyamide , Polyimide, Ethylene Chloride • Ethylene Acetate Copolymer, Polytetrafluoroethylene, Polyethylene Diene, etc. Furthermore, a composite material formed by these two types may be used. Among the above, particularly preferred is polyethylene terephthalate. The thickness of the support is usually 5 to 50 micrometers, preferably 10 to 50 micrometers compared to -29-200537242. The support in the present invention, on the other hand, is a laminate of resin containing fine particles, and the average particle diameter of the fine particles is preferably 0. 01 ~ 5. 0 microns, more preferably 〇. 〇2 ~ 4. 0 micron 'is particularly preferably from 0.03 to 3. 0 microns. When this average particle size is less than 0. 〇 When it is 1 micron, workability such as coiling tends to deteriorate; when it exceeds 5. At 0 microns, there is a tendency for resolution and sensitivity to decrease. The amount of the fine particles to be mixed varies, for example, with the base resin constituting the resin layer, the type and average particle size of the fine particles, and predetermined physical properties, etc., but it is usually 0 · based on 100 parts by mass of the resin. 〇5 ~ 5 mass parts. The fine particles mentioned above can be, for example, inorganic particles such as silica, kaolin, talc, alumina, calcium phosphate, titanium dioxide, calcium carbonate, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, etc. Cross-linked polymer particles, organic particles of calcium oxalate, etc .; from the viewpoint of transparency, silica particles are preferred. These systems can be used alone or in combination. Use 2 or more types. The thickness of the aforementioned resin layer is preferably 0. 〇1 ~ 5. 0 microns, more preferably Φ 0. 05 ~ 3_0 microns, especially preferred is 0 · 1 ~ 2. 0 microns, excellent is 0. 1 ~ 1_0 microns. When the thickness is less than 0 μm, the effect of the present invention will not be obtained. When it exceeds 5 μm, the transparency of the polyester film will deteriorate, and the sensitivity and resolution will tend to deteriorate. On the other hand, the method of laminating the resin layer is not particularly limited, and it can be performed by a known method such as coating. Examples of a commercially available product of polyethylene terephthalate on which a resin layer containing fine particles has been laminated may be, for example, Kosmoserin A1517, K1531 (thickness: 16 micron, 25 micron), Emperor-30- 200537242 • X91 (thickness: 15. by Ren DuPont Films Co., Ltd.) 5 18 microns), Mitsubishi Chemical Polyester Film Co., Ltd. (2 16 microns). Any of these can be used as the photosensitive layer of the photosensitive transfer sheet. The surface of the fine particles of the body may be formed on the uncoated surface, and the roll after the photosensitive resin composition is applied is preferably a photosensitive layer formed on the surface of the uncoated fine particles. Second • Place the protective film as described above. The protective film mentioned above may be, for example, a material used for the aforementioned support, paper made of ethylene, polypropylene, or the like. Particularly good is that the thickness of the protective film of the polyethylene film is usually 5 to 100 microns. When it is more suitable, the pulling force A of the photosensitive resin layer and the support body A and the adhesive force B of the protective film must be A > B ^ protective film Examples of combinations, for example, examples. Such as its glycol esters / polypropylene, polyethylene terephthalate / polyethoxylate, polyimide / polypropylene, etc. In addition to the method of selecting different kinds of substances from the protective film and the surface of at least one of the protective film and the protective film, the connection can be made. In general, the surface treatment of the support is for adhesion between the lipid layers. For example, it can be applied by electrocoating, flame treatment, ultraviolet irradiation treatment, high-light discharge irradiation treatment, activated plasma irradiation treatment, or lightning. In addition, the static electricity between the support and the protective film, micron, 17. 5 micron, R340G 1 6 (thickness: as a support. The shirt is coated with support, but from the stability of the photoresist surface, the top. Further examples are provided on the photosensitive layer, for example, and paper, or Laminated with poly, polypropylene film. I 1 0 ~ 50 microns. This is related to the photosensitive resin layer and L. The support / poly may be polyethylene terephthalate, polyvinyl chloride / the support described above. It is also important to increase the friction coefficients of the photoresist undercoat, corona radiation treatment, and glow light treatment by focusing on the support to meet the aforementioned requirements. 