201030046 六、發明說明： 【發明所屬之技術領域】 本發明關於適合於多層印刷電路板的絕緣層形成之環 氧樹脂組成物。 【先前技術】 近年來，電子機器係往小型化、高性能化進展，在多 層印刷電路板中’所建立的層被複層化，要求線路的微細 化及高密度化。 對於此進行各式各樣的努力硏究。例如，專利文獻1 中揭示含有環氧樹脂、特定的酚系硬化劑、苯氧樹脂、橡 膠粒子之環氧樹脂組成物，而且專利文獻2中揭示含有環 氧樹脂、特定的酚系硬化劑、聚乙烯縮醛樹脂之環氧樹脂 組成物。雖然此等組成物所形成的絕緣層係可達成低粗糙 度且所鍍敷形成的導體層之剝離強度的並存，但是低線膨 © 脹率的槪念係完全沒有揭示或指示。 [專利文獻1]特開2007-254709號公報 [專利文獻2]特開2007-25471 0號公報 【發明內容】 發明所欲解決的問題 本發明的課題係提供儘管使環氧樹脂組成物的硬化物 表面經粗化處理之粗化面的粗糙度比較小，該粗化面對於 鍍敷導體也能顯示高密接力，且可達成絕緣層的低線膨脹 -5- 201030046 率化之環氧樹脂組成物。 解決問題的手段 本發明者爲了解決上述問題，進行專心致力的硏究， 結果發現配合有環氧樹脂、活性酯化合物及含脂環式構造 之苯氧樹脂之特定環氧樹脂組成物，終於完成本發明。 即，本發明包括以下的內容。 [1] 一種環氧樹脂組成物，其特徵係含有（A)環氧樹 脂、（B)活性酯化合物及（C)含脂環式構造之苯氧樹 脂。 [2] 如上述[1]記載的環氧樹脂組成物，其中上述（C )苯氧樹脂的脂環式構造係萜烯構造及/或三甲基環己烷 構造。上述（C)苯氧樹脂的脂環式構造係萜烯構造及/或 三甲基環己烷構造。 [3] 如上述[1]或[2]記載的環氧樹脂組成物，其中上述 苯氧樹脂的重量平均分子量係10000〜50000。 [4] 如上述[1]〜[3]中任一項的環氧樹脂組成物，其中 當環氧樹脂組成物的不揮發成分爲100重量％時，成分（ A)的含量係10〜50重量％，成分（C)的含量係1〜20 重量％ ’且存在於環氧樹脂組成物中之環氧基與環氧硬化 劑的反應基之比率係1 : 0.4〜1 : 1.1。 [5] 如上述[1]〜[4]中任一項的環氧樹脂組成物，其係 進一步含有（D)無機塡充料。 [6] 如上述[5]記載的環氧樹脂組成物，其中當環氧樹 201030046 脂組成物的不揮發成分爲100重量％時，（D)無機塡充 料的含量係10〜70重量％。 [7] 如上述[1]〜[6]中任一項的環氧樹脂組成物，其係 進一步含有（E )硬化促進劑。 [8] 如上述[7]記載的環氧樹脂組成物，其中當環氧樹 脂組成物中所含有的環氧樹脂與苯酚性硬化劑的總量係 1 〇〇重量％時，（E )硬化促進劑的含量係〇. 1〜5重量。/〇。 〇 [9] 一種黏著薄膜，其特徵係在支持薄膜上形成有上 述[1 ]〜[8]中任一項記載的環氧樹脂組成物之層。 [10] —種預浸物，其特徵係在由纖維所成的薄片狀纖 維基材中含浸有上述[1]〜[8]中任一項記載的環氧樹脂組 成物。 [11] 一種多層印刷電路板，其特徵係藉由上述[1]〜 [8 ]中任一項記載的環氧樹脂組成物的硬化物來形成絕緣 層。 Φ [12] —種多層印刷電路板之製造方法，係包含在內層 線路基板上形成絕緣層的步驟及在該絕緣層上形成導體層 的步驟之多層印刷電路板之製造方法，其特徵係：該絕緣 層係由將上述[1]〜[8]中任一項記載的環氧樹脂組成物熱 硬化而形成，該導體層係藉由在該絕緣層表面經粗化處理 的粗化面上鍍敷而形成。 [13]—種多層印刷電路板之製造方法，係包含在內層 線路基板上形成絕緣層的步驟及在該絕緣層上形成導體層 的步驟之多層印刷電路板之製造方法，其特徵係：絕緣層 201030046 係由在內層線路基板上層合上述[9]記載的黏著薄膜，且 在剝離或不剝離支持薄膜下，將環氧樹脂組成物熱硬化， 並於硬化後在支持薄膜存在時，剝離支持薄膜而形成，而 該導體層係由在該絕緣層表面經粗化處理的粗化面上鍍敷 而形成。 [14] 一種多層印刷電路板之製造方法，係包含在內層 線路基板上形成絕緣層的步驟及在該絕緣層上形成導體層 的步驟之多層印刷電路板之製造方法，其特徵係：絕緣層 係由在內層線路基板上層合上述[10]記載的預浸物，且將 環氧樹脂組成物熱硬化而形成，而該導體層係由在該絕緣 層表面經粗化處理的粗化面上鍍敷而形成。 [15] 如上述[12]〜[14]中任一項記載之製造方法，其 中粗化處理係使用鹸性過錳酸溶液來進行。 發明的效果 藉由配合有環氧樹脂、活性酯化合物及含脂環式構造 0 之苯氧樹脂的特定環氧樹脂組成物，儘管硬化物表面經粗 化處理的粗化面之粗糙度比較小，該粗化面對於所鍍敷的 導體也顯示高密接力，且可達成絕緣層的低線膨脹率化。 【實施方式】 實施發明的形態 本發明係配合有環氧樹脂、活性酯化合物及含脂環式 構造之苯氧樹脂的特定環氧樹脂組成物。 -8- 201030046 [成分（A)的環氧樹脂] 本發明中的成分（A)之環氧樹脂係沒有特別的限定 ，例如可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、 苯酚-酚醛清漆型環氧樹脂、第三丁基兒茶酚型環氧樹脂 、萘型環氧樹脂、縮水甘油基胺型環氧樹脂、甲酚-酚醛 清漆型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂 φ 、脂環式環氧樹脂、雜環式環氧樹脂、含螺環的環氧樹脂 、環己烷二甲醇型環氧樹脂、三羥甲基型環氧樹脂、鹵化 環氧樹脂等。本發明的環氧樹脂可使用1種或2種以上。 含有1分子中具有2個以上環氧基的環氧樹脂。當環 氧樹脂組成物的不揮發成分爲1 〇〇重量％時，較佳係至少 50重量％以上係1分子中具有2個以上環氧基的環氧樹脂 。再者，較佳的態樣包含1分子中具有2以上環氧基，在 溫度20 °C爲液狀的芳香族系環氧樹脂之環氧樹脂，及1分 ❹ 子中具有3以上環氧基，在溫度20t爲固體狀的芳香族糸 環氧樹脂。尙且，本發明中所言的芳香族系環氧樹脂係意 味其分子內具有芳香環構造的環氧樹脂。又，環氧當量（ g/eq)係每1個環氧基的分子量。作爲環氧樹脂，藉由使 用液狀環氧樹脂與固形環氧樹脂，當以黏著薄膜的形態使 用環氧樹脂組成物時，顯示充分的可撓性，可形成操作性 優異的黏著薄膜，同時提高環氧樹脂組成物的硬化物之斷 裂強度’提高多層印刷電路板的耐久性。 又，作爲環氧樹脂，當併用液狀環氧樹脂與固形環氧 201030046 樹脂時，其配合比例（液狀：固形）以重量比計較佳係1 :0.1〜1: 2的範圍。若超過該範圍而液狀環氧樹脂的比 例過多，則環氧樹脂組成物的黏著性變高，以黏著薄膜的 形態使用的情況，真空層合時的脫氣性降低而變容易發生 空隙的傾向。而且，真空層合時保護薄膜或支持薄膜的剝 離性降低，或硬化後的耐熱性有降低的傾向。又，在環氧 樹脂組成物的硬化物，有難以得到充分的斷裂強度之傾向 。另一方面，若超過該範圍而固形環氧樹脂的比例過多， 則以黏著薄膜的形態使用之情況，得不到充分的可撓性， 操作性降低，在層合之際有難以得到充分的流動性等之傾 向。 於本發明的環氧樹脂組成物中，當環氧樹脂組成物的 不揮發成分爲100重量％時，環氧樹脂的含量較佳係10〜 50重量％，尤佳係20〜40重量％，更佳係20〜35量量％ 。環氧樹脂（A)的含量若在此範圍以外，則樹脂組成物 的硬化性有降低的傾向。 [成分（B)的活性酯化合物] 本發明中的（B)活性酯化合物，只要具有當作環氧 樹脂之硬化劑的機能之活性酯即可，並沒有特別的限制。 較佳係1分子中具有2個以上活性酯基的化合物，尤佳係 由具有多價羧酸的化合物與具有苯酚性羥基的芳香族化合 物所得之1分子中具有2個以上活性酯基的芳香族化合物 ，更佳係由1分子中具有至少2個以上羧酸的化合物與具 -10- 201030046 有苯酚性羥基的芳香族化合物所得之芳香族化合物，而且 該芳香族化合物的分子中具有2個以上酯基的芳香族化合 物。又，亦可含有直鏈狀或多支鏈狀高分子。而且，若爲 1分子中具有至少2個以上羧酸的化合物係含脂肪族鏈的 化合物，則可提高與環氧樹脂（A)的相溶性，若爲具有 芳香族環的化合物，則可提高耐熱性。特別地，從耐熱性 等的觀點來看，較佳係由羧酸化合物與苯酚化合物或萘酚 φ 化合物所得之活性酯化合物。作爲羧酸化合物，具體地可 舉出苯甲酸、醋酸、琥珀酸、馬來酸、伊康酸、苯二甲酸 、間苯二甲酸、對苯二甲酸、苯均四酸等。其中，從耐熱 性的觀點來看，更佳係琥珀酸、馬來酸、伊康酸、苯二甲 酸、間苯二甲酸、對苯二甲酸、間苯二甲酸、對苯二甲酸 。作爲硫羧酸化合物，具體地可舉出硫乙酸、硫苯甲酸等 。作爲苯酚化合物或萘酚化合物，具體體可舉出氫醌、間 苯二酚、雙酚A、雙酚F、雙酚S、酚酞啉、甲基化雙酚 φ A'甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲 酚、對甲酚、兒茶酚、α-萘酚、β·萘酚、丨，5·二羥基萘、 1,6-二羥基萘' 2,6-二羥基萘、二羥基二苯甲酮、三羥基 二苯甲酮、四羥基二苯甲酮、均苯三酚、苯三酚、二環戊 二烯基二酚、苯酚-酚醛清漆等。其中’從耐熱性、溶解 性的觀點來看，較佳係雙酚A、雙酚F、雙酚s、甲基化 雙酚A、甲基化雙酚F、甲基化雙酚S、兒茶酚、1，5 -二 羥基萘、1，6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮 、三羥基二苯甲酮、四羥基二苯甲酮、均苯三酚、苯三酚 -11 - 201030046 、二環戊二烯基二酚、苯酚-酚醛清漆，尤佳係兒茶酚、 1,5-二羥基萘、1，6-二羥基萘、2,6-二羥基萘、二羥基二 苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、均苯三酚、 苯三酚、二環戊二烯基二酚、苯酚-酚醛清漆，更佳係 1，5-二羥基萘、1，6-二羥基萘、2,6-二羥基萘、二羥基二 苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯 基二酚、苯酚-酚醛清漆，尤更佳係二羥基二苯甲酮、三 羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯基二酚、苯 φ 酚-酚醛清漆，又更佳係二環戊二烯基二酚、苯酚-酚醛清 漆，特佳係二環戊二烯基二酚。作爲硫醇化合物，具體地 可舉出苯二硫醇、三哄二硫醇等。活性酯化合物係可倂用 2種以上。作爲活性酯化合物，可使用特開2004-427761 號公報中所揭示的活性酯化合物，而且亦可以使用市售者 。作爲市售的活性酯化合物，具體地較佳係含有二環戊二 烯基二酚構造者、苯酚-酚醛清漆的乙醯基化物、苯酚-酚 醛清漆的苯甲醯基化物，其中更佳係含有二環戊二烯基二 @ 酚構造者。作爲含有二環戊二烯基二酚構造者，可舉出 EXB-945 1、EXB-9460 ( DIC (股）製），作爲苯酚-酚醛 清漆的乙醯基化物，可舉出DC808，作爲苯酚-酚醛清漆 的苯甲醯基化物，可舉出 YLH1026C日本環氧樹脂（股 )製）。 本發明的活性酯化合物可使用1種或2種以上。 活性酯化合物的製造方法係沒有特別的限制，可藉由 眾所周知的方法來製造，具體地可藉由羧酸化合物及/或 -12- 201030046 硫羧酸化合物與羥基化合物及/或硫醇化合物的縮合反應 而獲得。 於本發明中，以玻璃轉移溫度的提高等爲目的，活性 酯以外的環氧硬化劑亦可與活性酯化合物倂用。作爲活性 酯以外的環氧硬化劑，可舉出TD2090、TD2131、LA7052 、LA7054、LA3018、LA1 3 56 ( DIC (股）製）、MEH-7600 ' MEH-78 5 1、MEH - 8 000H (明和化成（股）製）、 ❿ NHN、CBN、GPH-65，GPH-103 (曰本化藥（股）製）、 SN170 ' SN180 ' SN190 、 SN475 、 SN485 ' SN495 ' SN375 、SN395 (東都化成（股）製）等的酚系硬化劑、F-a、P-d(四國化成（股）製）、HFB2006M (昭和高分子（股） 襲）等的苯并噚畊化合物、甲基六氫苯二甲酸酐、甲基納 狄克（nadic )酸酐、氫化甲基納狄克酸酐等的酸酐等。 特佳係具有苯酚性羥基的化合物之酚系硬化劑。當倂用活 性酯化合物與其它硬化劑時，若環氧樹脂組成物中的全部 φ 環氧硬化劑（含活性酯化合物）爲重量1 〇〇%，則活性酯 化合物的重量％較佳係10〜100%，更佳係20〜100%。又 ，若環氧樹脂組成物中的全部環氧硬化劑（含活性酯化合 物）爲重量100%，則酚系硬化劑的重量％較佳係〇〜30% ，更佳係〇〜20%。 藉由倂用活性酯化合物與苯酚化合物（酚系硬化劑） ，可取得絕緣層表面的算術平均粗糙度與線膨脹率的平衡 。於此情況下，苯酚化合物的比例若多，則絕緣層表面的 算術平均粗糙度有增大的傾向，苯酚化合物的比例若小， -13- 201030046 則線膨脹率有增大的傾向。 於本發明中，環氧樹脂組成物中含有成分（B )活性 酯化合物之環氧硬化劑的量，較佳係使環氧樹脂組成物中 所存在的環氧基之合計數與環氧硬化劑的反應基之合計數 的比率成爲1 : 0.4〜1 : 1.1之量。再者，環氧樹脂組成 物中所存在的環氧基之合計數，係指將各環氧樹脂的固體 成分重量除以環氧當量後的値就全部環氧樹脂而言所合計 之値，環氧硬化劑的反應基（活性酯基、活性羥基等）的 @ 合計數係指將各硬化劑的固體成分重量除以反應基當量後 的値就全部硬化劑而言所合計之値。硬化劑的含量若在該 較佳範圍以外，則將環氧樹脂組成物硬化所得之硬化物的 耐熱性係有變不足的傾向。 [成分（C)之含脂環式構造之苯氧樹脂] 於本發明中，含脂環式構造之苯氧樹脂只要是具有脂 環式構造之苯氧樹脂，則沒有特別的限制。此處，"脂環 ❹ 式構造"係指「於碳原子以環狀鍵結的構造之有機化合物 中，去掉芳香族化合物者」、「彙總飽和烴（環烷）與不 飽和烴在環內含有1個雙鍵者（環烯）者」。 作爲具有脂環式構造之苯氧樹脂，可舉出具有環己烷 構造者、具有三甲基環己烷構造者、具有萜烯構造者等。 其中，從可更達成本發明的效果之觀點來看，更佳係具有 三甲基環己烷構造者、具有萜烯構造者，更佳係具有萜烯 構造者。 -14- 201030046 例如，作爲具有三甲基環己烷構造之苯氧樹脂，可舉 出特開200 6-176658號公報中所揭示之苯氧樹脂。 作爲具有萜烯構造之苯氧樹脂，可舉出在特開2006-1 766 5 8號公報中所揭示的苯氧樹脂中，作爲原料的2價 苯酚化合物’代替雙（4-羥苯基）-3,3，5-三甲基環己烷， 使用萜烯二酚所合成的苯氧樹脂等。 本發明的具有脂環式構造之苯氧樹脂係可使用1種或 ❹ 2種以上。 該含脂環式構造之苯氧樹脂之重量平均分子量的上限 値，從防止粗糙度的增加及熱膨脹率的增加之觀點來看， 較佳係1 〇〇〇〇〇，尤佳係60000，更佳係50000 ’尤更佳係 45000，再更佳係40000，特佳係35000。另一方面，該苯 氧樹脂的重量平均分子量之下限値’從充分得到與導體層 的剝離強度之觀點來看，較佳係2000 ’尤佳係1 0000 ’更 佳係1 2000，尤更佳係1 5000’再更佳係1 7000，特佳係 ❸ 20000。數量平均分子量係以凝膠滲透層析術（GPC法（ 聚苯乙烯換算）所測定之値。GPC法的數量平均分子量’ 具體地可使用（股）島津製作所製LC-9A/RID-6A當作測 定裝置，使用昭和電工（股）公司製Shodex K-800P/K-804L/K-804L當作管柱，使用N-甲基吡咯烷酮中溶解有0 〜4重量％的溴化鋰之溶液當作移動相，在管柱溫度40°C 進行測定，使用標準聚苯乙烯的校正曲線來算出。 此等苯氧樹脂的製造方法係沒有特別的限制’可藉由 如以下的方法來製造。可藉由以具有三甲基環己烷構造的 -15- 201030046 雙酚化合物或具有萜烯構造的雙酚化合物與2官能環氧樹 脂當作原料，依照眾所周知的苯氧樹脂之製法，以環氧基 與苯酚性羥基的當量比在約1: 0·9〜1: 1.1的範圍使反 應而容易製造。 再者，於發揮本發明的效果之範圍內’可混合使用含 脂環式構造之苯氧樹脂以外之苯氧樹脂。作爲其它苯氧樹 脂，可舉出日本環氧樹脂（股）製1256、4250、ΥΧ8100 、ΥΧ6954 ' YL7553、YL7482 等。 於本發明的環氧樹脂組成物中，當環氧樹脂組成物的 不揮發成分爲100重量％時，當該苯氧樹脂的含量較佳係 1〜2 0重量％，更佳係5〜1 0重量％。若低於1重量％，則 得不到充分的可撓性，操作性降低，或鍍敷所形成的導體 層之剝離強度有無法充分得到的傾向，而若超過20重量 %，則層合時得不到充分的流動性，或粗糙度有變過大的 傾向。 [無機塡充料] 本發明的環氧樹脂組成物’以更降低線膨脹率等爲目 的’可更含有無機塡充料。作爲無機塡充料，例如可舉出 矽石、氧化鋁、硫酸鋇、滑石、黏土、雲母粉、氫氧化鋁 、氫氧化鎂、碳酸鈣 '碳酸鎂、氧化鎂、氮化硼、硼酸鋁 、鈦酸鋇、鈦酸緦、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、 锆酸鋇、銷酸鈣等’於此等之中’特別合適爲無定形矽石 、熔融矽石、結晶矽石 '合成矽石等的矽石。可使用1種 -16- 201030046 或2種以上的無機塡充料。 作爲矽石，較佳係球狀者。無機塡充料的平均粒徑較 佳係Ιμπι以下’更佳係〇·8μιη以下，特佳係0.7μιη以下 。當平均粒徑超過Ιμιη時，鏟敷所形成的導體層之剝離 強度有降低的傾向。再者，無機塡充料的平均粒徑若過小 ’則在以環氧樹脂組成物當作樹脂清漆時，由於清漆的黏 度上升’操作性有降低的傾向，故平均粒徑較佳係 ® 以上。再者，爲了提高耐濕性，無機塡充料較佳 係經環氧基矽烷偶合劑、胺基矽烷偶合劑、鈦酸酯系偶合 劑等的表面處理劑所表面處理者。 上述無機塡充料的平均粒徑係可以米氏（Mie)散射 理論爲基礎’藉由雷射繞射•散射法來測定。具體地可藉 由雷射繞射式粒度分布測定裝置，以體積基準作成無機塡 充料的粒度分布’測定其中位徑當作平均粒徑。測定樣品 &佳可使用無機塡充料經超音波分散在水中者。作爲雷射 ^ 繞射式粒度分布測定裝置，可使用（股）堀場製作所製 LA-500 等。 配合該無機塡充料時的含量，當以環氧樹脂組成物的 不揮發成分爲100重量％時，亦隨著樹脂組成物所要求的 特性而不同’但較佳係10〜70重量。/。，更佳係15〜60重 胃％ °無機塡充料的含量若過小，則硬化物的線膨脹率有 變高的傾向’而含量若過大，則在調製黏著薄膜之際，薄 膜化變困難’或硬化物有變脆的傾向。 -17- 201030046 [硬化促進劑] 本發明的環氧樹脂組成物，以調製硬化時間及硬化溫 度等爲目的，亦可含有硬化促進劑。作爲硬化促進劑，例 如可舉出 TPP、TPP-K、TPP-S、TPTP-S (北興化學工業 (股）商品名）等的有機膦化合物、Curezol 2MZ、 2E4MZ ' C11Z、C11Z-CN' C11Z-CNS' C11Z-A' 2MZ-OK 、2MA-OK、2PHZ (四國化成工業（股）商品名）等的咪 哩化合物、Novacure (旭化成工業（股）商品名）、 Novacure(富士化成工業（股）商品名）等的胺加成化合 物、1，8-二氮雜雙環[5,4,0]十一烯-7、4-二甲胺基吡啶、 苄基二甲基胺、2,4,6-三（二甲胺基甲基）酚等的胺化合 物。硬化促進劑係可使用1種或2種以上。於本發明的環 氧樹脂組成物中，硬化促進劑的含量，當環氧樹脂組成物 中所含有的環氧樹脂與苯酚性硬化劑的總量係1 00重量％ (不揮發成分）時，較佳係0.1〜5重量％。 [橡膠粒子] 本發明的環氧樹脂組成物，以提高硬化物的機械強度 、應力緩和效果等爲目的，亦可含有固體狀的橡膠粒子。 本發明的橡膠粒子，係不溶解在調製環氧樹脂組成物時的 有機溶劑中，也不與環氧樹脂等的樹脂組成物中之成分相 溶，而在環氧樹脂組成物的清漆中以分散狀態存在。如此 的橡膠粒子，一般係藉由使橡膠成分的分子量大到不溶解 在有機溶劑或樹脂中的程度爲止，而成爲粒子狀來調製。 -18- 201030046 作爲橡膠粒子，例如可舉出芯殻型橡膠粒子、交聯丙烯腈 丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸橡 膠粒子等。芯殼型橡膠粒子係粒子具有芯層與殼層的橡膠 粒子，例如可舉出外層的殼層爲玻璃狀聚合物，內層的芯 層由橡膠狀聚合物所構成的2層構造，或外層的殼層爲玻 璃狀聚合物，中間層爲橡膠狀聚合物，芯層由玻璃狀聚合 物所構成的3層構造者等。玻璃層例如由甲基丙烯酸甲酯 ❹ 的聚合物等所構成，橡膠狀聚合物層例如由丙烯酸丁酯聚 合物（丁基橡膠）等所構成。作爲芯殼型橡膠粒子的具體 例，可舉出 Stafilrod AC3832、AC3816N(GANZ 化成（ 股）商品名）、Metabren W-5500 (三菱嫘縈（股）商品 名）。作爲丙烯腈丁二烯橡膠（NBR )粒子的具體例，可 舉出XER-91 (平均粒徑0·5μιη，JSR (股）製）等。作爲 苯乙烯丁二烯橡膠（SBR )粒子的具體例，可舉出XSK-500(平均粒徑0·5μιη，JSR (股）製）等。丙烯酸橡膠粒 ® 子的具體例，可舉出Metabren 3 00Α (平均粒徑〇·1 μιη) 、W4 50A (平均粒徑0·5μιη)(三菱嫘縈（股）製）。橡 膠粒子可使用1種或2種以上。 所配合的橡膠粒子之平均粒徑較佳係0.005〜Ιμιη的 範圍，更佳係0.2〜0·6μηι的範圍。本發明中的橡膠粒子 之平均粒徑係可使用動態光散射法來測定。例如，藉由超 音波等使橡膠粒子均勻分散在適當的有機溶劑中，使用 FPRA-10 00 (大塚電子（股）公司製），以重量基準作成 橡膠粒子的粒度分布，將其中位徑當作平均粒徑而測定。 -19- 201030046 當配合該橡膠粒子時，若環氧樹脂組成物的不揮發成 分爲1 00重量％，則環氧樹脂組成物中的含量較佳係0.5 〜10重量％，更佳係1〜4重量％。 [其它熱硬化性樹脂] 本發明的環氧樹脂組成物，按照需要在不損害本發明 的效果之範圍內，亦可配合氰酸酯樹脂或馬來醯亞胺化合 物、雙烯丙基納迪醯亞胺（bis-allyl-nadi-imide )化合物 Q 、乙烯基苄基樹脂、乙烯基苄基醚樹脂等的熱硬化性樹脂 。作爲氰酸酯樹脂，可舉出 BADCY、LECY、BA230S70 ' PT15 ' PT30 ' PT60 ( LONZA公司製）’作爲馬來醯亞 胺樹脂，可舉出 BMI1000、BMI2000、BMI3000、 BMI4000、BMI5 100 (大和化成工業（股）製）、BMI、 BMI-70、BMI-80 ( KI 化成（股）製）、ANILIX-MI (三 井化學精密（股）製造），作爲雙烯丙基納迪醯亞胺化合 物ΒΑΝΙ·Μ、BANI-X (九善石油化學工業（股）製）， @ 作爲乙烯基苄基樹脂，可舉出V5 000 (昭和高分子（股） 製），作爲乙烯基苄基醚樹脂，可舉出 V1000X、V1100X (昭和高分子（股）製）。其它熱硬化性樹脂係可使用1 種或2種以上。 [難燃劑] 本發明的環氧樹脂組成物，在不損害本發明的效果之 範圍內，亦可含有難燃劑。作爲難燃劑，例如可舉出有機 -20- 201030046 磷系難燃劑、有機系含氮的磷化合物、氮化合物、聚矽氧 系難燃劑、金屬氫氧化物等。作爲有機磷系難燃劑，可舉 出三光（股）製的HCA、HCA-HQ、HCA-NQ等的膦化合 物、昭和高分子（股）製的HFB-2 00 6M等之含磷的苯并 噚阱化合物、味之素精密科技（股）製的Rheophos 30、 50、65、90、1 10、TPP、RPD、BAPP、CPD、TCP、TXP 、TBP、TOP、KP140、ΤΙΒΡ、北興化學工業（股）製的 φ PPQ、CLARIANT (股）製的 ΟΡ930 '大八化學（股）製 的 ΡΧ200等之磷酸酯化合物、東都化成（股）製的 FX2 89、FX3 10等之含磷環氧樹脂、東都化成（股）製的 ERF00 1等之含磷苯氧樹脂等。作爲有機系含氮的磷化合 物，可舉出四國化成工業（股）製的SP670、SP7 03等的 磷酸酯醯胺化合物、大塚化學（股）公司製的SPB100、 SPE 100等之磷腈化合物等。作爲金屬氫氧化物，可舉出 宇部材料（股）製的UD65、UD650、UD653等的氫氧化 β 鎂、巴工業（股）公司製的Β-30、Β-325、Β-315、Β-308 、B-303、UFH-20等之氫氧化鋁等。難燃劑可使用1種或 2種以上。 [樹脂添加劑] 本發明的環氧樹脂組成物，在發揮本發明的效果之範 圍內’可任意含有上述以外的其它各種樹脂添加劑。