201031707 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等的線路基板之絕 緣層形成的樹脂組成物、及由該樹脂組成物所得的黏著薄 膜、預浸物等的絕緣樹脂薄片、以及由該樹脂組成物的硬 化物形成絕緣層的線路基板。 φ 【先前技術】 隨著近年的電子機器之小型化、高性能化，要求線路 基板的更微細配線化。於將絕緣層表面粗化後，藉由鏟敷 以形成導體層時，若增大粗糙度，則剝離強度增大，而不 利於微細配線化。因此，希望儘可能地以低粗糙度來提高 導體層的剝離強度同時滿足與其相反的性能。 例如，有揭示混有環氧樹脂、特定的酚系硬化劑、聚 乙烯縮醛樹脂之環氧樹脂組成物，但使用於多層印刷電路 Φ 板的絕緣層時，所得之粗化面即使粗糙度比較小，也能與 導體以高的密接力來密接（專利文獻1)。 [先前技術文獻] [專利文獻] [專利文獻1]特開2007-2547 1 0號公報 【發明內容】 發明所欲解決的問題 本發明之目的爲提供一種樹脂組成物，其係適合於線 -5- 201031707 路基板的絕緣層形成之樹脂組成物，即使將該樹脂組成物 硬化所得之絕緣層表面的粗糙度低，也能形成具有高的剝 離強度之導體層。 解決問題的手段 鑒於上述問題，本發明者們著眼於樹脂組成物中的硬 化促進劑之影響。於是，本發明者們發現在含有多官能環 氧樹脂、熱塑性樹脂、無機塡充劑的樹脂組成物中，藉由 @ 組合使用特定的硬化劑與特定的磷系硬化劑，於將該樹脂 組成物硬化所形成的絕緣層中，即使絕緣層表面係低粗糙 度，所形成的導體層具有高的剝離強度，而完成本發明。 即，本發明亦包含以下的內容。 [1] 一種樹脂組成物，其含有（A)多官能環氧樹脂、 (B )酚系硬化劑及/或活性酯系硬化劑、（C )熱塑性樹 脂' (D)無機塡充材、（E)由四丁基鳞癸酸鹽、（4-甲 基苯基）三苯基鋳硫氰酸酯、四苯基錢硫氰酸酯、丁基三 Θ 苯基鱗硫氰酸酯所選出的1種以上之4級鱗系硬化促進劑 〇[Technical Field] The present invention relates to a resin composition suitable for forming an insulating layer of a wiring board such as a multilayer printed wiring board, and an adhesive film, a prepreg, and the like obtained from the resin composition. The insulating resin sheet and the wiring substrate in which the insulating layer is formed of the cured product of the resin composition. φ [Prior Art] With the miniaturization and high performance of electronic devices in recent years, finer wiring of circuit boards is required. When the surface of the insulating layer is roughened and the conductor layer is formed by shoveling, if the roughness is increased, the peeling strength is increased, which is disadvantageous for fine wiring. Therefore, it is desirable to increase the peel strength of the conductor layer with low roughness as much as possible while satisfying the opposite performance. For example, there is disclosed an epoxy resin composition in which an epoxy resin, a specific phenolic curing agent, and a polyvinyl acetal resin are mixed, but when used in an insulating layer of a multilayer printed circuit Φ board, the obtained roughened surface is even rough. It is relatively small and can be closely adhered to the conductor with a high adhesion (Patent Document 1). [Prior Art Document] [Patent Document 1] [Patent Document 1] JP-A-2007-2547 No. 1-0 SUMMARY OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a resin composition which is suitable for a wire- 5-201031707 The resin composition formed of the insulating layer of the circuit board can form a conductor layer having high peel strength even if the surface roughness of the insulating layer obtained by curing the resin composition is low. Means for Solving the Problems In view of the above problems, the inventors focused on the influence of a hardening accelerator in a resin composition. Then, the present inventors have found that in a resin composition containing a polyfunctional epoxy resin, a thermoplastic resin, or an inorganic chelating agent, a specific hardener and a specific phosphorus-based hardener are combined by @, and the resin is composed of the resin. In the insulating layer formed by the hardening of the object, even if the surface of the insulating layer is low in roughness, the formed conductor layer has high peeling strength, and the present invention has been completed. That is, the present invention also includes the following contents. [1] A resin composition comprising (A) a polyfunctional epoxy resin, (B) a phenolic curing agent and/or an active ester curing agent, and (C) a thermoplastic resin '(D) an inorganic chelating material, ( E) selected from tetrabutyl sulphonate, (4-methylphenyl) triphenyl sulfonate, tetraphenyl thiocyanate, butyl triphenyl phenyl thiocyanate One or more grade 4 scale hardening accelerators〇
[2 ]如上述[1 ]記載的樹脂組成物，其中以相對於成分 (A)與成分（B)的不揮發份之合計質量而言，成分（E )的質量之比率成爲1〇〇:〇·〇5〜100:2之範圍含有成分（E )。 [3]如上述[1]或[2]記載的樹脂組成物，其中以存在於 樹脂組成物中的環氧基與成分（B)之硬化劑的反應基之 -6 - 201031707 比率係莫耳比成爲1 :0.3〜1:1之範圍含有成分（B)。 [4] 如上述[1]〜[3]中任一項記載的樹脂組成物，其中 當樹脂組成物的不揮發份爲1 00質量％時，成分（C )的 含量係1〜20質量％。 [5] 如上述[1]〜[4]中任一項記載的樹脂組成物，其中 當樹脂組成物的不揮發份爲1 00質量％時，成分（D )的 含量係1 〇〜7 0質量％。 ❹ [6]如上述[1]〜[5]中任一項記載的樹脂組成物，其剝 離強度係 〇.4kgf/cm〜2kgf/em，表面粗糙度係 30nm〜 4 OOnm ° [7] —種黏著薄膜，其係在支持體上形成有[1]〜[6]中 任一項之樹脂組成物的層。 [8] —種預浸物，其係將[1]〜[6]中任一項之樹脂組成 物含浸在薄片狀纖維基材中。 [9] 一種線路基板，其係將[1]〜[6]中任一項之樹脂組 Φ 成物的硬化物形成絕緣層。 發明的效果 本發明的樹脂組成物係適合於線路基板的絕緣層形成 ，即使將該樹脂組成物硬化所得之絕緣層係表面粗糙度， 也可形成具有高剝離強度的導體層，變成有利於線路基板 的微細配線化。 【實施方式】 201031707 實施發明的形態 本發明係以含有（A)多官能環氧樹脂、（B)酚系硬 化劑及/或括性酯系硬化劑、（C )熱塑性樹脂、（D )無 機塡充材' (E)特定的硬化促進劑當作特徵的樹脂組成 物。 [(A)多官能環氧樹脂] 本發明中的成分（A)多官能環氧樹脂，只要能達成 ❹ 本發明的效果，則沒有特別的限定，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-酚醛清禁型環氧樹脂、聯苯型 環氧樹脂、線狀脂肪族環氧樹脂、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。 亦可倂用2種以上的環氧樹脂，較佳爲含有1分子中 · 具有2個以上的環氧基之環氧樹脂。當樹脂組成物中的不 揮發成分爲1〇〇質量％時，較佳爲至少50質量％以上係1 分子中具有2個以上的環氧基之環氧樹脂。再者，較佳的 態樣包含1分子中具有2以上的環氧基，在溫度20°C爲液 狀的芳香族系環氧樹脂之環氧樹脂’及1分子中具有3以 上的環氧基，在溫度20°C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。 -8- 201031707 又’作爲環氧樹脂，當倂用液狀環氧樹脂與固形環氧 樹脂時’其配合比例（液狀：固形）以質量比計較佳係 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有變容易發生孔洞 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，在樹脂組成 φ 物的硬化物中，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。 於本發明的樹脂組成物中，當樹脂組成物的不揮發成 分爲100質量％時，環氧樹脂的含量較佳係10〜50質量％ ，尤佳係20〜45質量％，更佳係25〜42質量％。環氧樹 脂（A )的含量若在此範圍外，則樹脂組成物的硬化性有 φ 降低的傾向。 [(B )酚系硬化劑及/或活性酯系硬化劑] 本發明中的成分（B)之酚系硬化劑及/或活性酯系硬 化劑，只要能達成本發明的效果，則沒有特別的限定，可 各自單獨使用，也可混合使用。特別地，從硬化物的機械 特性之觀點來看，較佳爲酚系硬化劑。 酚系硬化劑係含有苯酚骨架或萘酚骨架的化合物，指 具有環氧樹脂的硬化作用者。作爲酚系硬化劑，從耐熱性 -9 - 201031707 、耐水性之觀點來看，較佳爲具有酚醛清漆構造的苯酚系 硬化劑或具有酚醛清漆構造的萘酚系硬化劑。作爲市售品 ，例如可舉出 MEH-7700、MEH-7810、MEH-78 5 1 (明和 化成公司製）、NHN、CBN、GPH (日本化藥（股）製） 、SN170 、 SN180 、 SN190 、 SN475 、 SN485 、 SN495 、 SN375、SN395 (東都化成（股）製）、LA 7052、LA 7054 (大日本油墨化學工業（股）製）。活性酯系硬化劑係指 苯酚酯類、苯硫酚酯類、N-羥基胺酯類、雜環羥基化合 @ 物的酯類等之具有反應活性高的酯基，具有環氧樹脂的硬 化作用者。