200537242 «-Required. The isostatic friction coefficient is preferably 0. 3 ~ 1.4, especially good for 0. 5 ~ 1. 2. When it is less than 0 · 3, curling may occur when it is rolled into a cylinder because it is too slippery. When it exceeds 1 · 4, it is rolled into a good cylindrical shape. The protective film may be surface-treated. The surface treatment is performed to reduce the adhesion to the photosensitive resin layer. For example, an undercoat layer such as polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride, or polyvinyl alcohol may be provided on the surface of the protective film. The formation of the undercoat layer is generally performed by coating the above-mentioned polymer coating solution on the surface of the protective film, and then drying it at 30 ~ 150 ° C (especially • 50 ~ 120 ° C). It took ~ 30 minutes. The photosensitive transfer sheet of the present invention is very suitable for manufacturing a printed circuit board having through holes or through holes. A method of manufacturing a printed circuit board having a through hole using the photosensitive transfer sheet of the present invention will be described with reference to FIG. 3 of the accompanying drawings. As shown in FIG. 3 (A), a printed circuit board manufacturing substrate 21 having a through hole 22 and a surface covered with a metal layer 23 was prepared. A copper laminated substrate and a substrate formed with a copper coating on an insulating substrate such as glass-epoxy can be used as the printed circuit board manufacturing substrate 21. Next, as shown in FIG. 3 (B), the second photosensitive layer 13 of the photosensitive transfer sheet 10 of the present invention is pressed against the surface of the printed circuit board forming substrate 21 using a pressure roller 31. Thereby, the printed circuit board forming substrate 21, the second photosensitive layer 1, 3, the first photosensitive layer 1, 2, and the support 11 are laminated in this order to obtain a laminated body. The lamination of the photosensitive transfer sheet can be performed at room temperature (15 ~ 30 ° C) or under heating (30 ~ 180 ° C). It is particularly desirable to carry out at 60 ~ 140 ° C. -32- 200537242. In addition, the photosensitive transfer sheet used may be changed, and the second photosensitive resin composition solution and the first photosensitive resin for manufacturing the photosensitive transfer sheet may be directly coated on the surface of the printed circuit board forming substrate in order. The composition solution is dried to obtain a laminated body obtained by laminating the printed circuit board forming substrate, the second photosensitive layer, and the first photosensitive layer in this order. Next, as shown in Fig. 3 (C), light is irradiated from the surface of the support body 11 side of the laminated body to harden the photosensitive layer. The circuit pattern forming area of the printed circuit board forming substrate 21 is irradiated with a predetermined pattern of light amount required to harden the second # photosensitive layer 13 to form a hardened layer 15 for circuit pattern forming. (Circuit Department Exposure Project). The openings and the surroundings of the through holes 22 of the printed circuit board forming substrate are irradiated with light of a light amount required to harden the first photosensitive layer 12 and the second photosensitive layer 13, respectively, to form metal layers of the through holes. Protect the area of the hardened layer 16 (exposure process of holes). The circuit portion exposure process and the hole portion exposure process can be performed independently and preferably in parallel. The exposure can be performed by irradiating light that has passed through the mask, or irradiating laser light using a laser exposure device. The light source used for exposure can use the transmission support 11 and can generate electromagnetic waves that are active to the photopolymerization initiator used, and the wavelength is 3 1 0 ~ 7 0 0 nm (more preferably 3 500 ~ 500 nanometers) in the range of ultraviolet to visible light. For example, (ultra-high pressure) mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, fluorescent tubes for