作爲 樹脂添加劑，例如可舉出矽粉、耐隆粉、氟粉等的有機塡 充劑、歐魯本（〇rben )、片通（Benton )等的增黏劑、 -21 - 201030046 聚矽氧系、氟系、高分子系的消泡劑或均平劑、咪唑系、 噻唑系、三唑系、矽烷偶合劑等的密接性賦予劑、酞花青 藍、酞花青綠、碘綠、雙偶氮黃、碳黑等的著色劑等。樹 脂添加劑可使用1種或2種以上。 本發明的樹脂組成物之用途係沒有特別的限定，可使 用於黏著薄膜、預浸物等的絕緣樹脂薄片、線路基板、阻 焊劑、底部塡充材、固晶材料、半導體密封材、埋孔樹脂 、埋入零件的樹脂等需要樹脂組成物的用途之廣範圍。 [黏著薄膜] 本發明的樹脂組成物少可藉由在支持薄膜上塗布而形 成樹脂組成物層，當作多層印刷電路板用的黏著薄膜。本 發明的樹脂組成物亦可在線路基板塗佈而形成絕緣層，但 工業上一般係作爲黏著薄膜的形態而用於絕緣層形成。 本發明的黏著薄膜係可藉由本業者所公知的方法，例 如調製有機溶劑中溶解有樹脂組成物的樹脂清漆，以支持 薄膜當作支持體，塗佈此樹脂清漆，再藉由加熱或熱風噴 吹等以使有機溶劑乾燥，而形成樹脂組成物層來製造。 作爲有機溶劑，例如可舉出丙酮、甲基乙基酮、環己 酮等的酮類、醋酸乙酯、醋酸丁酯、纖維素醋酸酯、丙二 醇單甲基醚醋酸酯、卡必醇醋酸酯等的醋酸酯類、溶纖劑 、丁基卡必醇等的卡必醇類、甲苯、二甲苯等的芳香族烴 類、二甲基甲醯胺、二甲基乙醯胺、N_甲基吡咯烷酮等的 醯胺系溶劑等。有機溶劑可組合2種以上來使用。 201030046 乾燥條件係沒有特別的限定，以有機溶劑對樹脂組成 物層的含有比例成爲1 〇重量％以下、較佳5重量％以下使 乾燥。乾燥條件係可藉由簡單的實驗而設定適宜、合適的 乾燥條件。雖然隨著清漆中的有機溶劑量亦不同’但是例 如可在50〜150 °C使含有30〜60重量％的有機溶劑之清漆 乾燥3〜10分鐘。 黏著薄膜中所形成的樹脂組成物層之厚度，通常爲導 φ 體層的厚度以上。由於具有線路基板的導體層之厚度通常 爲5〜80μιη的範圍，樹脂組成物層的厚度較佳係具有1〇 〜100 μιη的厚度。樹脂組成物層亦可被後述的保護薄膜所 保護。藉由保護薄膜來保護，可防止灰塵等對樹脂組成物 層表面的附著或損傷。 作爲本發明中的支持薄膜及保護薄膜，可舉出聚乙烯 、聚丙烯、聚氯乙烯等的聚烯烴、聚對苯二甲酸乙二酯（ 以下簡稱「PET」）、聚萘二甲酸乙二酯等的聚酯、聚碳 〇 酸酯、聚醯亞胺，以及脫模紙或銅箔、鋁箔等的金屬箔等 。再者，支持薄膜及保護薄膜係可被施予消光處理、電暈 處理及脫模處理。 支持薄膜的厚度係沒有特別的限定，較佳使用1 0〜 150μπι，更佳使用25〜50μιη。又，保護薄膜的厚度亦沒 有特別的限定，較佳使用1〜40μιη，更佳使用10〜30μιη 。再者，如後述地，在黏著薄膜的製造步驟中作爲支持體 所用的支持薄膜，亦可當作保護樹脂組成物層表面的保護 薄膜來使用。 -23- 201030046 本發明中的支持薄膜，在層合於線路基板上後，或在 經由加熱硬化而形成絕緣層後，被剝離。於將黏著薄膜加 熱硬化後，若剝離支持薄膜，則可在硬化步驟中防止灰塵 等的附著，而且可提高硬化後的絕緣層之表面平.滑性。於 硬化後剝離時，較佳係對支持薄膜預先施予脫模處理。再 者，支持薄膜上所形成的樹脂組成物層，較佳係以層的面 積比支持薄膜的面積小的方式來形成。又，黏著薄膜係可 捲繞成輥狀而保存、儲藏。 @ [預浸物] 本發明的樹脂組成物係可對於薄片狀補強基材（編入 纖維者），以熱熔法或溶劑法含浸，加熱成爲半硬化，而 成爲預浸物。薄片狀補強基材係沒有特別的限制，亦可使 用預浸物中所常用者。具體地，可使用由玻璃布或芳族聚 醯胺纖維等的預浸物用纖維所構成者。 熱熔法係不將本發明的樹脂組成物溶解在有機溶劑中 φ ，而在一旦塗佈於與該樹脂的剝離性良好之塗佈紙上後， 將其層合於薄片狀補強基材，或是不將樹脂溶解在有機溶 劑中，而藉由口模式塗佈機直接塗佈在薄片狀補強基材上 等，以製造預浸物的方法。又，溶劑法係與黏著薄膜同樣 地，將樹脂溶解在有機溶劑中以調製樹脂清漆，將薄片狀 補強基材浸漬在此清漆中，使薄片狀補強基材含浸樹脂清 漆，然後使乾燥的方法。 -24- 201030046 [多層印刷電路板] 藉由使用本發明的黏著薄膜或預浸物，更可製造多層 印刷電路板。 茲說明使用本發明的黏著薄膜來製造本發明的多層印 刷電路板之方法。當樹脂組成物層爲經保護薄膜所保護時 ，剝離此等後，以樹脂組成物層直接接觸線路基板的方式 ，層合在線路基板的一面或兩面上。於本發明的黏著薄膜 φ 中，藉由真空層合法在減壓下層合在線路基板上的方法係 較合適使用。層合的方法可爲分批式或藉由輥的連續式。 又，於進行層合之前，視需要可預先加熱（預熱）黏著薄 膜及線路基板。 層合的條件就壓黏溫度（層合溫度）而言較佳70〜 140 °C，就壓黏壓力而言較佳係1〜llkgf/cm2 ( 9·8χ104〜 107.9xl〇4N/m2 )，就空氣壓而言較佳係 20mmHg ( 26.7hPa)以下的減壓下進行層合。 9 真空層合係可使用市售的真空層合機來進行。作爲市 售的真空層合機，例如可舉出Nichigo-Morton (股）製真 空施力機、（股）名機製作所製真空加壓式層合機、（股 )曰立工業製輥式乾塗機、日立AIC (股）製真空層合機 等。 本發明中的內層線路基板係主要指在玻璃環氧樹脂、 金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱 硬化型聚苯醚基板等的基板之一面或兩面上形成有圖型加 工的導體層（線路）者。又，於製造導體層與絕緣層交互 -25- 201030046 地層形成，一面或兩面經圖型加工的導體層（線路）之多 層印刷電路板時，用於形成絕緣層及導體層的中間製造物 亦包含在本發明的內層線路基板中。於內層線路基板中， 導體線路層表面經粗化處理等而預先施有粗化處理者，從 絕緣層對內層線路基板的密接之觀點來看係較佳。 如此地在線路基板層合黏著薄膜後，剝離支持薄膜的 情況，可藉由熱硬化而在線路基板上形成絕緣層。加熱硬 化的條件可在150 °C〜220 °C、20分鐘〜180分鐘的範圍作 _ 選擇，更佳係160 °C〜200 °C、30〜120分鐘。 在形成絕緣層後，於硬化前不剝離支持薄膜的情況， 係在此處剝離。接著，對線路基板上所形成的絕緣層進行 開孔，而形成通孔、貫穿孔。開孔例如可藉由鑽孔、雷射 、電漿等眾所周知的方法，而且按照需要可組合此等方法 來進行，二氧化碳雷射、YAG雷射等的雷射之開孔係最 一般的方法。 接著，對絕緣層表面進行粗化處理。本發明中的粗化 @ 處理較佳係以用氧化劑的濕式粗化方法來進行。作爲氧化 劑，可舉出過錳酸塩（過錳酸鉀、過錳酸鈉等）、重鉻酸 鹽、臭氧、過氧化氫/硫酸、硝酸等。較佳係增層法的多 層印刷電路板之製造中絕緣層的粗化所通用的氧化劑，即 用鹼性過錳酸溶液（例如過錳酸鉀、過錳酸鈉的氫氧化鈉 水溶液）來進行粗化係較佳。 絕緣層表面經粗化處理之粗化面的粗糙度，在形成微 細線路時，Ra値較佳係0.5 μτη以下。再者，Ra値係表示 -26- 201030046 表面粗糙度的數値之一種，被稱爲算術平均粗糙度，具體 地自平均線的表面起，測量測定範圍內所變化的高度之絕 對値，進行算術平均。例如，可使用VEECO儀器公司製 WYKO NT3 3 00，藉由VSI接觸模式、50倍透鏡，由測定 範圍爲121μιηχ92μιη所得之數値來求得。 接著，於經由粗化處理而形成有凸凹的錨之樹脂組成 物層表面上，藉由組合無電解鏟敷與電解鍍敷的方法，形 φ 成導體層。又，亦可以形成與導體層相反圖型的鍍敷光阻 ，僅藉由無電解鍍敷來形成導體層。再者，於導體層形成 後，藉由在 150〜200 °C進行20〜90分鐘退火（anneal) 處理，可更提高導體層的剝離強度，使安定化。導體層的 剝離強度較佳係〇.6kgf/cm以上。 又，作爲對導體層進行圖型加工以形成線路的方法， 例如可使用本業者眾所周知的減成法、半加成法等。 本發明的預浸物係可在由纖維所成的薄片狀纖維基材 ® 中，藉由熱熔法或溶劑法使含浸本發明的樹脂組成物，經 由加熱使半硬化而製造。即，可成爲預浸物，其爲在由纖 維所成的薄片狀纖維基材中含浸本發明的樹脂組成物之狀 態。 作爲由纖維所成的薄片狀纖維基材，例如可使用玻璃 布或芳族聚醯胺纖維等作爲預浸物用纖維所常用者》 熱熔法係不將樹脂溶解在有機溶劑中，而在一旦將樹 脂塗佈在與樹脂的剝離性良好的塗佈紙上後，將其層合於 薄片狀纖維基材，或是藉由口模式塗佈機直接塗佈等，以 -27- 201030046 製造預浸物的方法。又，溶劑法係與黏著薄膜同樣地，將 樹脂溶解在有機溶劑中以調製樹脂清漆，將薄片狀補強基 材浸漬在此清漆中，使薄片狀纖維基材含浸樹脂清漆，然 後使乾燥的方法。 茲說明使用本發明的預浸物來製造本發明的多層印刷 電路板之方法。於線路基板上，重叠一片或視需要數片的 本發明之預浸物，隔著脫模薄膜，夾著金屬板，在加壓. 加熱條件下，進行加壓層合。壓力較佳係5〜40kgf/cm2 ( 49χ104〜392xl04N/m2)，溫度較佳係120〜200t，較佳 係以20〜100分鐘來成型。又，亦可與黏著薄膜同樣地， 藉由真空層合法層合在線路基板上後，進行加熱硬化而製 造。然後’可前述方法同樣地，將經由氧化劑所硬化的預 浸物表面粗化後，藉由鍍敷來形成導體層，而製造多層印 刷電路板。 [實施例] @ 以下使用實施例及比較例來更詳細說明本發明，惟在 任何意思中本發明也不受此等所限制。再者，於以下的記 載中，「份」係意味「重量份」。 (實驗例1 ) 於15份的甲基乙基酮（以下簡稱r MEK」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 氧樹脂（環氧當量180，曰本環氧樹脂（股）製「 -28 - 291 201030046 jER82 8EL」）與30份的聯苯型環氧樹脂（環氧當量 ，日本化藥（股）製「NC3000H」）。於其中，混名 份的活性酯化合物（DIC (股）製「EXB9460-65T」 性酯當量223，固體成分65%的甲苯溶液）、0.5份 化促進劑（廣榮化學工業（股）製，「4-二甲胺基吡 )、120份的球形矽石（平均粒徑〇·5μιη，附胺基矽 理「SO-C2」（股）ADMATECHS製）、40份的苯氧 φ (與特開平2006-176658號公報的實施例1同樣地， (4-羥苯基）-3,3,5-三甲基環己烷與 3,3’，5,5’-四弓 4,4’-二酚二縮水甘油醚所合成的苯氧樹脂，不揮發夕 重量％的ΜΕΚ與環己酮的1:1溶液，重量平均分 3 0 000 )，藉由高速旋轉混合機進行均勻分散，以製 脂清漆（固體成分244份，矽石49重量％，環氧基 氧硬化劑的反應基之比率1 : 0.87 )。 接著，以乾燥後的樹脂厚度成爲4〇 μηι的方式， 〇 口模式塗佈機，將該樹脂清漆塗佈在聚對苯二甲酸乙 (厚度38μιη，以下簡稱「PET」）上，在80〜120°C 均1 〇〇°C )乾燥6分鐘（殘留溶劑量約2重量％ )。 ，在樹脂組成物的表面上，邊貼合厚度15μπι的聚丙 膜邊捲繞成輥狀。將輥狀的黏著薄膜切割（slit)成 507mm，藉此而得到507x336mm大小的薄片狀黏著 (實驗例2 ) Ϊ· 80 ，活 的硬 啶」 烷處 樹脂 由雙 3基- h 30 子量 作樹 與環 藉由 二酯 (平 接著 烯薄 寬度 薄膜 -29- 201030046 於15份的甲基乙基酮（以下簡稱「ΜΕΚ」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 氧樹脂（環氧當量18〇，日本環氧樹脂（股）製「 JER828EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3000H」）。於其中，混合40 份的活性酯化合物（DIC (股）製「EXB9460-65T」，活 性酯當量223，固體成分65%的甲苯溶液）、15份的酚系 硬化劑LA7052 ( DIC (股）製，含有三畊構造的苯酚-酚 醛清漆樹脂，苯酚性羥基當量120，固體成分60%的MEK 溶液）、〇.5份的硬化促進劑（廣榮化學工業（股）製， 「4-二甲胺基吡啶」）、100份的球形矽石（平均粒徑 0.5μπι，附胺基矽烷處理「SO-C2」（股）ADMATECHS 製）、4〇份的苯氧樹脂（與特開平2006-176658號公報 的實施例1同樣地，由雙（4-羥苯基）-3,3,5-三甲基環己 院與3，3’，5,5’·四甲基-4,4’-二酚二縮水甘油醚所合成的苯 氧樹脂，不揮發分30重量％的ΜΕΚ與環己酮的1 : 1溶 液，重量平均分子量30000 )，藉由高速旋轉混合機進行 均勻分散，以製作樹脂清漆（固體成分207份，矽石48 重量％，環氧基與環氧硬化劑的反應基之比率1:0.72) 。接著，使用該樹脂清漆，與實施例1完全同樣地得到黏 著薄膜。 (實驗例3) 於15份的甲基乙基酮（以下簡稱「ΜΕΚ」）、15份 201030046 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 氧樹脂（環氧當量180，日本環氧樹脂（股）製「 JER82 8EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3000H」）。於其中’混合40 份的活性酯化合物（DIC (股）製「EXB9460-65T」，活 性酯當量223，固體成分65 %的甲苯溶液）、15份的酚系 硬化劑LA7〇52 ( DIC (股）製，含有三哄構造的苯酚-酚 φ 醛清漆樹脂，苯酚性羥基當量120，固體成分60%的MEK 溶液）、〇.5份的硬化促進劑（廣榮化學工業（股）製， 「4-二甲胺基吡啶」）、100份的球形矽石（平均粒徑 0.5μπι，附胺基矽烷處理「SO-C2」（股）ADMATECHS 製）、30份的苯氧樹脂（特開平2006-176658號公報的 實施例1中’代替雙（4 -羥苯基）-3，3,5-三甲基環己烷， 使用萜儲二酚而同樣合成的苯氧樹脂，不揮發分40重量 %的ΜΕΚ與環己酮的1: 1溶液，重量平均分子量30000 Ο ) ’藉由高速旋轉混合機進行均勻分散，以製作樹脂清漆 (固體成分207份’矽石48重量％，環氧基與環氧硬化 劑的反應基之比率1:0.72)。接著，使用該樹脂清漆， 與實施例1完全同樣地得到黏著薄膜。 (實驗例4 ) 於15份的甲基乙基酮（以下簡稱「ΜΕΚ」）、15份 的環己酮中’邊擾拌邊加熱溶解份的液狀雙酣Α型環 氧樹脂（環氧當量180’日本環氧樹脂（股）製「 ~ 31 - 201030046 jER828EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3 000H」）。於其中，混合80 份的活性酯化合物（DIC (股）製「EXB9460-65T」，活 性酯當量223，固體成分65%的甲苯溶液）、〇.5份.的硬 化促進劑（廣榮化學工業（股）製，「4-二甲胺基吡啶」 )、130份的球形矽石（平均粒徑〇·5μπι，附胺基矽烷處 理「SO-C2」（股）ADMATECHS製）、40份的苯氧樹脂 (與特開平2006-176658號公報的實施例1同樣地，由雙 (4-羥苯基）-3,3,5-三甲基環己烷與3,3’，5,5’-四甲基-4，4’-二酚二縮水甘油醚所合成的苯氧樹脂，不揮發分30 重量％的ΜΕΚ與環己酮的1:1溶液，重量平均分子量 3 0000 )，藉由高速旋轉混合機進行均勻分散，以製作樹 脂清漆（固體成分252份，矽石50重量％，環氧基與環 氧硬化劑的反應基之比率1 : 0.87 )。接著，使用該樹脂 清漆，與實施例1完全同樣地得到黏著薄膜。 (比較例1 ) 於15份的甲基乙基酮（以下簡稱「ΜΕΚ」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚Α型環 氧樹脂（環氧當量18〇，日本環氧樹脂（股）製「 JER82 8EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3000H」）。於其中，混合80 份的活性酯化合物（DIC (股）製「EXB9460-65T」，活 性酯當量223，固體成分65 %的甲苯溶液）、〇.5份的硬 -32- 201030046 化促進劑（廣榮化學工業（股）製，「4-二甲胺基吡啶」 )、120份的球形矽石（平均粒徑0.5 μιη，附胺基矽烷處 理「SO-C2」（股）ADMATECHS製）、30份的苯氧樹脂 (重量平均分子量 50000，日本環氧樹脂（股）製「 1 256B40」雙酚A構造苯氧樹脂，不揮發分40重量％的 MEK溶液），藉由高速旋轉混合機進行均勻分散，以製 作樹脂清漆（固體成分244份，矽石49重量％，環氧基 ©與環氧硬化劑的反應基之比率1:0.87)。接著，使用該 樹脂清漆，與實施例1完全同樣地得到黏著薄膜。 例 較 比 於15份的甲基乙基酮（以下簡稱「ΜΕΚ」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 氧樹脂（環氧當量 180，日本環氧樹脂（股）製「 jER82 8EL」）與30份的聯苯型環氧樹脂（環氧當量291 Φ ，日本化藥（股）製「NC3 00 0H」）。於其中，混合40 份的活性酯化合物（DIC (股）製「EXB946 0-65T」，活 性酯當量223，固體成分65%的甲苯溶液）、15份的酚系 硬化劑LA7052 ( DIC (股）製，含有三哄構造的苯酚-酚 醛清漆樹脂，苯酚性羥基當量120，固體成分60%的MEK 溶液）、0.5份的硬化促進劑（廣榮化學工業（股）製， 「4-二甲胺基吡啶」）、1 00份的球形矽石（平均粒徑 0·5μιη，附胺基矽烷處理「SO-C2」（股）ADMATECHS 製）、30份的苯氧樹脂（重量平均分子量50000，日本環 -33- 201030046 氧樹脂（股）製「125όΒ40」（雙酚a構造苯氧樹脂，不 揮發分40重量％的MEK溶液），藉由高速旋轉混合機進 行均句分散’以製作樹脂清漆（固體成分207份，矽石 48重量％，環氧基與環氧硬化劑的反應基之比率1 : 〇 72 )。接著，使用該樹脂清漆’與實施例1完全同樣地得到 黏著薄膜。201030046 VI. Description of the Invention: [Technical Field] The present invention relates to an epoxy resin composition suitable for forming an insulating layer of a multilayer printed circuit board. [Prior Art] In recent years, electronic devices have been miniaturized and high-performance, and layers established in multi-layer printed circuit boards have been layered, requiring miniaturization and high density of circuits. A variety of efforts have been made for this. For example, Patent Document 1 discloses an epoxy resin composition containing an epoxy resin, a specific phenolic curing agent, a phenoxy resin, and rubber particles, and Patent Document 2 discloses an epoxy resin, a specific phenolic curing agent, and An epoxy resin composition of a polyvinyl acetal resin. Although the insulating layer formed by these compositions can achieve low roughness and the peeling strength of the conductor layer formed by plating, the lingering of the low expansion ratio is not disclosed or indicated at all. [Patent Document 1] JP-A-2007-254709 [Patent Document 2] JP-A-2007-25471 A SUMMARY OF INVENTION Problems to be Solved by the Invention An object of the present invention is to provide hardening of an epoxy resin composition. The roughness of the roughened surface of the surface of the object is relatively small, and the roughened surface can also exhibit high adhesion to the plated conductor, and can achieve low-line expansion of the insulating layer - 5 - 201030046 Things. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention conducted intensive efforts and found that a specific epoxy resin composition containing an epoxy resin, an active ester compound, and a phenoxy resin having an alicyclic structure was finally completed. this invention. That is, the present invention includes the following contents. [1] An epoxy resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an alicyclic resin having an alicyclic structure. [2] The epoxy resin composition according to the above [1], wherein the alicyclic structure of the (C) phenoxy resin is a terpene structure and/or a trimethylcyclohexane structure. The alicyclic structure of the above (C) phenoxy resin is a terpene structure and/or a trimethylcyclohexane structure. [3] The epoxy resin composition according to the above [1] or [2] wherein the phenoxy resin has a weight average molecular weight of 10,000 to 50,000. [4] The epoxy resin composition according to any one of the above [1] to [3] wherein, when the nonvolatile content of the epoxy resin composition is 100% by weight, the content of the component (A) is 10 to 50. The weight %, the content of the component (C) is 1 to 20% by weight 'and the ratio of the epoxy group present in the epoxy resin composition to the reactive group of the epoxy hardener is 1: 0. 