作爲活性酯系硬化劑，可舉出EXB-9460 (大 日本油墨化學工業（股）製）、DC808、YLH1O30 (日本 環氧樹脂（股）製）。 於本發明中，樹脂組成物中的酚系硬化劑及/或活性 酯系硬化劑之含量，較佳係使樹脂組成物中所存的環氧樹 脂之環氧基的合計數與硬化劑的反應基之合計數的比率成 爲1:0.3〜1:2之量，再者更佳係成爲1:0.4〜1:1.5之量。 @ 尙且，樹脂組成物中所存在的環氧樹脂之環氧基的合計數 ，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，硬化劑的反應基（活性 羥基、活性酯基等）的合計數係指將各硬化劑的固體成分 質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外，則將樹脂組成物硬化 所得之硬化物的耐熱性係有變不足等的傾向。 -10- 201031707 [(c )熱塑性樹脂] 本發明中的成分（C)熱塑性樹脂，只要能達成本發 明的效果，則沒有特別的限定，例如可舉出苯氧樹脂、聚 乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚 碾樹脂、聚颯樹脂等，較佳爲苯氧樹脂、聚乙烯縮醛樹脂 ，特佳爲苯氧樹脂。熱塑性樹脂亦可混合2種以上來使用 。熱塑性樹脂的含量，相對於1 〇〇質量％的樹脂組成物中 φ 之不揮發份而言，較佳爲1〜20質量％的範圍，更佳爲5 〜1 5質量％的範圍。含量若過少，則硬化物的可撓有降低 的傾向，而含量若過多，則樹脂組成物的黏度變過高，層 合性降低，線路上的配線圖型之埋入等有變困難的傾向。 熱塑性樹脂的重量平均分子量較佳爲8000〜70000的範圍 ，尤佳爲 10000〜60000，更佳爲 20000〜60000。分子量 若過小，則導體層的剝離強度有降低的傾向，而分子量若 過大，則粗糙度容易變大，熱膨脹率有容易變大等的傾向 # 。重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。GPC法的重量平均分子量，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，使用氯仿等當作移動相，在管柱溫度 4〇°C進行測定，使用標準聚苯乙烯的校正曲線來算出。 作爲苯氧樹脂，可舉出具有由雙酚A骨架、雙酚F骨 架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯 骨架、莽骨架、二環戊二烯骨架、原冰片烯骨架、萘骨架 -11 - 201031707 、蒽骨架、金剛烷骨架、萜烯骨架、三甲基環己烷骨架所 選出的1種以上之骨架者。苯氧樹脂亦可混合2種以上來 使用。苯氧樹脂的末端也可爲酚性羥基、環氧基等的任一 種官能基。作爲市售品，例如可舉出日本環氧樹脂（股） 製1256、4250(含有雙酚A骨架的苯氧樹脂）、日本環 氧樹脂製YX8 1〇〇 (含有雙酚S骨架的苯氧樹脂）、日本 環氧樹脂製YX6954 (含有雙酚苯乙酮骨架的苯氧樹脂） 、或其它東都化成（股）製FX280、FX293、日本環氧樹 © 脂（股）製 YL7 5 53、YL6794、YL7213、YL7290、 YL7482 等。 作爲聚乙烯縮醛樹脂的具體例，可舉出電氣化學工業 (股）製的電化 BUTYRAL 4000-2、5000-A ' 6000-C、 6000-EP、積水化學工業（股）製S-LEC BH系歹IJ、BX系 列、KS系列、BL系歹[J、BM系列等。作爲聚醯亞胺樹脂 的具體例，可舉出新日本理化（股）製的聚醯亞胺「 Rikacoat SN20」及「Rikacoat PN20」。又，可舉出使 2 . 官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐 反應而得之線狀聚醯亞胺（特開2006-3 7083號公報記載 者）、含有聚矽氧烷骨架的聚醯亞胺（特開2002-12667 號公報、特開2000-3 1 93 86號公報等中記載者）等的改性 聚醯亞胺。作爲聚醯胺醯亞胺樹脂的具體例，可舉出東洋 紡績（股）製的聚醯胺醯亞胺「Vylomax HR11NN」及「 Vylomax HR16NN」。又，可舉出日立化成工業（股）製 的含有聚矽氧烷骨架之聚醯胺醯亞胺「KS9 100」、「 -12- 201031707 KS9300」等的改性聚醯胺醯亞胺。作爲聚醚楓樹脂的具體 例，可舉出住友化學（股）公司製的聚醚颯「PES5003P」 等。作爲聚碾樹脂的具體例，可舉出索羅門先進聚合物（ 股）公司製的聚颯「P1700」、「P3500」等。此等各種熱 塑性樹脂亦可混合2種以上來使用。 [(D)的無機塡充材] # 本發明中的成分（D)無機塡充材，只要能達成本發 明的效果’則沒有特別的限定，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、鉻酸鋇、锆酸 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。矽石較佳爲球狀者。無機 塡充材亦可組合2種以上來使用。 ® 無機塡充材的平均粒徑較佳爲Ιμηι以下，更佳爲 〇·8μιη以下’特佳爲〇·7μηι以下。平均粒徑超過時， 鍍敷所形成的導體層之剝離強度有降低的傾向。再者，無 機塡充材的平均粒徑若過小，則在以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 平均粒徑較佳爲〇.〇5μιη以上。無機塡充材的平均粒徑可 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材的粒度分布，測定其中位（ -13- 201031707 median )徑當作平均粒徑。測定樣品較佳可使用無機塡充 材經由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。 爲了提高耐濕性、分散性等，無機塡充材亦可經胺丙 基甲氧基矽烷、胺丙基三乙氧基矽烷、脲基丙基三乙氧基 矽烷、N-苯基胺丙基三甲氧基矽烷、N-2 (胺乙基）胺丙 基三甲氧基矽烷等的胺基矽烷系偶合劑、環氧丙氧基丙基 三甲氧基矽烷、環氧丙氧基丙基三乙氧基矽烷、環氧丙氧 @ 基丙基甲基二乙氧基矽烷、縮水甘油基丁基三甲氧基矽烷 、（3,4-環氧基環己基）乙基三甲氧基矽烷等的環氧矽烷 系偶合劑、锍基丙基三甲氧基矽烷、巯基丙基三乙氧基矽 烷等的锍基矽烷系偶合劑、甲基三甲氧基矽烷、十八基三 甲氧基矽烷、苯基三甲氧基矽烷、甲基丙烯醯氧基丙基三 甲氧基矽烷、咪唑矽烷、三哄矽烷等的矽烷系偶合劑、六 甲基二矽氮烷、六苯基二矽氮烷、二甲基胺基三甲基矽烷 、三矽氮烷、環三矽氮烷、1，1，3,3,5,5-六甲基環三矽氮烷 ® 等的有機矽氮烷化合物、鈦酸丁酯二聚物、鈦辛烯乙醇酸 酯、二異丙氧基鈦雙（三乙醇胺化物）、二羥基鈦雙乳酸 酯、二羥基雙（乳酸銨）鈦、雙（磷酸氫二辛酯）乙烯鈦 酸酯、雙（磷酸氫二辛酯）氧基醋酸酯鈦酸酯、三正丁氧 基鈦單硬脂酸酯、鈦酸四正丁酯、鈦酸四（2-乙基己基） 酯、四異丙基雙（磷酸氫二辛酯）鈦酸酯、四辛基雙（亞 磷酸貳十三酯）鈦酸酯、四（2,2-二烯丙氧基甲基-1_ 丁基 )雙（貳十三基）亞磷酸酯鈦酸酯、異丙基參十八醯基鈦 -14 - 201031707 酸酯、異丙基三枯基苯基欽酸酯、異丙基三異硬脂酸基鈦 酸酯、異丙基異硬脂醯基二丙烯醯基鈦酸酯、異丙基二甲 基丙烯醯基異硬脂醯基鈦酸酯、異丙基三（磷酸氫二辛酯 )鈦酸酯、異丙基參十二基苯磺醯基鈦酸酯、異丙基三（ 磷酸氫二辛酯）鈦酸酯、異丙基三（N-醯胺基乙基•胺乙 基）鈦酸酯的鈦酸酯系偶合劑等之1種以上的表面處理劑 所處理。 φ 無機塡充材的平均粒徑可以米氏（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材的 粒度分布，測定其中位徑當作平均粒徑。測定樣品較佳可 使用無機塡充材經由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 。 無機塡充材的含量，相對於100質量％的樹脂組成物 中之不揮發份而言，較佳爲10〜70質量％的範圍，尤佳爲 15〜65質量％的範圍，更佳爲20〜60質量％的範圍。無機 充塡劑的含量若過少，則熱膨脹率有上升的傾向，而含量 若過多，則絕緣樹脂薄片的可撓性有降低的傾向。 [4級鳞系硬化促進劑] 本發明中的成分（E ) 4級鳞系硬化促進劑，只要能 達成本發明的效果，則沒有特別的限定，此處所謂的4級 ’表示由烷基、芳烷基、芳基所選出的官能基。具體地， -15- 201031707 可舉出4級鱗硫氰酸酯、4級鍈長鏈脂肪酸鹽。特別地， 較佳爲四丁基錢癸酸鹽、（4-甲基苯基）三苯基鳞硫氰酸 酯、四苯基鱗硫氰酸酯、丁基三苯基鳞硫氰酸酯。相對於 成分（A)與成分（B)的不揮發份之合計質而S，成分 (Ε )的含量（質量％ )之下限値較佳爲〇.〇5，尤佳爲 0.07，更佳爲0.09，尤更佳爲0.11，再更佳爲0.13，特佳 爲0.15。相對於成分（Α)與成分（Β)的不揮發份之合 計質量而言，成分（Ε )的含量（質量％ )之上限値較佳 φ 爲2，尤佳爲1，更佳爲0.8，尤更佳爲0.7，再更佳爲0.6 ，特佳爲0.5。成分（Ε)的比率若未達〇.〇5 ’則有難以得 到目的之低粗糙度的效果之傾向，而若超過2，則剝離強 度有降低的傾向。 本發明的樹脂組成物係提供一種含有（Α)成分、（Β )成分、（C)成分、（D)成分、（Ε)成分之樹脂組成 物，即使將該樹脂組成物硬化所得之絕緣層表面的粗糙度 低，也可形成具有高剝離強度的導體層。 ® 本發明之含有（Α)成分、（B)成分、（C)成分、 (D)成分、（E)成分的樹脂組成物之硬化物的剝離強度 ，係可藉由後述的 <鏟敷導體層的拉剝強度（剝離強度） )之測定及評價 > 中記載的測定方法來掌握。 本發明的樹脂組成物之硬化物的剝離強度（kgf/cm ) 之上限値較佳爲〇·8，尤佳爲0.9，更佳爲1.0，尤更佳爲 1 .1，再更佳爲1.2，特佳爲2。本發明的樹脂組成物之硬 化物的剝離強度（kgf/cm)之下限値較佳爲0.4，尤佳爲 -16- 201031707 〇 . 5，更佳爲0.6。 本發明之含有（Α)成分、（B)成分、（C)成分、 (D)成分、（E )成分的樹脂組成物之硬化物的表面粗糙 度，係可藉由後述的 < 粗化後的表面粗糙度（Ra値）之 測定及評價 > 中記載的測定方法來掌握。 本發明的樹脂組成物之硬化物的表面粗糙度（nm )之 上限値較佳爲700，尤佳爲500，更佳爲400，尤更佳爲 φ 300，再更佳爲200，特佳爲170。本發明的樹脂組成物之 硬化物的表面粗糙度（nm)之下限値較佳爲150，尤佳爲 120，更佳爲90，尤更佳爲70，再更佳爲50，特佳爲30 [橡膠粒子] 本發明的樹脂組成物，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。橡膠 # 粒子較佳爲亦不溶於在調製樹脂組成物之際的有機溶劑中 ，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。作爲橡膠粒子， 例如可舉出芯殼型橡膠粒子、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。芯殻 型橡膠粒子係粒子具有芯層與殻層的橡膠粒子，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 -17- 201031707 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。作爲芯殻型橡膠粒子的具體例，可舉出 Stafilrod AC3832、AC3816N(GANZ 化成（股）商品名） 、Metabren KW-4426 (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 φ (平均粒徑0.5 μιη，J SR (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 C平均粒 徑〇·5μιη，JSR (股）製）等。作爲丙烯酸橡膠粒子的具 體例，可舉出 Metabren W300A (平均粒徑 0·1μιη)、 W450A (平均粒徑0.5μιη)(三菱嫘縈（股）製）。 所配合的橡膠粒子之平均粒徑較佳爲0.005〜Ιμηι的 範圍，更佳爲0.2〜0.6 μπι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-1000 (大塚電子（股）公司製），以質量基準作成 橡膠粒子的粒度分布，將其中位徑當作平均粒徑而測定。 當配合該橡膠粒子時，相對於1 〇〇質量％的樹脂組成 物中之不揮發份而言，較佳爲1〜1〇質量％的範圍，更佳 爲2〜5質量％的範圍。 [其它熱硬化性樹脂] -18- 201031707 本發明的樹脂組成物，按照需要在發揮本發明的效果 之範圍內，亦可配合馬來醯亞胺化合物、雙烯丙基納迪醯 亞胺（bis-allyl-nadi-imide )化合物、乙烯基苄基樹脂、 乙烯基苄基醚樹脂等的其它熱硬化性樹脂。如此的熱硬化 性樹脂亦可混合2種以上來使用。