copying, and semiconductor lasers can be used. Next, as shown in FIG. 3 (D), the support 11 is peeled from the laminated body. Next, as shown in FIG. 3 (E), the first photosensitive layer 12 and the second photosensitive layer 13 on the printed circuit board-forming substrate 21 are printed in an appropriate developing solution -33-200537242 f. The hardened area is dissolved and removed, and the hardened layer 15 for circuit pattern formation and the hardened layer 16 for protecting the metal layer of the through hole are developed to expose the metal layer 23 on the surface of the substrate (imaging process). As the developing solution, for example, it can be, for example, an alkaline aqueous solution (for example, a sodium carbonate solution), an alkaline aqueous solution containing an organic solvent, and an organic solvent. Next, as shown in FIG. 3 (F), the exposed metal layer 23 on the substrate surface is dissolved and removed with an etching solution (etching process). Thereby, a circuit pattern 24 is formed on the printed circuit board forming substrate 21. In the case where the metal layer 23 # is formed of copper, the etching solution may be an aqueous solution of ferrous chloride, an aqueous solution of copper chloride, or an aqueous solution of cuprous chloride. Next, as shown in FIG. 3 (G), the hardened layers 15 and 16 are removed from the substrate for forming a printed circuit board in a strongly alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to form a release sheet 17 ( Removal of hardened layer). [Example] Microparticles in a supporting film (K1531 (with a resin layer containing silicon having an average particle diameter of 0_06 microns): a 25 micron thick polyethylene terephthalate film made by Toyobo Corporation) On the uncoated side of the layer, a first photosensitive resin composition solution composed of the following composition was applied and dried to form a 25 micron-thick photosensitive layer (first photosensitive layer). -34- 200537242 m-[Composition of the first photosensitive resin composition solution] methyl methacrylate / 2-ethylhexyl acrylate / benzyl 15 parts by mass methacrylate / methacrylic acid copolymer (copolymerization Composition (Morr ratio: 55/1 1. 7/4. 5/28. 8. Mass average molecular weight: 90,000, Tg: 7 (TC)) 6. 5 parts by mass 1. 5 parts by mass 0 4 parts by mass 1. 0 parts by mass 0. 5 parts by mass 0 2 parts by mass 0. 0 1 part by mass 0. 2 parts by mass 1 part by mass 30 parts by mass twelve polypropylene glycol diacrylate tetraethylene glycol dimethacrylate 4-4'-bis (diethylamino) benzophenone B benzophenone P -tosylsulfonamide peacock Phytic acid salt 3-morpholinemethyl-1 -benzotriazole-2-thione Colorless crystal violet tribromomethylphenyl methyl ethyl ketone Next, the first photosensitive layer was coated with the following composition The second photosensitive resin composition solution was dried to form a 5 micron-thick photosensitive layer (second photosensitive layer). -35-200537242 [Composition of the second photosensitive resin composition solution] methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (mol Ratio: 55/1 1. 7/4. 5/28. 8. Mass average molecular weight: 90,000, Tg: 50 ° C)) 1 5 parts by mass Dodecyl polypropylene glycol diacrylate 6. 5 parts by mass of tetraethylene glycol dimethacrylate 1.5 parts by mass of 4-4 '· bis (diethylamino) benzophenone 0.4 parts by mass of benzophenone 3-part of p-toluene 0.5 parts by mass of peacock green grass acid salt 0.002 parts by mass 3 -morpholinemethyl-1 -benzotriazole-2 -thione 0.001 parts by mass of colorless crystal violet 0 _ 2 parts by mass 30 parts by mass of tribromomethylphenyloxo-1 part by mass of methyl ethyl ketone, and finally a 20 micron thick polyethylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. The sensitivity of the photosensitive transfer sheet obtained by this method was measured by the following method. As a result, the light amount A required to harden the second photosensitive layer was 4 mJ / cm2, which was used to photosensitize the first photosensitive layer. The amount of light B required to harden the layer is 40 mJ / cm2, and the amount of light C required to start curing of the first photosensitive layer is 14 mJ / cm2 (the difference between the amount of light C and the amount of light A is 10 mJ / cm2). [Measurement Method of Sensitivity]-36- 200537242 On the photosensitive layer of the photosensitive transfer sheet, a high-pressure mercury lamp was used to irradiate from the polyethylene terephthalate