4~1 : 1. 1. [5] The epoxy resin composition according to any one of the above [1] to [4] further comprising (D) an inorganic cerium filling. [6] The epoxy resin composition according to the above [5], wherein the content of the (D) inorganic cerium filling is 10 to 70% by weight when the nonvolatile content of the epoxy resin 201030046 is 10% by weight. . [7] The epoxy resin composition according to any one of the above [1] to [6] further comprising (E) a curing accelerator. [8] The epoxy resin composition according to the above [7], wherein (E) hardening is carried out when the total amount of the epoxy resin and the phenolic hardener contained in the epoxy resin composition is 1% by weight The content of the accelerator is 〇. 1 to 5 weight. /〇. [9] An adhesive film comprising the layer of the epoxy resin composition according to any one of the above [1] to [8]. [10] A prepreg characterized in that the epoxy resin composition according to any one of the above [1] to [8] is impregnated with a sheet-like fibrous base material made of a fiber. [11] A multilayer printed circuit board comprising the cured layer of the epoxy resin composition according to any one of the above [1] to [8]. Φ [12] A method of manufacturing a multilayer printed circuit board, comprising the steps of forming an insulating layer on an inner layer circuit substrate and manufacturing a multilayer printed circuit board having the step of forming a conductor layer on the insulating layer, the characteristics of which are The insulating layer is formed by thermally curing the epoxy resin composition according to any one of the above [1] to [8], wherein the conductor layer is roughened by roughening the surface of the insulating layer. It is formed by plating. [13] A method of manufacturing a multilayer printed circuit board, comprising the steps of: forming an insulating layer on an inner layer circuit substrate; and manufacturing a multilayer printed circuit board having the step of forming a conductor layer on the insulating layer, wherein: The insulating layer 201030046 is formed by laminating the adhesive film according to the above [9] on the inner layer circuit substrate, and thermally curing the epoxy resin composition under the peeling or non-stripping support film, and in the presence of the support film after hardening, The support film is formed by peeling off, and the conductor layer is formed by plating on a roughened surface on which the surface of the insulating layer is roughened. [14] A method of manufacturing a multilayer printed circuit board, comprising the steps of: forming an insulating layer on an inner layer circuit substrate; and manufacturing a multilayer printed circuit board having the step of forming a conductor layer on the insulating layer, characterized in that: The layer is formed by laminating the prepreg according to the above [10] on the inner layer wiring substrate and thermally curing the epoxy resin composition, and the conductor layer is roughened by roughening the surface of the insulating layer. It is formed by plating on the surface. [15] The production method according to any one of [12] to [14] wherein the roughening treatment is carried out using an inert permanganic acid solution. The effect of the invention is achieved by blending an epoxy resin, an active ester compound, and a specific epoxy resin composition of a phenoxy resin having an alicyclic structure of 0, although the roughened surface of the surface of the cured product has a roughened surface roughness. The roughened surface also exhibits a high adhesion to the plated conductor, and a low linear expansion ratio of the insulating layer can be achieved. [Embodiment] The present invention is a specific epoxy resin composition containing an epoxy resin, an active ester compound, and a phenoxy resin having an alicyclic structure. -8-201030046 [Epoxy resin of the component (A)] The epoxy resin of the component (A) in the invention is not particularly limited, and examples thereof include a bisphenol A epoxy resin and a bisphenol F epoxy resin. Resin, phenol-novolac epoxy resin, t-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, cresol novolac epoxy resin, biphenyl Epoxy resin, linear aliphatic epoxy resin φ, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol epoxy resin, trimethylol Epoxy resin, halogenated epoxy resin, etc. The epoxy resin of the present invention may be used alone or in combination of two or more. An epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin composition is 1% by weight, it is preferably at least 50% by weight or more based on the epoxy resin having two or more epoxy groups in one molecule. Further, a preferred embodiment includes an epoxy resin having an epoxy group having 2 or more epoxy groups in one molecule and a liquid epoxy resin at a temperature of 20 ° C, and 3 or more epoxy resins in 1 minute oxime. Base, an aromatic fluorene epoxy resin which is solid at a temperature of 20t. Further, the aromatic epoxy resin described in the present invention means an epoxy resin having an aromatic ring structure in its molecule. Further, the epoxy equivalent (g/eq) is the molecular weight per one epoxy group. By using a liquid epoxy resin and a solid epoxy resin as an epoxy resin, when an epoxy resin composition is used in the form of an adhesive film, sufficient flexibility is exhibited, and an adhesive film excellent in handleability can be formed. Increasing the breaking strength of the cured product of the epoxy resin composition' improves the durability of the multilayer printed circuit board. Further, as the epoxy resin, when the liquid epoxy resin and the solid epoxy 201030046 resin are used in combination, the mixing ratio (liquid: solid) is preferably 1:0 by weight. 1 to 1: 2 range. When the ratio of the liquid epoxy resin is too large, the adhesiveness of the epoxy resin composition is increased, and when it is used as a film, the degassing property at the time of vacuum lamination is lowered, and voids are likely to occur. tendency. Further, the peeling property of the protective film or the support film at the time of vacuum lamination is lowered, or the heat resistance after curing tends to be lowered. Further, in the cured product of the epoxy resin composition, it is difficult to obtain sufficient breaking strength. On the other hand, when the ratio of the solid epoxy resin is too large, the resin is used in the form of an adhesive film, and sufficient flexibility is not obtained, and workability is lowered, and it is difficult to obtain sufficient lamination at the time of lamination. The tendency of liquidity, etc. In the epoxy resin composition of the present invention, when the nonvolatile content of the epoxy resin composition is 100% by weight, the content of the epoxy resin is preferably 10 to 50% by weight, particularly preferably 20 to 40% by weight. More preferably 20 to 35 parts by volume. When the content of the epoxy resin (A) is outside this range, the curability of the resin composition tends to be lowered. [Active ester compound of the component (B)] The (B) active ester compound in the invention is not particularly limited as long as it has an active ester which is a function as a curing agent for the epoxy resin. It is preferably a compound having two or more active ester groups in one molecule, and particularly preferably a compound having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. More preferably, the compound is an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group in -10-201030046, and the aromatic compound has two molecules in the molecule. An aromatic compound of the above ester group. Further, it may contain a linear or multi-chain polymer. In addition, when the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the epoxy resin (A) can be improved, and when it is a compound having an aromatic ring, the compound can be improved. Heat resistance. Particularly, from the viewpoint of heat resistance and the like, an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol φ compound is preferred. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, isophthalic acid, and terephthalic acid are more preferable from the viewpoint of heat resistance. Specific examples of the sulfur carboxylic acid compound include sulfuric acid, thiobenzoic acid, and the like. Specific examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol porphyrin, and methylated bisphenol φ A′ methylated bisphenol F. , methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, anthracene, 5·dihydroxynaphthalene, 1,6-dihydroxy Naphthalene' 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol - Novolak, etc. Among them, from the viewpoint of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol s, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, and children are preferred. Tea phenol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, homobenzene Trisphenol, benzenetriol-11 - 201030046, dicyclopentadienyl diphenol, phenol-novolac varnish, especially catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol-novolac, More preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bicyclo Pentadienyl diphenol, phenol-novolak, especially dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, benzene φ phenol - Novolak, more preferably dicyclopentadienyl diphenol, phenol - Aldehyde varnish, particularly preferably based dicyclopentadiene diphenol. Specific examples of the thiol compound include benzenedithiol and triterpene dithiol. The active ester compound may be used in combination of two or more kinds. As the active ester compound, the active ester compound disclosed in JP-A-2004-427761 can be used, and a commercially available one can also be used. As a commercially available active ester compound, specifically, it is preferably a dicyclopentadienyl diphenol constructor, an acetonitrile-based phenol-phenol novolak, a benzamidine phenol-phenol novolak, and a better one. Contains dicyclopentadienyl bisphenol structure. Examples of the structure containing a dicyclopentadienyl diphenol include EXB-945 1 and EXB-9460 (manufactured by DIC Co., Ltd.), and as the acetylation of the phenol-novolac phenol, DC808 is used as the phenol. The benzyl hydrazide of the novolak is