作爲馬來醯亞胺樹脂， 可舉出 BMI 1000、BMI 2000、BMI 3000、BMI 4000、 BMI 5100 (大和化成工業（股）製）、：BMI、BMI-70、 φ 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，可舉出 BAN1-M、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）。 [難燃劑] φ 本發明的樹脂組成物，在發揮本發明的效果之範圍內 ，亦可含有難燃劑。難燃劑亦可混合2種以上來使用。作 爲難燃劑，例如可舉出有機磷系難燃劑、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 006M等之含磷的苯并噚哄化合物、味之素精密科 技（股）製的 Rheophos 30 > 50 、 65 、 90 、 110' TPP 、 RPD 、 BAPP 、 CPD 、 TCP 、 TXP 、 TBP 、 TOP 、 KP140 、 -19- 201031707 ΤΙΒΡ、北興化學工業（股）製的PPQ、CLARIANT (股） 製的OP930、大八化學（股）製的PX200等之磷酸酯化合 物、東都化成（股）製的FX289、FX310等之含隣環氧樹 脂、東都化成（股）製的ERF001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、SP703等的磷酸酯醯胺化合物、大塚化學（ 股）公司製的SPB100、SPE100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 ' φ UD650、UD653等的氫氧化鎂、巴工業（股）公司製的B-30、 B-325 ' B-315、 B-308、 B-303、 UFH-20 等之氫氧化 鋁等。 [樹脂添加劑] 本發明的樹脂組成物，在發揮本發明的效果之範圍內 ’亦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 Θ 劑、歐魯本（Orben )、片通（Benton )等的增黏劑 '聚 矽氧系、氟系、高分子系的消泡劑或均平劑、矽烷偶合劑 、***化合物、噻唑化合物、三哄化合物、卟啉化合物等 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。又，可舉出Curezol 2MZ、2E4MZ 、C11Z、Cl 1Z-CN、C11Z-CNS 、 C11Z-A、2MZ-OK、 2MA-OK ' 2PHZ (四國化成工業（股）商品名）等的咪唑 化合物；N〇vacure (旭化成工業（股）商品名）、 -20- 201031707[2] The resin composition according to the above [1], wherein the ratio of the mass of the component (E) to the total mass of the nonvolatile matter of the component (A) and the component (B) is 1 : The range of 〇·〇5~100:2 contains the component (E). [3] The resin composition according to the above [1] or [2] wherein the ratio of the reactive group of the epoxy group present in the resin composition to the hardener of the component (B) is -6 - 201031707 The ratio (B) is contained in the range of 1:0.3 to 1:1. [4] The resin composition according to any one of the above [1], wherein the content of the component (C) is 1 to 20% by mass when the nonvolatile content of the resin composition is 100% by mass. . [5] The resin composition according to any one of the above [1], wherein the content of the component (D) is 1 〇 to 7 0 when the nonvolatile content of the resin composition is 100% by mass. quality%. [6] The resin composition according to any one of [1] to [5], wherein the peeling strength is 44 kgf/cm 2 kgf/em, and the surface roughness is 30 nm to 4 00 nm ° [7]. The adhesive film is a layer in which the resin composition of any one of [1] to [6] is formed on the support. [8] A prepreg in which the resin composition of any one of [1] to [6] is impregnated into a sheet-like fibrous base material. [9] A circuit board in which the cured product of the resin group Φ of any one of [1] to [6] is formed into an insulating layer. Advantageous Effects of Invention The resin composition of the present invention is suitable for the formation of an insulating layer of a wiring board, and even if the surface roughness of the insulating layer obtained by curing the resin composition is formed, a conductor layer having high peeling strength can be formed, which is advantageous for the wiring. The wiring of the substrate is finely wired. [Embodiment] 201031707 Embodiment of the Invention The present invention contains (A) a polyfunctional epoxy resin, (B) a phenolic curing agent and/or a styling ester curing agent, (C) a thermoplastic resin, and (D) inorganic塡 Filling material '(E) A specific hardening accelerator is used as a characteristic resin composition. [(A) Polyfunctional Epoxy Resin] The component (A) polyfunctional epoxy resin in the present invention is not particularly limited as long as it can achieve the effects of the present invention, and examples thereof include bisphenol A epoxy resin. , bisphenol F epoxy resin, phenol-novolac epoxy resin, t-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, cresol-phenolic acid Forbidden epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type ring Oxygen resin, trimethylol epoxy resin, halogenated epoxy resin, and the like. Two or more kinds of epoxy resins may be used, and an epoxy resin having two or more epoxy groups in one molecule is preferable. When the nonvolatile content in the resin composition is 1% by mass, it is preferably at least 50% by mass or more of an epoxy resin having 2 or more epoxy groups in one molecule. Further, a preferred embodiment includes an epoxy resin having 2 or more epoxy groups in one molecule and an aromatic epoxy resin having a liquidity at a temperature of 20 ° C, and an epoxy having 3 or more in one molecule. The base is an aromatic fluorene epoxy resin which is solid at a temperature of 20 ° C. Further, the aromatic epoxy resin described in the present invention means an epoxy resin having an aromatic ring structure in its molecule. -8- 201031707 Also as 'epoxy resin, when the liquid epoxy resin and the solid epoxy resin are used, the mixing ratio (liquid: solid) is preferably in the range of 1:0.1 to 1:2 by mass ratio. . When the ratio of the liquid epoxy resin is too large, the adhesiveness of the resin composition is increased, and when it is used as a film, the degassing property at the time of vacuum lamination is lowered, and the tendency to cause voids tends to occur. . 