film side at a distance of 2 1/2 times from 0_1 mJ / cm2 to 100 mJ / cm2 of different light levels. Next, the polyethylene terephthalate film was peeled off, and the unexposed portion of the photosensitive layer was dissolved and removed with an aqueous sodium carbonate solution, the hardened layer was developed, and the thickness of the hardened layer was measured. Secondly, a sensitivity curve is obtained by plotting the relationship between the amount of light exposure and the thickness of the hardened layer. The sensitivity curve obtained by this method reads the light amount (light amount A) when the thickness of the hardened layer becomes 5 microns, the light amount (light amount #B) when the thickness of the hardened layer becomes 30 microns, and the thickness of the hardened layer exceeds 5 microns. The amount of light (light amount C). [Manufacture of printed circuit board] A copper coating is provided on the inner wall, with a through hole having a diameter of 3 mm, and the surface is covered with a polished and dried copper layer. The peeled polyethylene terephthalate The second photosensitive layer of the photosensitive transfer sheet of the alcohol ester film is overlapped, and the heat-roll laminator is used to press and bond without causing air bubbles to run in. The copper sheet is laminated, the second photosensitive layer, the first photosensitive layer, and then The polyethylene terephthalate film was laminated in this order to obtain a laminated body. From above the obtained polyethylene terephthalate film, the copper laminate was irradiated with light of 4 mJ / cm2 in a predetermined pattern using an exposure device having a blue laser light source of 405 nm. The circuit pattern forming area of the board; on the other hand, the opening of the through-hole of the copper laminated board and the surrounding area were irradiated with light of 40 mJ / cm2 to expose the photosensitive layer. After the exposure, the polyethylene terephthalate film was peeled from the laminate, and then the concentration was 1 mass. /. An aqueous solution of sodium picolinate is sprayed on the surface of the second photosensitive layer, and the uncured areas of the first photosensitive layer and the second photosensitive layer are dissolved and removed to obtain a hardened layer relief. -37-200537242 When observing the hardened layer pattern of the copper laminated board, no defects such as scratches and damages were found on the hardened layer on the circuit pattern formation area and the hardened layer on the opening of the through hole. When the thickness of the hardened layer was measured, the thickness of the hardened layer on the circuit pattern formation area was 5 m, and the thickness of the hardened layer on the opening portion of the through hole was 30 m. Furthermore, no defects such as defects were observed on the pattern. Next, the surface of the copper laminate is spray-coated with a ferric chloride etchant (an etching solution containing ferric chloride) to dissolve and remove the copper layer in the area that is not covered by the hardened layer, and then spray the concentration to 2 quality. /. Sodium hydroxide solution was dissolved in water to remove the hardened relief, and a printed circuit board with through-holes and a copper layer with a circuit pattern on the surface was obtained. When the through-holes of the obtained printed circuit board were visually observed, no abnormality was observed on the copper coating layer on the inner wall of the through-holes. [Brief Description of the Drawings] FIG. 1 is a cross-sectional view of an example of a photosensitive transfer sheet according to the present invention. Fig. 2 is a graph showing a sensitivity curve 1 showing the relationship between the light irradiation amount and the thickness of the hardened layer when the photosensitive transfer sheet of the present invention is irradiated with light from the support side. Fig. 3 is a diagram showing a manufacturing process of a printed circuit board having a through hole according to the present invention. [Explanation of component symbols] 10 Photosensitive transfer sheet 11 Support 12 First photosensitive layer 13 Second photosensitive layer -38- 200537242 14 Protective film 15 Circuit pattern 16 Gold of through-hole 17 Release sheet 2 1 Printed circuit board 22 Through Hole 23 Metal layer 24 Circuit pattern 31 Pressure roller
成用之硬化層 屬層保護用之硬化層 形成用基板Production hardened layer Hardened layer for metal layer protection Substrate for forming
-39--39-