YLH1026C (made by Japan Epoxy Resin Co., Ltd.). The active ester compound of the present invention may be used alone or in combination of two or more. The method for producing the active ester compound is not particularly limited and can be produced by a well-known method, specifically, a carboxylic acid compound and/or a -12-201030046 thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Obtained by a condensation reaction. In the present invention, an epoxy curing agent other than the active ester may be used together with the active ester compound for the purpose of improving the glass transition temperature and the like. Examples of the epoxy curing agent other than the active ester include TD2090, TD2131, LA7052, LA7054, LA3018, LA1 3 56 (made by DIC), MEH-7600 'MEH-78 5 1 and MEH - 8 000H (Minghe Chemical (share) system, ❿ NHN, CBN, GPH-65, GPH-103 (Sakamoto Chemical Co., Ltd.), SN170 'SN180 ' SN190, SN475, SN485 'SN495 ' SN375, SN395 (Dongdu Huacheng) a phenolic curing agent such as a system, a benzoic acid compound such as Fa, Pd (manufactured by Shikoku Chemical Co., Ltd.), HFB2006M (Showa Polymer Co., Ltd.), and methyl hexahydrophthalic anhydride. An acid anhydride such as nadic acid anhydride or hydrogenated methyl naduccinic acid anhydride. A phenolic curing agent which is a compound having a phenolic hydroxyl group is particularly preferred. When the active ester compound and other hardeners are used, if the total φ epoxy hardener (containing the active ester compound) in the epoxy resin composition is 1% by weight, the weight % of the active ester compound is preferably 10 ~100%, better system 20~100%. Further, when all of the epoxy curing agent (including the active ester compound) in the epoxy resin composition is 100% by weight, the weight % of the phenolic curing agent is preferably 〇30%, more preferably 〇20%. By using an active ester compound and a phenol compound (phenolic curing agent), the balance between the arithmetic mean roughness and the coefficient of linear expansion of the surface of the insulating layer can be obtained. In this case, if the ratio of the phenol compound is large, the arithmetic mean roughness of the surface of the insulating layer tends to increase, and if the ratio of the phenol compound is small, the linear expansion ratio tends to increase from -13 to 201030046. In the present invention, the epoxy resin composition contains the epoxy hardener of the component (B) active ester compound, preferably the total number of epoxy groups present in the epoxy resin composition and epoxy hardening. The ratio of the total number of reactive groups of the agent becomes 1:0. 4~1 : 1. 1 amount. In addition, the total number of epoxy groups present in the epoxy resin composition is the total amount of the epoxy resin after dividing the weight of the solid content of each epoxy resin by the epoxy equivalent. The total number of the reactive groups (active ester groups, active hydroxyl groups, and the like) of the epoxy curing agent is the total amount of the hardeners obtained by dividing the solid content of each curing agent by the reaction group equivalent weight. When the content of the curing agent is outside the preferred range, the heat resistance of the cured product obtained by curing the epoxy resin composition tends to be insufficient. [Phenoxy resin having an alicyclic structure of the component (C)] In the present invention, the phenoxy resin having an alicyclic structure is not particularly limited as long as it is a phenoxy resin having an alicyclic structure. Here, "alicyclic structure" means "in the organic compound of a carbon atom ring-bonded structure, the aromatic compound is removed", "summary saturated hydrocarbon (cycloalkane) and unsaturated hydrocarbon A person with a double bond (cycloolefin) in the ring. Examples of the phenoxy resin having an alicyclic structure include a cyclohexane structure, a trimethylcyclohexane structure, and a terpene structure. Among them, from the viewpoint of further achieving the effects of the present invention, it is more preferable to have a trimethylcyclohexane structure, a terpene structure, and more preferably a terpene structure. In the case of the phenoxy resin having a trimethylcyclohexane structure, a phenoxy resin disclosed in JP-A-200-176658 is exemplified. The phenoxy resin having a terpene structure, in the phenoxy resin disclosed in JP-A-2006-1 766 528, the divalent phenol compound as a raw material instead of bis(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, a phenoxy resin synthesized using terpene diphenol or the like. The phenoxy resin having an alicyclic structure of the present invention may be used alone or in combination of two or more. The upper limit 重量 of the weight average molecular weight of the phenoxy resin having an alicyclic structure is preferably 1 〇〇〇〇〇, particularly preferably 60,000, from the viewpoint of preventing an increase in roughness and an increase in thermal expansion coefficient. Jiajia 50000 'You are better than 45000, and then better 40000, especially good 35000. On the other hand, the lower limit 重量 of the weight average molecular weight of the phenoxy resin is preferably from the viewpoint of sufficiently obtaining the peeling strength from the conductor layer, and is preferably 2000'. Department 1 5000' and then better 1 7000, especially good system 20000. The number average molecular weight is determined by gel permeation chromatography (GPC method (polystyrene conversion). The number average molecular weight of the GPC method' can be specifically used by the LC-9A/RID-6A manufactured by Shimadzu Corporation. As a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. was used as a column, and a solution of 0 to 4% by weight of lithium bromide dissolved in N-methylpyrrolidone was used as a mobile device. The phase was measured at a column temperature of 40 ° C and was calculated using a calibration curve of standard polystyrene. The method for producing the phenoxy resin is not particularly limited, and can be produced by the following method. -15-201030046 bisphenol compound having a trimethylcyclohexane structure or a bisphenol compound having a terpene structure and a bifunctional epoxy resin as a raw material, according to a well-known method for preparing a phenoxy resin, an epoxy group and The equivalent ratio of the phenolic hydroxyl group is about 1:0·9~1: 1. The range of 1 makes the reaction easy to manufacture. Further, in the range in which the effects of the present invention are exerted, a phenoxy resin other than the phenoxy resin having an alicyclic structure may be used in combination. Examples of the other phenoxy resin include 1256, 4250, ΥΧ8100, ΥΧ6954' YL7553, and YL7482 manufactured by Nippon Epoxy Resin Co., Ltd. In the epoxy resin composition of the present invention, when the nonvolatile content of the epoxy resin composition is 100% by weight, the content of the phenoxy resin is preferably from 1 to 20% by weight, more preferably from 5 to 1%. 0% by weight. When it is less than 1% by weight, sufficient flexibility cannot be obtained, workability is lowered, or the peel strength of the conductor layer formed by plating tends to be insufficiently obtained, and when it exceeds 20% by weight, lamination is required. There is insufficient liquidity, or the roughness tends to become excessive. [Inorganic bismuth filling] The epoxy resin composition of the present invention may further contain an inorganic cerium filling for the purpose of further reducing the linear expansion ratio and the like. Examples of the inorganic cerium filling include vermiculite, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate 'magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and the like. Barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium sulphate, etc. are particularly suitable for amorphous vermiculite, molten vermiculite, Crystalline vermiculite 'synthesis of vermiculite such as vermiculite. One type of -16-201030046 or more than two kinds of inorganic cerium fillings can be used. As the vermiculite, it is preferably a spherical one. The average particle size of the inorganic cerium charge is preferably less than πμπι or less than -8 μmη, especially excellent. 7μιη below. When the average particle diameter exceeds Ιμηη, the peeling strength of the conductor layer formed by the shovel tends to decrease. In addition, when the average particle diameter of the inorganic cerium charge is too small, when the epoxy resin composition is used as the resin varnish, the operability is lowered due to the increase in the viscosity of the varnish. Therefore, the average particle diameter is preferably ≥ or more. . Further, in order to improve the moisture resistance, the inorganic cerium filling material is preferably a surface treated with a surface treating agent such as an epoxy decane coupling agent, an amino decane coupling agent or a titanate coupling agent. The average particle size of the above inorganic cerium charge can be determined by laser diffraction/scattering method based on the Mie scattering theory. Specifically, the laser particle size distribution measuring apparatus can be used to determine the particle size distribution of the inorganic cerium charge on a volume basis to determine the median diameter as the average particle diameter. The sample is measured and the inorganic ruthenium charge is dispersed in the water by ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used. When the amount of the non-volatile component of the epoxy resin composition is 100% by weight, the content of the epoxy resin composition varies depending on the characteristics required for the resin composition, but is preferably 10 to 70% by weight. /. More preferably, if the content of the inorganic cerium filling is too small, the linear expansion ratio of the cured product tends to be high, and if the content is too large, the thinning becomes difficult when the adhesive film is prepared. 