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 resin composition φ, it is difficult to obtain sufficient breaking strength. On the other hand, when the ratio of the solid epoxy resin is too large, the ratio of the solid epoxy resin is too large, and sufficient flexibility is not obtained, and the workability is lowered, so that it is difficult to obtain sufficient lamination at the time of lamination. The tendency of liquidity, etc. In the resin composition of the present invention, when the nonvolatile content of the resin composition is 100% by mass, the content of the epoxy resin is preferably 10 to 50% by mass, particularly preferably 20 to 45% by mass, more preferably 25 ~ 42% by mass. When the content of the epoxy resin (A) is outside this range, the curability of the resin composition tends to decrease φ. [(B) Phenolic curing agent and/or active ester curing agent] The phenolic curing agent and/or the active ester curing agent of the component (B) in the present invention are not particularly limited as long as the effects of the present invention can be achieved. The limits can be used individually or in combination. In particular, a phenolic curing agent is preferred from the viewpoint of mechanical properties of the cured product. The phenolic curing agent is a compound containing a phenol skeleton or a naphthol skeleton, and means a curing agent having an epoxy resin. The phenol-based curing agent is preferably a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure from the viewpoint of heat resistance -9 - 201031707 and water resistance. Examples of commercially available products include MEH-7700, MEH-7810, MEH-78 5 1 (manufactured by Minwa Kasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, and SN190. SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), LA 7052, LA 7054 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). The active ester-based curing agent refers to a highly reactive ester group such as a phenol ester, a thiophenol ester, an N-hydroxylamine ester, or an ester of a heterocyclic hydroxy compound, and has an epoxy resin hardening action. By. Examples of the active ester-based curing agent include EXB-9460 (manufactured by Dainippon Ink Chemicals Co., Ltd.), DC808, and YLH1O30 (manufactured by Nippon Epoxy Resin Co., Ltd.). In the present invention, the content of the phenolic curing agent and/or the active ester curing agent in the resin composition is preferably such that the total number of epoxy groups of the epoxy resin present in the resin composition reacts with the curing agent. The ratio of the total number of bases is 1:0.3 to 1:2, and more preferably, it is 1:0.4 to 1:1.5. @ 尙, the total number of epoxy groups of the epoxy resin present in the resin composition is the total amount of the epoxy resin after dividing the solid component weight of each epoxy resin by the epoxy equivalent. Thereafter, the total number of reactive groups (active hydroxyl groups, active ester groups, and the like) of the curing agent is defined as the total amount of the hardeners obtained by dividing the solid content of each curing agent by the reaction group equivalent. When the content of the curing agent is outside the preferred range, the heat resistance of the cured product obtained by curing the resin composition tends to be insufficient. -10-201031707 [(c) thermoplastic resin] The component (C) thermoplastic resin in the present invention is not particularly limited as long as the effect of the present invention can be attained, and examples thereof include a phenoxy resin and a polyvinyl acetal resin. The polyimine resin, the polyamidimide resin, the polyether mill resin, the polyfluorene resin, etc. are preferably a phenoxy resin or a polyvinyl acetal resin, and particularly preferably a phenoxy resin. The thermoplastic resin may be used in combination of two or more kinds. The content of the thermoplastic resin is preferably in the range of 1 to 20% by mass, more preferably in the range of 5 to 15% by mass, based on the nonvolatile content of φ in the resin composition of 1% by mass. When the content is too small, the flexibility of the cured product tends to decrease, and if the content is too large, the viscosity of the resin composition becomes too high, the laminate property is lowered, and the wiring pattern on the line tends to become difficult to be embedded. . The weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, particularly preferably 10,000 to 60,000, more preferably 20,000 to 60,000. When the molecular weight is too small, the peel strength of the conductor layer tends to decrease, and if the molecular weight is too large, the roughness tends to increase, and the coefficient of thermal expansion tends to become large. The weight average molecular weight was measured by gel permeation chromatography (GPC) (polystyrene conversion). For the weight average molecular weight of the GPC method, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. is used. As a column, chloroform or the like was used as a mobile phase, and the column temperature was measured at 4 ° C, and was calculated using a calibration curve of standard polystyrene. Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentadiene skeleton. One or more kinds of skeletons selected from the original norbornene skeleton, the naphthalene skeleton-11 - 201031707, the anthracene skeleton, the adamantane skeleton, the terpene skeleton, and the trimethylcyclohexane skeleton. The phenoxy resin may be used in combination of two or more kinds. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Examples of the commercially available product include 1256 and 4250 (phenoxy resin containing a bisphenol A skeleton) manufactured by Nippon Epoxy Resin Co., Ltd., and YX8 1〇〇 (a phenoxy group containing a bisphenol S skeleton). Resin), Japanese epoxy resin YX6954 (phenoxy resin containing bisphenol acetophenone skeleton), or other FX280, FX293, Japan Ethylene Chemical Co., Ltd. YL7 5 53, YL6794 , YL7213, YL7290, YL7482, etc. Specific examples of the polyvinyl acetal resin include electrochemically produced BUTYRAL 4000-2, 5000-A '6000-C, 6000-EP, and S-LEC BH manufactured by Sekisui Chemical Co., Ltd. System IJ, BX series, KS series, BL system 歹 [J, BM series, etc. Specific examples of the polyimine resin include polyimine "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a functional hydroxyl terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-3 7083) and containing a polyfluorene A modified polyimine such as a polyimine of the oxyalkylene skeleton (described in JP-A-2002-12667, JP-A-2000-3, 193, and the like). Specific examples of the polyamidoximine resin include polyamido imidate "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Further, modified polyamidoquinone imines such as polyacrylamide skeleton "KS9 100" and "-12-201031707 KS9300" containing a polyoxyalkylene skeleton manufactured by Hitachi Chemical Co., Ltd. can be cited. Specific examples of the polyether maple resin include polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the poly-rolling resin include polysulfonium "P1700" and "P3500" manufactured by Solomon Advanced Polymers Co., Ltd. These various thermoplastic resins may be used in combination of two or more kinds. [Inorganic 塡 filling material of (D)] The component (D) in the present invention is not particularly limited as long as the effect of the present invention can be achieved, and examples thereof include vermiculite, alumina, and barium sulfate. , talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, titanic acid Among them, niobium, titanium oxide, strontium chromate, calcium zirconate, and the like are particularly suitable as vermiculite such as amorphous vermiculite, molten vermiculite, crystalline vermiculite, and synthetic vermiculite. The vermiculite is preferably a spherical one. Inorganic enamel materials can also be used in combination of two or more kinds. The average particle diameter of the inorganic filler is preferably Ιμηι or less, more preferably 〇·8μηη or less, and particularly preferably 〇·7μηι or less. When the average particle diameter exceeds, the peel strength of the conductor layer formed by plating tends to decrease. In addition, when the average particle diameter of the inorganic cerium material is too small, when the resin composition is used as the resin varnish, the operability is lowered because the viscosity of the varnish is increased, so the average particle diameter is preferably 〇.5 μm the above. The average particle size of the inorganic cerium filler can be determined by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material can be prepared on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter of -13 - 201031707 median can be determined as the average particle diameter. The measurement sample is preferably one in which an inorganic cerium filler is dispersed in the water via ultrasonic waves. As the laser diffraction type particle size distribution measuring device, a LA-500 manufactured by Horiba, Ltd., or the like can be used. In order to improve moisture resistance, dispersibility, etc., the inorganic ruthenium can also be substituted with aminopropyl methoxy decane, aminopropyl triethoxy decane, ureidopropyl triethoxy decane, N-phenyl amide Amino decane coupling agent such as trimethoxy decane, N-2 (aminoethyl) amine propyl trimethoxy decane, glycidoxypropyl trimethoxy decane, glycidoxypropyl three Ethoxy decane, glycidoxy@propylpropyldiethoxy decane, glycidyl butyl trimethoxy decane, (3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc. A decyl decane coupling agent such as an epoxy decane coupling agent, mercaptopropyltrimethoxydecane or mercaptopropyltriethoxydecane, methyltrimethoxydecane, octadecyltrimethoxydecane, or phenyl a decane coupling agent such as trimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium or trioxane, hexamethyldiazepine, hexaphenyldioxane, dimethyl Organic germanium nitrogen such as aminotrimethylnonane, triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane® Compound, butyl titanate dimer, titanium octene glycolate, diisopropoxy titanium bis(triethanolamine), dihydroxy titanium dilactate, dihydroxy bis(ammonium lactate) titanium, bis (phosphoric acid) Dioctyl hydride) ethylene titanate, bis(dioctyl phosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, titanic acid tetrakis -ethylhexyl)ester, tetraisopropylbis(dioctylphosphonate) titanate, tetraoctylbis(ruthenium phosphite) titanate, tetrakis(2,2-dipropenyloxy) Methyl-1_butyl)bis(decyltridecyl)phosphite titanate, isopropyl sulfenyltitanium-14 - 201031707 acid ester, isopropyltricumylphenyl acid ester, different Propyl triisostearate titanate, isopropyl isostearyl decyl bis decyl decyl titanate, isopropyl dimethyl propylene decyl isostearyl decyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl dodecylbenzenesulfonate titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl tris(N-decylamine Titanium with ethyl ethylamine ethyl titanate Esters of the above coupling agents of one kind of the treated surface treating agent. The average particle diameter of the φ inorganic cerium material can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material can be determined on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be determined as the average particle diameter. The measurement sample is preferably one in which an inorganic ruthenium material is dispersed in the water via ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, a LA-500 manufactured by Horiba, Ltd., or the like can be used. The content of the inorganic cerium filler is preferably in the range of 10 to 70% by mass, particularly preferably 15 to 65% by mass, more preferably 20%, based on 100% by mass of the nonvolatile content of the resin composition. ~60% by mass range. When the content of the inorganic filler is too small, the coefficient of thermal expansion tends to increase, and if the content is too large, the flexibility of the insulating resin sheet tends to decrease. [4th-order scale-hardening accelerator] The component (E) 4-grade scale-hardening accelerator in the present invention is not particularly limited as long as the effect of the present invention can be attained, and the so-called "four-stage" herein means an alkyl group. a functional group selected from an aralkyl group or an aryl group. Specifically, -15-201031707 includes a grade 4 scale thiocyanate and a grade 4 long chain fatty acid salt. In particular, tetrabutyl citrate, (4-methylphenyl)triphenyl sulfonate, tetraphenyl scaly thiocyanate, butyl triphenyl squadinyl thiocyanate are preferred. . The lower limit of the content (% by mass) of the component (A) relative to the total amount of the non-volatile components of the component (A) and the component (B) is preferably 〇.〇5, particularly preferably 0.07, more preferably 0.09, especially preferably 0.11, more preferably 0.13, and particularly preferably 0.15. The upper limit 成分 of the content (% by mass) of the component (Ε) is preferably 2, more preferably 1, more preferably 0.8, based on the total mass of the non-volatile matter of the component (Α) and the component (Β). Especially better is 0.7, more preferably 0.6, and especially better 0.5. If the ratio of the component (Ε) is less than 〇5〇, there is a tendency that the effect of low roughness is hard to be obtained, and if it exceeds 2, the peeling strength tends to decrease. The resin composition of the present invention provides a resin composition containing a (Α) component, a (Β) component, a (C) component, a (D) component, and a (Ε) component, even if the resin composition is cured. The surface roughness is low, and a conductor layer having high peel strength can also be formed. The peeling strength of the cured product of the resin composition containing the (Α) component, the component (B), the component (C), the component (D), and the component (E) of the present invention can be reduced by the following The measurement method described in the measurement and evaluation of the peeling strength (peeling strength) of the conductor layer was grasped. The upper limit 剥离 of the peel strength (kgf/cm) of the cured product of the resin composition of the present invention is preferably 〇·8, particularly preferably 0.9, more preferably 1.0, still more preferably 1.1, still more preferably 1.2. , especially good for 2. The lower limit 剥离 of the peel strength (kgf/cm) of the cured resin of the resin composition of the present invention is preferably 0.4, particularly preferably -16 to 201031707 〇 . 5 , more preferably 0.6. The surface roughness of the cured product of the resin composition containing the (Α) component, the component (B), the component (C), the component (D), and the component (E) of the present invention can be coarsened by the following. The measurement method described in the measurement and evaluation of the surface roughness (Ra値) is grasped. The upper limit 表面 of the surface roughness (nm) of the cured product of the resin composition of the present invention is preferably 700, particularly preferably 500, more preferably 400, still more preferably φ 300, still more preferably 200, particularly preferably 170. The lower limit 表面 of the surface roughness (nm) of the cured product of the resin composition of the present invention is preferably 150, particularly preferably 120, more preferably 90, still more preferably 70, still more preferably 50, and particularly preferably 30. [Rubber Particles] The resin composition of the present invention may contain solid rubber particles for the purpose of improving the mechanical strength and stress relaxation effect of the cured product. The rubber # particles are preferably not dissolved in the organic solvent at the time of preparing the resin composition, nor are they compatible with the components in the resin composition such as an epoxy resin, but are present in a dispersed state in the varnish of the resin composition. . Such rubber particles are usually 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. 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 for example, the shell layer of the outer layer is a glassy polymer, and the core layer of the inner layer is composed of two layers of rubbery polymerization -17-201031707. The structure or the outer 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 or the like, and the rubber-like polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-shell type rubber particles include Stafilrod AC3832, AC3816N (GANZ Chemicals Co., Ltd.), and Metarren KW-4426 (Mitsubishi® (trade name) trade name). Specific examples of the acrylonitrile butadiene rubber (NBR) particles include XER-91 φ (average particle diameter: 0.5 μm, manufactured by J SR). Specific examples of the styrene butadiene rubber (SBR) particles include XSK-500 C average particle diameter 5·5 μmη, manufactured by JSR Co., Ltd., and the like. Specific examples of the acrylic rubber particles include Metabren W300A (average particle diameter: 0·1 μm) and W450A (average particle diameter: 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.). The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to Ιμηι, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles in the present invention can be measured by a dynamic light scattering method. For example, FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.) is used to uniformly disperse the rubber particles in a suitable organic solvent, and the particle size distribution of the rubber particles is determined on a mass basis. Measured by the average particle size. When the rubber particles are blended, the nonvolatile content in