'Or the hardened material has a tendency to become brittle. -17- 201030046 [Curing accelerator] The epoxy resin composition of the present invention may contain a curing accelerator for the purpose of preparing a curing time and a curing temperature. Examples of the curing accelerator include organic phosphine compounds such as TPP, TPP-K, TPP-S, and TPTP-S (Beixing Chemical Industry Co., Ltd.), Curezol 2MZ, 2E4MZ 'C11Z, C11Z-CN' C11Z. -CNS' C11Z-A' 2MZ-OK, 2MA-OK, 2PHZ (Miyako Kasei Industrial Co., Ltd. product name), etc., No 哩 compound, Novacure (Asahi Kasei Industrial Co., Ltd. trade name), Novacure (Fuji Chemical Industry Co., Ltd. An amine addition compound such as a trade name), 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2, An amine compound such as 4,6-tris(dimethylaminomethyl)phenol. One type or two or more types of hardening accelerators can be used. In the epoxy resin composition of the present invention, the content of the hardening accelerator is, when the total amount of the epoxy resin and the phenolic hardener contained in the epoxy resin composition is 100% by weight (nonvolatile matter), Preferably, it is 0. 1 to 5 wt%. [Rubber Particles] The epoxy resin composition of the present invention may contain solid rubber particles for the purpose of improving the mechanical strength of the cured product, the stress relieving effect, and the like. The rubber particles of the present invention are not dissolved in the organic solvent in the preparation of the epoxy resin composition, and are not compatible with the components in the resin composition such as an epoxy resin, but are in the varnish of the epoxy resin composition. A decentralized state exists. Such rubber particles are generally prepared in a particulate form by making the molecular weight of the rubber component large so as not to be dissolved in the organic solvent or the resin. -18- 201030046 Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particle-based particles have rubber particles of a core layer and a shell layer, and examples thereof include a two-layer structure in which a shell layer of an outer layer is a glassy polymer, and a core layer of an inner layer is a rubber-like polymer, or an outer layer. The shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glass layer is composed of, for example, a polymer of methyl methacrylate oxime, and the rubber-like polymer layer is composed of, for example, butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Stafilrod AC3832, AC3816N (GANZ Chemicals Co., Ltd.), and Metabren W-5500 (Mitsubishi® (trade name)). Specific examples of the acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber pellets include Metarren 3 00 Α (average particle diameter 〇·1 μιη) and W4 50A (average particle diameter 0·5 μιη) (manufactured by Mitsubishi Rayon Co., Ltd.). One or two or more kinds of rubber particles can be used. The average particle diameter of the rubber particles to be blended is preferably 0. 005~Ιμιη range, better system 0. 2~0·6μηι range. The average particle diameter of the rubber particles in the present invention can be measured by a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and FPRA-10 00 (manufactured by Otsuka Electronics Co., Ltd.) is used to prepare the particle size distribution of the rubber particles on a weight basis, and the position of the rubber particles is regarded as Measured by the average particle size. -19- 201030046 When the rubber particles are blended, if the non-volatile content of the epoxy resin composition is 100% by weight, the content of the epoxy resin composition is preferably 0. 5 to 10% by weight, more preferably 1 to 4% by weight. [Other thermosetting resin] The epoxy resin composition of the present invention may be blended with a cyanate resin or a maleic imine compound or a bisallyl nadi, as long as the effects of the present invention are not impaired. A thermosetting resin such as bis-allyl-nadi-imide compound Q, vinyl benzyl resin or vinyl benzyl ether resin. Examples of the cyanate resin include BADCY, LECY, and BA230S70 ' PT15 ' PT30 ' PT60 (manufactured by LONZA Co., Ltd.) as a maleimide resin, and examples thereof include BMI1000, BMI2000, BMI3000, BMI4000, and BMI5100. Industrial (share) system, BMI, BMI-70, BMI-80 (KI Chemical Co., Ltd.), ANILIX-MI (manufactured by Mitsui Chemicals Co., Ltd.), as a bisallyl nadiimide compound ΒΑΝΙ ·Μ, BANI-X (made by Jiushan Petrochemical Industry Co., Ltd.), @ As a vinyl benzyl resin, V5 000 (made by Showa Polymer Co., Ltd.) can be used as a vinyl benzyl ether resin. V1000X, V1100X (Showa Polymer Co., Ltd.). Other thermosetting resins may be used alone or in combination of two or more. [Flame Retardant] The epoxy resin composition of the present invention may contain a flame retardant insofar as the effects of the present invention are not impaired. Examples of the flame retardant include organic -20-201030046 phosphorus-based flame retardant, organic nitrogen-containing phosphorus compound, nitrogen compound, polyfluorene-based flame retardant, and metal hydroxide. Examples of the organic phosphorus-based flame retardant include a phosphine compound such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and a phosphorus-containing benzene such as HFB-2 00 6M manufactured by Showa Polymer Co., Ltd. Rheuphos 30, 50, 65, 90, 1 10, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, ΤΙΒΡ, Beixing Chemical Industry, 噚 化合物 compound, Ajinomoto Precision Technology Co., Ltd. φ PPQ, CLARIANT (manufactured by φ ΟΡ ΟΡ ΟΡ ΟΡ ΟΡ ΟΡ ΟΡ ΟΡ ' ' ' ' ' ' 化学 化学 磷酸 磷酸 磷酸 磷酸 磷酸 磷酸 磷酸 等 等 等 等 等 等 等 FX FX FX FX FX FX FX FX FX FX FX FX FX FX FX 环氧树脂 环氧树脂 环氧树脂Phosphorus-containing phenoxy resin such as ERF00 1 manufactured by Dongdu Chemical Co., Ltd. Examples of the organic nitrogen-containing phosphorus compound include a phosphate amide compound such as SP670 and SP7 03 manufactured by Shikoku Chemicals Co., Ltd., and a phosphazene compound such as SPB100 and SPE 100 manufactured by Otsuka Chemical Co., Ltd. Wait. Examples of the metal hydroxides include yttrium hydroxide UD65, UD650, UD653, etc., Β-30, Β-325, Β-315, Β-made by U.S.A. 305, B-303, UFH-20 and other aluminum hydroxide. One or two or more kinds of the flame retardant can be used. [Resin additive] The epoxy resin composition of the present invention may optionally contain various other resin additives other than the above in the range in which the effects of the present invention are exerted. Examples of the resin additive include organic chelating agents such as strontium powder, strontium powder, and fluoro powder, viscous agents such as 〇rben and Benton, and -21 - 201030046 polyoxyl An anti-foaming agent or a leveling agent, an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent, an adhesion-promoting agent, a phthalocyanine blue, a phthalocyanine green, an iodine green, a double A coloring agent such as azo yellow or carbon black. One or two or more kinds of the resin additives may be used. The use of the resin composition of the present invention is not particularly limited, and it can be used for an insulating resin sheet for an adhesive film, a prepreg, etc., a wiring substrate, a solder resist, a bottom slab, a die bonding material, a semiconductor sealing material, and a buried hole. A resin, a resin embedded in a part, and the like require a wide range of uses of the resin composition. [Adhesive film] The resin composition of the present invention is formed by coating a support film to form a resin composition layer, and is used as an adhesive film for a multilayer printed wiring board. The resin composition of the present invention may be applied to a wiring substrate to form an insulating layer. However, it is generally used in the form of an adhesive film for the formation of an insulating layer. The adhesive film of the present invention can be prepared by a method known to those skilled in the art, for example, by dissolving a resin varnish in which a resin composition is dissolved in an organic solvent to support the film as a support, coating the resin varnish, and then spraying by heating or hot air. Blowing or the like to dry the organic solvent to form a resin composition layer is produced. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate, cellosolve, carbitol, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-A A guanamine-based solvent such as a pyrrolidone or the like. Two or more types of organic solvents can be used in combination. 201030046 The drying conditions are not particularly limited, and the content of the organic solvent to the resin composition layer is 1% by weight or less, preferably 5% by weight or less, and is dried. Drying conditions allow suitable and suitable drying conditions to be set by simple experimentation. Although the amount of the organic solvent in the varnish is different', for example, the varnish containing 30 to 60% by weight of the organic solvent may be dried at 50 to 150 ° C for 3 to 10 minutes. The thickness of the resin composition layer formed in the adhesive film is usually equal to or greater than the thickness of the φ body layer. Since the thickness of the conductor layer having the wiring substrate is usually in the range of 5 to 80 μm, the thickness of the resin composition layer preferably has a thickness of 1 Å to 100 μm. The resin composition layer can also be protected by a protective film described later. By protecting the film, it is possible to prevent adhesion or damage of dust or the like to the surface of the resin composition layer. Examples of the support film and the protective film in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), and polyethylene naphthalate. A polyester such as an ester, a polycarbonate, a polyimide, a metal foil such as a release paper, a copper foil, or an aluminum foil. Further, the support film and the protective film can be subjected to a matting treatment, a corona treatment, and a mold release treatment. The thickness of the support film is not particularly limited, and it is preferably 10 to 150 μm, more preferably 25 to 50 μm. Further, the thickness of the protective film is also not particularly limited, and it is preferably 1 to 40 μm, more preferably 10 to 30 μm. Further, as will be described later, the support film used as the support in the production step of the adhesive film can also be used as a protective film for protecting the surface of the resin composition layer. -23- 201030046 The support film of the present invention is peeled off after being laminated on a wiring board or after forming an insulating layer by heat curing. After the adhesive film is heat-cured, if the support film is peeled off, adhesion of dust or the like can be prevented in the hardening step, and the surface of the hardened insulating