the resin composition of 1% by mass is preferably in the range of 1 to 1% by mass, more preferably 2 to 5% by mass. [Other thermosetting resin] -18- 201031707 The resin composition of the present invention may be blended with a maleic imine compound or a bisallyl nadiimide in the range in which the effects of the present invention are exerted as needed. Bis-allyl-nadi-imide compound, other thermosetting resin such as vinyl benzyl resin or vinyl benzyl ether resin. Such a thermosetting resin may be used in combination of two or more kinds. Examples of the maleimide resin include BMI 1000, BMI 2000, BMI 3000, BMI 4000, and BMI 5100 (manufactured by Daiwa Kasei Co., Ltd.), BMI, BMI-70, and φ BMI-80 (KI formation) (manufacturing), ANILIX-MI (manufactured by Mitsui Chemicals Co., Ltd.), and bisallyl nadiimide compound, BAN1-M, BANI-X (Kowloon Petrochemical Industry Co., Ltd.) The vinyl benzyl group resin is V5 000 (manufactured by Showa Polymer Co., Ltd.), and the vinyl benzyl ether resin is V1000X or V1100X (manufactured by Showa Polymer Co., Ltd.). [Flame Retardant] φ The resin composition of the present invention may contain a flame retardant within the range in which the effects of the present invention are exerted. The flame retardant may be used in combination of two or more kinds. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyfluorene-based flame retardant, and a metal hydroxide. Examples of the organophosphorus-based flame retardant include phosphorus-containing benzo compounds such as HCA, HCA-HQ 'HCA-NQ, and the like, and HFB-2 006M, which is manufactured by Showa Polymer Co., Ltd.噚哄 compound, Ajinomoto Precision Technology Co., Ltd. Rheophos 30 > 50, 65, 90, 110' TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, -19- 201031707 ΤΙΒΡ, PPQ, manufactured by Beixing Chemical Industry Co., Ltd., OP930 manufactured by CLARIANT Co., Ltd., PX200 manufactured by Daeba Chemical Co., Ltd., and epoxy resin containing FX289 and FX310 manufactured by Toho Chemical Co., Ltd. Phosphorus-containing phenoxy resin such as ERF001 manufactured by Dongdu Chemical Co., Ltd. Examples of the organic nitrogen-containing phosphorus compound include a phosphate amide compound such as SP670 and SP703 manufactured by Shikoku Chemicals Co., Ltd., a phosphazene compound such as SPB100 manufactured by Otsuka Chemical Co., Ltd., and SPE100. Examples of the metal hydroxides include magnesium hydroxide such as UD65' φ UD650 and UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325 'B-315, B-made by Baiya Kogyo Co., Ltd. 305, B-303, UFH-20, etc. [Resin additive] The 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 an organic cerium filling agent such as cerium powder, a tolerant powder, and a fluoro powder, and a tackifier such as Orben or Benton, and a fluorine-based system. , an antifoaming agent or a leveling agent, a decane coupling agent, a triazole compound, a thiazole compound, a triterpene compound, a porphyrin compound, and the like, an adhesion imparting agent, a phthalocyanine blue, a phthalocyanine green, an iodine green, A coloring agent such as disazo yellow or carbon black. Further, an imidazole compound such as Curezol 2MZ, 2E4MZ, C11Z, Cl 1Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK ' 2PHZ (Shikoku Chemical Industry Co., Ltd.) may be mentioned; N〇vacure (Asahi Kasei Industrial Co., Ltd.), -20- 201031707
Fujicure (富士化成工業（股）商品名）等的 合物；1，8-二氮雜雙環（5,4,0)十一烯_7(以_ )系四苯基硼酸鹽之3級胺化合物；等的胺系 等。 本發明的樹脂組成物之調製方法係沒有特 例如可舉出添加配合成分、視需要的溶劑等， 混合機等來混合的方法等。 φ 本發明的樹脂組成物之用途係沒有特別的 用於黏著薄膜、預浸物等的絕緣樹脂薄片、線 焊劑 '底部塡充材、固晶材、半導體密封材、 埋入零件的樹脂等需要樹脂組成物的用途之廣 ，較佳爲塗佈支持體上，形成樹脂組成物層而 膜，或在由纖維所成的薄片狀纖維基材中含浸 物而成爲預浸物。本發明的樹脂組成物亦可以 佈在線路基板上，而形成絕緣層，但工業上一 φ 爲黏著薄膜或預浸物等的薄片狀積層材料之形 緣層形成。 [黏著薄膜] 本發明的黏著薄膜係可藉由本業者所公知 如調製在有機溶劑中溶解有樹脂組成物的樹脂 持體上塗佈此樹脂清漆，再藉由加熱或熱風噴 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 胺加成物化 F簡稱DBU 硬化促進劑 別的限定， 使用旋轉式 限定，可使 路基板、阻 埋孔樹脂、 範圍。其中 成爲黏著薄 該樹脂組成 清漆狀態塗 般較佳係作 態而用於絕 的方法，例 清漆，在支 吹等以使有 基酮、環己 -21 - 201031707 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。有機溶劑可使用1種，也可組合2種以上 來使用。 乾燥條件係沒有特別的限定，以有機溶劑對樹脂組成 物層的含有比例較佳成爲10質量％以下、更佳成爲5質量 @ %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。雖然亦隨著清漆中的有機溶劑量而不 同，但是例如可在50〜150 °C使含有30〜60質量％的有機 溶劑之清漆乾燥3〜1 0分鐘左右。 黏著薄膜中所形成的樹脂組成物層之厚度，較佳爲導 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5〜70μιη的範圍，樹脂組成物層的厚度較佳爲具有10 〜1〇〇 μπι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體，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、聚碳酸酯、聚醯 亞胺等的塑膠薄膜。作爲塑膠薄膜，特佳爲PET。使用銅 箔、鋁箔等的金屬箔當作支持體，亦可成爲附金屬箔的黏 著薄膜。保護薄膜較佳爲使用同樣的塑膠薄膜。又，支持 -22- 201031707 體及保護薄膜’除了施予消光處理、電暈處理，亦可施予 脫模處理。還有’可用聚矽氧樹脂系脫模劑、醇酸樹脂系 脫模劑、氟樹脂系脫模劑等的脫模劑施予脫模處理。 支持體的厚度係沒有特別的限定，較佳爲10〜150μπι ，更佳爲25〜50μιη的範圍。又，保護薄膜的厚度亦沒有 特別的限定，較佳爲1〜40μπι的範圍，更佳爲以1〇〜 3 Ομηι的範圍來使用。 φ 本發明中的支持體’在層合於內層線路基板上後，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’若剝離支持體，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，較佳係對支持體預先施予脫模處理。再者 ’支持體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。 [使用黏著薄膜的多層印刷電路板等之製造方法] 接著’說明使用本發明的黏著薄膜來製造本發明的多 層印刷電路板等之線路基板的方法。當樹脂組成物層經保 護薄膜所保護時’在剝離此等後’以樹脂組成物層直接接 觸內層線路基板的方式，層合在內層線路基板的一面或兩 面上。於本發明的黏著薄膜中’藉由真空層合法在減壓下 層合在內層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 -23- 201031707 需要可預先加熱（預熱）黏著薄膜及內層線路基板。 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經圖型 加工的導體層（線路）者。又，於交互地層形成導體層與 絕緣層，成爲一面或兩面經圖型加工的導體層（線路）之 多層印刷電路板的製造之際，用於更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，導體線路層表面經黑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。 層合的條件就壓黏溫度（層合溫度）而言較爲70〜 140°C，就壓黏壓力而言較佳爲1〜ukgf/cm2 ( 9.8χ104〜 107_9xl〇4N/m2)，較佳爲在空氣壓力 20mmHg ( 26.7hPa )以下的減壓下進行層合。 真空層合係可使用市售的真空層合機來進行。作爲市 Ο 售的真空層合機，例如可舉出Nichigo-Morton (股）製真 空施加機、（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。 又’減壓下進行加熱及加壓的積層步驟，亦可使用一 般的真空熱壓來進行。例如，可藉由從支持體層側來加壓 經加熱的SUS板等金屬板。 