layer can be made flat. Slippery. When peeling after hardening, it is preferred to apply a release treatment to the support film in advance. Further, the resin composition layer formed on the support film is preferably formed such that the area of the layer is smaller than the area of the support film. Further, the adhesive film can be wound into a roll to be stored and stored. @ [Prepreg] The resin composition of the present invention can be impregnated with a hot-melt method or a solvent method for a sheet-like reinforcing substrate (fiber-incorporated), and is semi-hardened by heating to become a prepreg. The sheet-like reinforcing substrate is not particularly limited, and those conventionally used in the prepreg can also be used. Specifically, a fiber made of a prepreg such as a glass cloth or an aramid fiber can be used. The hot-melt method does not dissolve the resin composition of the present invention in an organic solvent φ, but after being applied to a coated paper having good releasability to the resin, it is laminated on a sheet-like reinforcing substrate, or A method of producing a prepreg by directly coating a resin on a sheet-like reinforcing substrate by a die coater without dissolving the resin in an organic solvent. In the same manner as the adhesive film, the solvent method is prepared by dissolving a resin in an organic solvent to prepare a resin varnish, immersing the flaky reinforcing substrate in the varnish, impregnating the flaky reinforcing substrate with a resin varnish, and then drying the resin. . -24- 201030046 [Multilayer printed circuit board] By using the adhesive film or prepreg of the present invention, a multilayer printed circuit board can be manufactured. A method of manufacturing the multilayer printed circuit board of the present invention using the adhesive film of the present invention will be described. When the resin composition layer is protected by the protective film, after peeling off, the resin composition layer is laminated on one or both sides of the circuit substrate so as to directly contact the circuit substrate. In the adhesive film φ of the present invention, a method of laminating on a circuit substrate under reduced pressure by vacuum lamination is suitably used. The lamination method can be batchwise or continuous by rolls. Further, the adhesive film and the wiring substrate may be preheated (preheated) as needed before lamination. The lamination condition is preferably 70 to 140 ° C in terms of the pressure bonding temperature (laminating temperature), and preferably 1 to 11 kgf/cm 2 in the pressure bonding pressure (9·8 χ 104 to 107. 9xl〇4N/m2), preferably 20mmHg in terms of air pressure. Lamination was carried out under reduced pressure at 7 hPa). 9 Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum presser made by Nichigo-Morton Co., Ltd., a vacuum press laminator made by a machine manufacturer, and a roll dryer made by a company. Coating machine, Hitachi AIC (stock) vacuum laminator, etc. The inner layer circuit substrate in the present invention is mainly formed on one or both sides of a substrate such as a glass epoxy resin, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. A conductor layer (line) with pattern processing. Moreover, in the case of manufacturing a multilayer printed circuit board in which a conductive layer and an insulating layer are formed to form a layer of one or both sides of a patterned conductor layer (line), an intermediate manufacturing material for forming an insulating layer and a conductor layer is also used. It is included in the inner layer wiring substrate of the present invention. In the inner layer circuit board, the surface of the conductor line layer is roughened beforehand, and the roughening process is performed in advance, and it is preferable from the viewpoint of the adhesion of the insulating layer to the inner layer circuit board. In this manner, after the adhesive film is laminated on the wiring substrate, the support film is peeled off, and the insulating layer can be formed on the wiring substrate by thermal curing. The conditions for heating and hardening can be selected from the range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 160 ° C to 200 ° C for 30 to 120 minutes. After the formation of the insulating layer, the support film is not peeled off before the hardening, and it is peeled off here. Next, the insulating layer formed on the wiring substrate is opened to form a via hole and a through hole. The opening can be carried out, for example, by well-known methods such as drilling, laser, plasma, etc., and can be carried out in combination as needed. The opening of a laser such as a carbon dioxide laser or a YAG laser is the most common method. Next, the surface of the insulating layer is roughened. The roughening @ treatment in the present invention is preferably carried out by a wet roughening method using an oxidizing agent. Examples of the oxidizing agent include barium permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. An oxidizing agent generally used for roughening an insulating layer in the manufacture of a multilayer printed circuit board, that is, an alkaline permanganic acid solution (for example, an aqueous solution of sodium permanganate or sodium permanganate) It is preferred to carry out the roughening. The roughness of the roughened surface of the surface of the insulating layer is roughened, and Ra is preferably 0 when forming a fine line. 5 μτη or less. Further, the Ra 値 system indicates a type of surface roughness of -26-201030046, which is called arithmetic mean roughness, specifically, from the surface of the average line, the absolute height of the height changed within the measurement range is measured. Arithmetic average. For example, WYKO NT3 3 00 manufactured by VEECO Instruments Co., Ltd. can be obtained by a VSI contact mode, a 50-fold lens, and a number obtained by measuring a range of 121 μm χ 92 μm. Next, on the surface of the resin composition layer on which the anchor having the unevenness is formed by the roughening treatment, the conductor layer is formed into a shape by a combination of electroless shovel plating and electrolytic plating. Further, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. Further, after the formation of the conductor layer, by annealing at 150 to 200 ° C for 20 to 90 minutes, the peel strength of the conductor layer can be further improved and stabilized. The peel strength of the conductor layer is better. 6kgf/cm or more. Further, as a method of patterning the conductor layer to form a wiring, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used. The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a flaky fibrous substrate ® made of fibers by a hot melt method or a solvent method, and semi-curing by heating. That is, it can be a prepreg which is in a state in which the resin composition of the present invention is impregnated into a sheet-like fibrous base material made of fibers. As the sheet-like fibrous base material made of the fiber, for example, a glass cloth or an aromatic polyamide fiber can be used as the fiber for the prepreg. The hot melt method does not dissolve the resin in an organic solvent, but Once the resin is applied onto a coated paper having good peelability from the resin, it is laminated on a sheet-like fibrous substrate, or directly coated by a die coater, etc., and manufactured by -27-201030046. The method of dip. In the same manner as the adhesive film, the solvent method is prepared by dissolving a resin in an organic solvent to prepare a resin varnish, immersing the flaky reinforcing substrate in the varnish, impregnating the flaky fiber substrate with a resin varnish, and then drying the resin. . A method of manufacturing the multilayer printed circuit board of the present invention using the prepreg of the present invention will now be described. On the circuit substrate, a prepreg of the present invention is overlapped with one piece or as needed, and the metal plate is sandwiched between the release film and the pressure. Pressurization lamination is carried out under heating. The pressure is preferably 5 to 40 kgf/cm 2 (49 χ 104 to 392 x 10 4 N/m 2 ), and the temperature is preferably 120 to 200 t, preferably 20 to 100 minutes. Further, in the same manner as the adhesive film, it can be laminated by heat-curing on a circuit board by vacuum lamination, and then heat-hardened. Then, in the same manner as described above, the surface of the prepreg cured by the oxidizing agent is roughened, and then the conductor layer is formed by plating to produce a multilayer printed circuit board. [Examples] @ The present invention will be described in more detail by way of the following examples and comparative examples, but the invention is not limited thereto in any sense. In the following description, "parts" means "parts by weight". (Experimental Example 1) Into 15 parts of methyl ethyl ketone (hereinafter referred to as r MEK) and 15 parts of cyclohexanone, 30 parts of liquid bisphenol A type epoxy resin (epoxy) was heated and dissolved while stirring. Equivalent 180, "-28 - 291 201030046 jER82 8EL" manufactured by Epoxy Epoxy Resin Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent, "Noked Chemical Co., Ltd." "NC3000H"). In this case, a mixed active ester compound ("EXB9460-65T" ester equivalent 223 (solid solution 65% toluene solution) made by DIC) was used. 5 parts of accelerator (Guangrong Chemical Industry Co., Ltd., "4-dimethylaminopyrrolidone", 120 parts of spherical vermiculite (average particle size 〇·5μιη, with amine-based treatment "SO-C2" ( 40 parts of phenoxy φ (produced in the same manner as in Example 1 of JP-A-2006-176658, (4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 3 , 3', 5, 5'-four-bow 4,4'-diphenol diglycidyl ether synthesized phenoxy resin, non-deoxygen% by weight of 1:1 solution of hydrazine and cyclohexanone, weight average of 3 0 000 ), uniformly dispersed by a high-speed rotary mixer to produce a fat varnish (244 parts solid content, 49% by weight of vermiculite, and a ratio of reactive groups of epoxy oxygen hardener 1: 0. 87). Next, the resin varnish was applied to polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as "PET") in a mouth-washing manner so that the thickness of the resin after drying became 4 μm. Dry at 120 ° C for 1 〇〇 ° C for 6 minutes (about 2% by weight of residual solvent). On the surface of the resin composition, a polypropylene film having a thickness of 15 μm was attached and wound into a roll. The roll-shaped adhesive film was slit into 507 mm, thereby obtaining a flaky adhesion of 507 x 336 mm (Experimental Example 2) Ϊ·80, and the resin of the living hard pyridine was made from the double 3 base-h 30 sub-quantity. The tree and the ring are heated and dissolved in 30 parts by stirring with a diester (flattened with a thin film -29-201030046 in 15 parts of methyl ethyl ketone (hereinafter referred to as "ΜΕΚ"), 15 parts of cyclohexanone Liquid bisphenol A type epoxy resin (epoxy equivalent 18 〇, "JER828EL" made by Nippon Epoxy Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, Nippon Chemical Co., Ltd. ("NC3000H"), in which 40 parts of active ester compound ("EXB9460-65T" manufactured by DIC, active ester equivalent 223, 65% solid solution in toluene) and 15 parts of phenolic hardener are mixed. LA7052 (made by DIC), a phenol-novolac resin containing a three-till structure, a phenolic hydroxyl equivalent of 120, a solid component of 60% MEK solution, 〇. 5 parts of hardening accelerator (manufactured by Guangrong Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 100 parts of spherical vermiculite (average particle diameter of 0. 5 μπι, amino decane treated with "SO-C2" (manufactured by ADMATECHS), and 4 parts by weight of phenoxy resin (in the same manner as in Example 1 of JP-A-2006-176658, bis(4-hydroxyphenyl) a phenoxy resin synthesized by -3,3,5-trimethylcyclohexan and 3,3',5,5'-tetramethyl-4,4'-diphenol diglycidyl ether, nonvolatile 30% by weight of a 1:1 solution of hydrazine and cyclohexanone, weight average molecular weight 30000), uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish (207 parts solid content, 48% by weight of vermiculite, epoxy group) The ratio of the reactive groups to the epoxy hardener is 1:0. 72). Then, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Experimental Example 3) In 15 parts of methyl ethyl ketone (hereinafter referred to as "ΜΕΚ"), 15 parts of 201030046 of cyclohexanone, 30 parts of liquid bisphenol A type epoxy resin was heated and dissolved while stirring. Oxygen equivalent weight 180, "JER82 8EL" manufactured by Nippon Epoxy Resin Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, manufactured by Nippon Kayaku Co., Ltd. "NC3000H"). Among them, 'mix 40 parts of active ester compound (EXB9460-65T made by DIC, active ester equivalent 223, 65% solid solution in toluene), and 15 parts of phenolic hardener LA7〇52 (DIC) ), a phenol-phenol aldehyde aldehyde varnish resin containing a triterpenoid structure, a phenolic hydroxyl equivalent of 120, a solid component of 60% MEK solution), 〇. 5 parts of hardening accelerator (manufactured by Guangrong Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 100 parts of spherical vermiculite (average particle diameter of 0. 5 μπι, amino decane treated with "SO-C2" (manufactured by ADMATECHS), and 30 parts of phenoxy resin (in the first embodiment of JP-A-2006-176658, 'in place of bis(4-hydroxyphenyl)-3) , 3,5-trimethylcyclohexane, a phenoxy resin synthesized by using bismuth diphenol, a non-volatile 40% by weight solution of ruthenium and cyclohexanone in a 1:1 solution, weight average molecular weight of 30,000 Ο) ' Uniform dispersion by a high-speed rotary mixer to produce a resin varnish (solid component 207 parts 'wurrite 48% by weight, the ratio of epoxy group to epoxy hardener reactive group 1:0. 72). Next, an adhesive film was obtained in the same manner as in Example 1 using this resin varnish. (Experimental Example 4) A liquid bismuth-type epoxy resin (epoxy) which was heated and dissolved in 15 parts of methyl ethyl ketone (hereinafter referred to as "ΜΕΚ") and 15 parts of cyclohexanone Equivalent 180' Japan Epoxy Resin Co., Ltd. "~ 31 - 201030046 jER828EL") and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, Nippon Chemical Co., Ltd. "NC3 000H"). Among them, 80 parts of an active ester compound (EXB9460-65T, manufactured by DIC, an active ester equivalent of 223, and a 65% solid solution in toluene) were mixed. 5 copies. Hardening accelerator ("4-dimethylaminopyridine" manufactured by Kwong Wing Chemical Industry Co., Ltd.), 130 parts of spherical vermiculite (average particle size 〇·5μπι, treated with amine decane "SO-C2" ( 40 parts of phenoxy resin (produced by bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane in the same manner as in Example 1 of JP-A-2006-176658) a phenoxy resin synthesized with 3,3',5,5'-tetramethyl-4,4'-diphenol diglycidyl ether, a non-volatile 1:1 solution of hydrazine and cyclohexanone , weight average molecular weight 3 0000), uniformly dispersed by a high-speed rotary mixer to produce a resin varnish (solid component 252 parts, vermiculite 50% by weight, ratio of epoxy group to epoxy hardener reactive group 1: 0 . 87). Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Comparative Example 1) Into 15 parts of methyl ethyl ketone (hereinafter referred to as "ΜΕΚ") and 15 parts of cyclohexanone, 30 parts of liquid bisphenol fluorene type epoxy resin (epoxy) was heated and dissolved while stirring. Equivalent to 18 〇, "JER82 8EL" made by Japan Epoxy Resin Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, "Noked Chemical Co., Ltd." "NC3000H"). In this, 80 parts of the active ester compound (EXB9460-65T, manufactured by DIC, an active ester equivalent of 223, and a solid solution of 65% in toluene) were mixed. 5 parts of hard-32-201030046 chemical accelerator (Guangrong Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 120 parts of spherical vermiculite (average particle size 0. 5 μιη, with amino decane treated with "SO-C2" (manufactured by ADMATECHS), 30 parts of phenoxy resin (weight average molecular weight 50,000, Japan epoxide resin) "1 256B40" bisphenol A structure phenoxy Resin, non-volatile 40% by weight MEK solution), uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish (244 parts solid content, 49% by weight of vermiculite, reaction of epoxy group with epoxy hardener) The ratio of the base is 1:0. 87). Then, an adhesive film was obtained in the same manner as in Example 1 using this resin varnish. For example, in 15 parts of methyl ethyl ketone (hereinafter referred to as "ΜΕΚ"), 15 parts of cyclohexanone, 30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent weight 180) is heated and dissolved while stirring. , "JER82 8EL" made by Japan Epoxy Resin Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291 Φ, "Nippon Chemical Co., Ltd." "NC3 00 0H"). 40 parts of the active ester compound (EXB946 0-65T, 223, active ester equivalent 223, 65% solids in toluene) and 15 parts of phenolic hardener LA7052 (DIC) A phenol-novolak resin containing a triterpene structure, a phenolic hydroxyl equivalent of 120, a solid component of 60% MEK solution, 0. 5 parts of hardening accelerator ("4-dimethylaminopyridine" manufactured by Kwong Wing Chemical Industry Co., Ltd.), 100 parts of spherical vermiculite (average particle size 0. 5 μιη, treated with amine decane "SO- C2" (share) ADMATECHS), 30 parts of phenoxy resin (weight average molecular weight 50000, Japan Ring-33-201030046 Oxygen resin (stock) "125όΒ40" (bisphenol a structure phenoxy resin, non-volatile 40 weight % MEK solution), uniformly dispersed by a high-speed rotary mixer to produce a resin varnish (207 parts solid content, 48% by weight of vermiculite, ratio of reactive groups of epoxy groups to epoxy hardeners 1: 〇72 Then, an adhesive film was obtained in the same manner as in Example 1 using this resin varnish.
(比較例3 ) Q 於15份的甲基乙基酮（以下簡稱「MEK」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 氧樹脂（環氧當量180’日本環氧樹脂（股）製「(Comparative Example 3) Q In a solution of 15 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 15 parts of cyclohexanone, 30 parts of liquid bisphenol A type epoxy resin was heated and dissolved while stirring. Oxygen equivalent 180' Japan epoxy resin (share) system
L jER828EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3000H」）《於其中，混合40 份的酚系硬化劑LA7052 ( DIC (股）製，含有三哄構造的 苯酚-酚醛清漆樹脂，苯酚性羥基當量120，固體成分60% 的Μ EK溶液）、0 · 5份的硬化促進劑（廣榮化學工業（股 ❿ )製，「4-二甲胺基吡啶」）、100份的球形矽石（平均 粒徑 0·5μιη，附胺基矽烷處理「SO-C2」（股） ADMATECHS製）、3 0份的苯氧樹脂（與特開平2 0 0 6-l 7 6 6 5 8 號 公報的 實施例 1 同樣地 ，由雙 （ 4 - 羥苯基 ） -3，3,5-三甲基環己烷與3,3，，5,5、四甲基_4,4，-二酚二縮水 甘油醚所合成的苯氧樹脂，不揮發分30重量％的ΜΕΚ與 環己酮的1:1溶液，重量平均分子量30000)，藉由高 速旋轉混合機進行均勻分散，以製作樹脂清漆（固體成分 -34- 201030046 1 9 6份，矽石5 1重量％，環氧基與環氧硬化劑的反應基之 比率1 : 0.75)。接著，使用該樹脂清漆，與實施例1完 全同樣地得到黏著薄膜。 (比較例4 ) 於15份的甲基乙基酮（以下簡稱「MEK」）、15份 的環己酮中，邊攪拌邊加熱溶解30份的液狀雙酚A型環 ❹ 氧樹脂（環氧當量180，日本環氧樹脂（股）製「 jER828EL」）與30份的聯苯型環氧樹脂（環氧當量291 ，日本化藥（股）製「NC3000H」）。於其中，混合60 份的SN485(東都化成（股）製，萘酚芳烷基型，苯酚性 羥基當量215)之50%MEK溶液、0.5份的硬化促進劑（ 廣榮化學工業（股）製，「4-二甲胺基吡啶」）、120份 的球形矽石（平均粒徑〇·5μιη，附胺基矽烷處理「SO-C2 」（股）ADMATECHS製）、40份的苯氧樹脂（與特開 Φ 平2006-176658號公報的實施例1同樣地，由雙（4-羥苯 基）-3,3,5-三甲基環己烷與3,3’，5,5’-四甲基-4,4’-二酚二 縮水甘油醚所合成的苯氧樹脂，不揮發分30重量％的 ΜΕΚ與環己酮的1: 1溶液，重量平均分子量30000) 、8 份的芯殻型丙烯酸橡膠粒子（三菱嫘縈（股）製，「 W450」），藉由高速旋轉混合機進行均勻分散，以製作 樹脂清漆（固體成分199·5份，矽石50重量％，環氧基與 環氧硬化劑的反應基之比率1:0.73)。接著，使用該樹 脂清漆，與實施例1完全同樣地得到黏著薄膜。 -35- 201030046 <剝離強度及Ra値側定用樣品的調製> (1) 層合板的基底處理 將形成有內層線路的玻璃布基材環氧樹脂兩面覆銅層 合板[銅箔的厚度18 μπι，基板厚度0.3 mm，松下電工（股 )製R5715ES]的兩面浸漬在MEC (股）製CZ8100中， 以進行銅表面的粗化處理。 (2) 黏著薄膜的層合 @ 使用分批式真空加壓層合機MVLP-500 C (股）名機 製作所製，商品名），將實施例及比較例所作成的黏著薄 膜層合在層合板的兩面。層合係進行30秒的減壓以使氣 壓成爲13hPa以下，然後在30秒、100°C、壓力〇.74MPa 下加壓而進行。 (3 )樹脂組成物的硬化 由所層合的黏著薄膜剝離PET薄膜，在180 °C、30分 鐘的硬化條件下將樹脂組成物硬化。 β (4 )粗化處理 於60°C將層合板浸漬在膨潤液的 ATOTECH日本（ 股）之含有二乙二醇單丁基醚的 Swelling Dip Securigand P中5分鐘，接著於8〇°C浸漬在作爲粗化液 的 ATOTECH 日本（股）之 Concentrate Compact P ( KMn04 : 60g/L，NaOH : 40g/L 的水溶液）中 20 分鐘， 最後於40°C浸漬在作爲中和液的 ATOTECH日本（股） 之 Reduction Solution Securigand P 中 5 分鐘。對於此粗 -36- 201030046 化處理後的層合板，進行絕緣層的算術表面粗糙度（Ra )之測定。 (5 )半加成法的鍍敷 爲了在絕緣層表面上形成線路，將層合板浸漬含 PdCl2的無電解鍍敷用溶液中，接著浸漬在無電解銅鍍敷 液中。於150°C加熱30分鐘以進行退火處理後，形成蝕刻 用光阻，藉由蝕刻形成圖型後，進行硫酸銅電解鍍敷，形 φ 成3 0±5μιη之厚度的導體層。接著，在180°C進行在60分 鐘的退火處理。對於此層合板，進行所鍍敷的銅之剝離強 度測定。 [鍍敷導體層的拉剝強度（剝離強度）] 在層合板的導體層中導入寬度l〇mm、長度100mm的 部分之切槽，剝離其一端且以夾具夾住（股份公司TSE Autocom型試驗機AC-50C-SL)，測定在室溫中以5 0mm/ ® 分鐘的速度在垂直方向中拉剝3 5mm時的荷重。 [粗化後的表面粗糙度] 使用非接觸型表面粗糙度計（VEECO儀器公司製 WYKO NT3 300 )，藉由 VSI接觸模式、50倍透鏡，由 測定範圍爲121μπι><92μιη所得之數値來求得算術平均粗 糙度（Ra )。又，藉由求得1 0點的平均粗糙度而測定 -37- 201030046 [線膨脹係數的測定] 將實施例1〜3及比較例1〜4所得之黏著薄膜在 190 °C熱硬化90分鐘而得到薄片狀的硬化物。將該硬化物 裁切成寬度約5mm、長度約15mm的試驗片，使用（股） RIGAKU 製熱機械分析裝置（Thermo Plus TMA83 1 0 )， 藉由拉伸加重法進行熱機械分析。將試驗片安裝在前述裝 置後，於荷重1克、升溫速度5 °c/分鐘的測定條件下連續 測定2次。算出第2次測定中從2 5 °C到1 5 0 °C爲止的平均 線熱膨脹率。 表1中顯示結果。 [表1] 配合(固體成分換算重量份） 實施 例1 比較 例1 實施 例2 實施 例3 比較 例2 比較 例3 實施 例4 比較 例4 環氧樹脂 1ER828EL 30 .30 30 30 30 30 .30 30 NC3000H 30 30 30 ' 30 30 30 30 30 活性酯化娜 EXB9460-65T 52 52 26 26 26 52 苯酚化合物 LA7052 9 9 9 24 SN485 30 硬化促進劑 4·二甲胺 .基吡啶 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 無機塡充料 SOC2 120 120 100 100 100 100 100 100 苯氧樹脂 含有三甲基 環己烷構造 12 12 12 12 12 含有萜烯構造 12 1256B40 12 12 橡膠粒子 W450 8 8 剝離強度化麵） 0.6 0.6 0.7 0.7 0.6 0.7 0.6 0.6 表面粗糙度（臟） reo 3¾) 300 280 320 600 230 300 線膨脹率（ppm) 48 55 35 34 40 35 51 60 201030046 如由實施例1與比較例1的比較可知，相對於使用雙 酷A構造的苯氧樹脂之比較例丨，使用含脂環式構造之苯 氧樹脂之實施例1，儘管表面粗糙度低，卻高剝離強度， 線膨脹率亦降低。同樣地，當比較實施例2、3與比較例 2時’可知比較例2中雖然對於實施例2、3將苯氧樹脂 換成雙酚A構造者，但是表面粗糙度及線膨脹率的値係 上升。 © 於實施例2、3中，倂用活性酯化合物與苯酚化合物 當作硬化劑’若與實施例1相比，雖然表面粗糙度有若 干上升的傾向’但是線膨脹率降低，可知藉由倂用而取 得雙方的平衡。又，比較例3中僅使用苯酚化合物當作 硬化劑’若與實施例2相比，則結果爲表面粗糙度大幅 上升。 實施例4與比較例4係含有橡膠粒子的組成，比較使 用活性酯化合物與苯酚化合物當作硬化劑的情況之不同， ® 使用活性酯化合物的實施例4者係表面粗糙度小，線膨脹 率亦爲低値。 產業上的利用可能性 可提供儘管使環氧樹脂組成物的硬化物表面經粗化處 理之粗化面的粗糙度比較小，該粗化面對鍍敷導體也能顯 示高密接力，且可達成線膨脹率小的絕緣層之環氧樹脂組 成物、黏著薄膜、預浸物、多層印刷電路板。再者，亦可 提供搭載有此等的電腦、攜帶式電話、數位照相機、電視 -39 - 201030046 等的電器製品，或自動二輪車、汽車、電車、船舶、飛機 等的交通工具。"L jER828EL") and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, "Nippon Chemical Co., Ltd." "NC3000H")", in which 40 parts of phenolic curing agent LA7052 (DIC) , a phenol-novolak resin containing a triterpene structure, a phenolic hydroxyl equivalent of 120, a 60% solids Μ EK solution, and 0.5 parts of a hardening accelerator (Guangrong Chemical Industry Co., Ltd., "4- Dimethylaminopyridine"), 100 parts of spheroidal vermiculite (average particle size 0. 5 μιη, treated with amine decane "SO-C2" (manufactured by ADMATECHS), 30 parts of phenoxy resin (with special opening) Example 1 of 2 0 0 6-l 7 6 6 5 8 Similarly, from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 3,3,,5, 5. A phenoxy resin synthesized by tetramethyl-4,4,-diphenol diglycidyl ether, a non-volatile 30% by weight 1:1 solution of hydrazine and cyclohexanone, weight average molecular weight 30000), by High-speed rotary mixer for uniform dispersion to make resin varnish (solid content -34- 201030046 196 parts, vermiculite 51% by weight, epoxy and epoxy hardener reaction Base ratio 1: 0.75). Then, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Comparative Example 4) Into 15 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 15 parts of cyclohexanone, 30 parts of liquid bisphenol A type cyclic oxirane resin was heated and dissolved while stirring. Oxygen equivalent weight 180, "JER828EL" manufactured by Nippon Epoxy Resin Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291, manufactured by Nippon Kayaku Co., Ltd. "NC3000H"). 60 parts of a 50% MEK solution of SN485 (made by Dongdu Chemical Co., Ltd., naphthol aralkyl type, phenolic hydroxyl equivalent 215) and 0.5 part of a hardening accelerator (manufactured by Guangrong Chemical Industry Co., Ltd.) , "4-dimethylaminopyridine"), 120 parts of spherical vermiculite (average particle size 〇·5μιη, treated with amine-based decane, "SO-C2" (manufactured by ADMATECHS)), 40 parts of phenoxy resin ( In the same manner as in Example 1 of JP-A-2006-176658, bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 3,3',5,5'- a phenoxy resin synthesized from tetramethyl-4,4'-diphenol diglycidyl ether, a non-volatile 30% by weight 1:1 solution of hydrazine and cyclohexanone, weight average molecular weight 30000), 8 parts core Shell-type acrylic rubber particles ("W450" manufactured by Mitsubishi Rayon Co., Ltd.) were uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish (solid content: 199. 5 parts, vermiculite 50% by weight, epoxy group) The ratio of the reactive groups to the epoxy hardener is 1:0.73). Then, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1. -35- 201030046 <Peel strength and preparation of Ra値 side fixed sample> (1) Base treatment of laminate sheet A glass cloth substrate epoxy resin double-sided copper-clad laminate in which an inner layer is formed [Copper foil The thickness of the substrate was 0.3 μm, the thickness of the substrate was 0.3 mm, and both sides of R5715ES manufactured by Matsushita Electric Works Co., Ltd. were immersed in CZ8100 manufactured by MEC Co., Ltd. to roughen the copper surface. (2) Lamination of adhesive film @ Using a batch-type vacuum pressure laminator MVLP-500 C (manufactured by Nihon Seiki Co., Ltd., trade name), the adhesive film made of the examples and the comparative examples was laminated on the layer. Both sides of the plywood. The laminating system was subjected to a pressure reduction of 30 seconds to bring the gas pressure to 13 hPa or less, and then pressurized at 30 sec, 100 ° C, and a pressure of 74 74 MPa. (3) Curing of the resin composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured at 180 ° C for 30 minutes. β (4 ) roughening treatment The laminate was immersed in a swelling solution of ATOTECH Japan (S) in Swelling Dip Securigand P containing diethylene glycol monobutyl ether at 60 ° C for 5 minutes, followed by impregnation at 8 ° C. In ATOTECH Japan's Concentrate Compact P (KMn04: 60g/L, NaOH: 40g/L aqueous solution) as a roughening solution for 20 minutes, and finally immersed in ATOTECH Japan as a neutralizing solution at 40 °C 5 minutes in the Reduction Solution Securigand P. For the laminate after the treatment of the thick -36-201030046, the arithmetic surface roughness (Ra) of the insulating layer was measured. (5) Plating by semi-additive method In order to form a wiring on the surface of the insulating layer, the laminate was immersed in a solution for electroless plating containing PdCl2, followed by immersion in an electroless copper plating solution. After heating at 150 ° C for 30 minutes for annealing treatment, a photoresist for etching was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 ± 5 μm. Next, annealing treatment was performed at 180 ° C for 60 minutes. For this laminate, the peel strength of the plated copper was measured. [Stretching strength (peeling strength) of the plated conductor layer] A groove having a width of 100 mm and a length of 100 mm was introduced into the conductor layer of the laminate, and one end was peeled off and clamped by a jig (the TSE Autocom type test of the joint stock company) AC-50C-SL), measured the load when peeling 35 mm in the vertical direction at a speed of 50 mm / ® minutes at room temperature. [Surface roughness after roughening] Using a non-contact surface roughness meter (WYKO NT3 300 manufactured by VEECO Instruments Co., Ltd.), the number obtained by the measurement range of 121 μm><92 μιη by VSI contact mode, 50-fold lens To find the arithmetic mean roughness (Ra ). Further, the average roughness of 10 points was measured to determine -37-201030046 [Measurement of coefficient of linear expansion] The adhesive films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were thermally cured at 190 ° C for 90 minutes. A flaky cured product was obtained. The cured product was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was carried out by a tensile weighting method using a thermoelectric mechanical analyzer (Thermo Plus TMA83 1 0). After the test piece was attached to the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C/min. The average coefficient of thermal expansion from 25 ° C to 150 ° C in the second measurement was calculated. The results are shown in Table 1. [Table 1] Formulation (solid content conversion by weight) Example 1 Comparative Example 1 Example 2 Example 3 Comparative Example 2 Comparative Example 3 Example 4 Comparative Example 4 Epoxy Resin 1 ER828EL 30 .30 30 30 30 30 .30 30 NC3000H 30 30 30 ' 30 30 30 30 30 Active esterification Na EXB9460-65T 52 52 26 26 26 52 Phenol compound LA7052 9 9 9 24 SN485 30 Hardening accelerator 4·Dimethylamine. Alkylpyridine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Inorganic germanium charge SOC2 120 120 100 100 100 100 100 100 phenoxy resin containing trimethylcyclohexane structure 12 12 12 12 12 containing terpene structure 12 1256B40 12 12 rubber particles W450 8 8 peel strength surface) 0.6 0.6 0.7 0.7 0.6 0.7 0.6 0.6 Surface roughness (dirty) reo 33⁄4) 300 280 320 600 230 300 Linear expansion ratio (ppm) 48 55 35 34 40 35 51 60 201030046 As can be seen from the comparison between Example 1 and Comparative Example 1, the relative In the comparative example of the phenoxy resin using the double-cool A structure, Example 1 using a phenoxy resin having an alicyclic structure, although the surface roughness is low, the peel strength is high, and the linear expansion ratio is also lowered. low. Similarly, when Comparative Examples 2 and 3 and Comparative Example 2 were compared, it was found that in Comparative Example 2, although the phenoxy resin was changed to the bisphenol A structure for Examples 2 and 3, the surface roughness and the coefficient of linear expansion were observed. The system rises. © In the examples 2 and 3, the active ester compound and the phenol compound are used as the curing agent. When compared with the first embodiment, although the surface roughness tends to increase somewhat, the linear expansion ratio is lowered, and it is known that Use to achieve the balance between the two sides. Further, in Comparative Example 3, only the phenol compound was used as the curing agent. As compared with Example 2, the surface roughness was greatly increased. In Example 4 and Comparative Example 4, the composition of the rubber particles was used, and the difference between the case where the active ester compound and the phenol compound were used as the curing agent was compared, and the example 4 in which the active ester compound was used had a small surface roughness and a linear expansion ratio. It is also low. Industrial Applicability Provided that although the roughness of the roughened surface of the surface of the cured product of the epoxy resin composition is relatively small, the roughening can exhibit high adhesion to the plated conductor and can be achieved. An epoxy resin composition, an adhesive film, a prepreg, and a multilayer printed circuit board of an insulating layer having a small coefficient of linear expansion. In addition, it is also possible to provide electrical appliances such as computers, portable telephones, digital cameras, televisions -39 - 201030046, or vehicles such as automatic two-wheelers, automobiles, trams, ships, and airplanes.
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