作爲加壓條件，減壓度較佳爲1 xl〇_2MPa以下，更佳 -24- 201031707 爲lxl(T3MPa以下。加熱及加壓亦可以i階段來進行，但 是從抑制樹脂的滲出之觀點來看，較佳爲以2階段以上分 開條件來進行。例如，第1階段的加壓較佳在溫度7 0〜 150°C、壓力1〜15kgf/cm2的範圍進行，第2階段目的加 壓較佳爲在溫度150〜2001：、壓力1〜40kg f/cm2的範圍 進行。各階段的時間較佳爲以30〜120分鐘來進行。在市 售的真空熱壓機中，例如可舉出MNPC-V-750-5 — 200 (股 φ )名機製作所製）、VH 1 - 1 603 (北川精機（股）製）等。 如此地在內層線路基板上層合黏著薄膜後，剝離支持 薄膜的情況’可藉由將樹脂組成物熱硬化而在內層線路基 板上形成絕緣層。加熱硬化的條件可在 15 0°C〜2 2(TC、20 分鐘〜180分鐘的範圍作選擇，更佳爲160 °C〜200 °C、30 〜1 20分鐘。 於形成絕緣層後，在硬化前不剝離支持薄膜的情況， 係在此處剝離。接著，對內層線路基板上所形成的絕緣層 φ 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 處理較佳以使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。較佳爲增層法的多 層印刷電路板之製造中絕緣層的粗化所通用的氧化劑，即 -25- 201031707 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的粗化面之粗糙度，在形成微 細配線時，Ra値較佳爲〇.5μιη〜0.5μιη。再者，Ra値係表 示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 NT3300，藉由VSI接觸模式、50倍透鏡，由測 _ 定範圍爲121μηι><92μπι所得之數値來求得。 其次，於經由粗化處理而形成有凹凸的錨之樹脂組成 物層表面上，藉由組合無電解鍍敷與電解鍍敷的方法，來 形成導體層。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 的剝離強度較佳爲〇.6kgf/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。 [預浸物] 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有本發明的樹脂組成物之 -26- 201031707 狀態。 作爲由纖維所成的薄片狀纖維基材，例如可使用玻璃 布或芳香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 薄片狀纖維基材上，或是藉由口模式塗佈機直接塗佈等， 以製造預浸物的方法。又，溶劑法係與黏著薄膜同樣地， φ 於在有機溶劑中溶解有樹脂的樹脂清漆中浸漬薄片狀纖維 基材，使薄片狀纖維基材含浸樹脂清漆，然後使乾燥的方 法。 [使用預浸物的多層印刷電路板等之製造方法] 其次，說明使用本發明的預浸物來製造本發明的多層 印刷電路板等之線路基板的方法。於內層線路基板上，重 疊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 較佳爲 5 〜40kgf/cm2(49xl04 〜392xl04N/m2)，溫度較 佳爲120〜200 °C ’較佳以20〜100分鐘的範圍來成型。又 ，亦可與黏著薄膜同樣地，藉由真空層合法層合在內層線 路基板上後，進行加熱硬化而製造。然後，可與前述方法 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之線路基板。 [實施例] -27- 201031707 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「質量份」。 (實施例1 ) 於10份的MEK、3份的環己酮中，邊攪拌邊加熱溶 解35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「jER828EL」）' 35份的聯苯型環氧 樹脂（環氧當量269，日本化藥（股）製「NC3000H」） 、40份的苯氧樹脂（重量平均分子量3 8 000，日本環氧樹 脂（股）製「YX6954」不揮發份30質量％的甲基乙基酮 (以下簡稱「MEK」）與環己酮之1:1溶液）。於其中， 混入45份的苯酚酚醛清漆系硬化劑（Die (股）製「LA-7054」 不 揮發份 60 質量 ％ 的 MEK 溶液， 酚性羥 基當量 1 24 )、2份的4級鳞系硬化促進劑之（4_甲基苯基）三苯 基鱗硫氰酸酯（北興化學工業（股）製，「TPTP-SCN」 參 不揮發份1〇質量％的二甲基甲醯胺（以下簡稱「DMF」） 溶液）、7〇份的球形矽石（平均粒徑0·5μιη，附胺基矽烷 處理的「SOC2」ADMATECHS公司製），藉由高速旋轉混 合機進行均勻分散’以製作樹脂清漆。其次，以乾燥後的 樹脂厚度成爲40μιη的方式，藉由口模式塗佈機，將該樹 脂清漆塗佈在聚對苯二甲酸乙二酯（厚度38μιη，以下簡 稱「PET」）上，於80〜120。(：（平均1〇〇。(：）乾燥6分鐘 (殘留溶劑量約2重量％ )。接著，在樹脂組成物的表面 •28- 201031707 上，邊貼合厚度15 μηι的聚丙烯薄膜邊捲繞成輥狀。將輕 狀的黏著薄膜切割（slit )成寬度507mm，藉此而得到 5 07x336mm大小的薄片狀黏著薄膜。 (實施例2) 除了將實施例1之2份的4級鳞系硬化促進劑之（4· 甲基苯基）三苯基銹硫氰酸酯（北興化學工業（股）製’ φ 「TPTP-SCN」不揮發份1〇質量％的DMF溶液）變更爲4 份的同樣4級鱗系硬化促進劑之四苯基錢硫氰酸酯（北興 化學工業（股）製，「TPP-SCN」不揮發份5質量％的 D MF溶液）以外，完全同樣地得到黏著薄膜。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。 (實施例3 ) 於8份的MEK ' 8份的環己酮中，邊攪拌邊加熱溶解 Ο 18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「jER828EL」）、20份的聯苯型環氧樹脂 (環氧當量269’日本化藥（股）製「NC3000L」）、6 份的萘型4官能環氧樹脂（環氧當量162，DIC (股）製 「HP-4700」）、12份的苯氧樹脂（重量平均分子量 38 00 0，日本環氧樹脂（股）製「YL75 5 3」不揮發份3〇質 量％的MEK與環己酮之1 :1溶液）。於其中，混入13份 的苯酚酚醛清漆系硬化劑（DIC (股）製「LA-7054」不揮 發份60質量％的MEK溶液，酚性羥基當量124) 、20份 -29- 201031707 的活性酯系硬化劑（DIC (股）製「EXB-9460」不揮發份 65質量％的甲苯溶液，活性酯當量223 ) 、0.2份的4級 鳞系硬化促進劑之四丁基鱗癸酸鹽（北興化學工業（股） 製，「TBP-DA」）、75份的球形矽石（平均粒徑0.5μιη ，附胺基矽烷處理的「SOC2」ADMATECHS公司製）、18 份的聚乙烯縮丁醛樹脂溶液（玻璃轉移溫度1 〇5 °C，積水 化學工業（股）製「KS-1」不揮發份15質量％的乙醇與 甲苯之1:1溶液），藉由高速旋轉混合機進行均勻分散， @ 以製作樹脂清漆。接著，使用該樹脂清漆，與實施例1全 完同樣地得到黏著薄膜。 (實施例4) 於5份的MEK、5份的環己酮中，邊攪拌邊加熱溶解 25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「jER828EL」）、25份的聯苯型環氧樹脂 (環氧當量269，日本化藥（股）製「NC3000L」）、6 Q 份的萘型4官能環氧樹脂（環氧當量162，DIC (股）製 「HP-4700」）、12份的苯氧樹脂（重量平均分子量 38000，日本環氧樹脂（股）製「YL7553」不揮發份30質 量％的MEK與環己酮之1:1溶液）。於其中，混入36份 的苯酚酚醛清漆系硬化劑（DIC (股）製「LA-7054」不揮 發份60質量％的MEK溶液，酚性羥基當量124) 、2份的a compound such as Fujicure (Fuji Chemical Industry Co., Ltd.); 1,8-diazabicyclo(5,4,0)undecene_7 (in _) tetraphenylborate grade 3 amine a compound; an amine system or the like. The method of preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a compounding component, a solvent as necessary, and the like, and mixing by a mixer or the like. φ The use of the resin composition of the present invention is not particularly required for an insulating resin sheet such as an adhesive film or a prepreg, a wire soldering agent, a bottom filling material, a solid crystal material, a semiconductor sealing material, and a resin embedded in a part. The resin composition is widely used, and it is preferable to form a resin composition layer on a coating support, or to impregnate a sheet-like fibrous base material made of fibers to form a prepreg. The resin composition of the present invention may be formed on a wiring board to form an insulating layer, but industrially, φ is formed as an edge layer of a sheet-like laminated material such as an adhesive film or a prepreg. [Adhesive film] The adhesive film of the present invention can be coated with a resin varnish prepared by dissolving a resin composition in an organic solvent, and dried by a heating or hot air jet solvent, as known in the art. A resin composition layer is formed to be produced. Examples of the organic solvent include acetone and methyl ethylamine addition physicochemical F, which is abbreviated as DBU hardening accelerator, and can be used in a rotary substrate to limit the range of the substrate and the barrier resin. Among them, it is a method of applying a varnish in a state in which the resin is varnished, and is used as a varnish, such as a varnish, a ketone having a ketone or a cyclohexyl-21 - 201031707 ketone, or ethyl acetate. Acetate such as butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, carbitol, butyl carbitol, toluene, xylene, etc. An aromatic hydrocarbon, a guanamine solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more. The drying condition is not particularly limited, and the content ratio of the organic solvent to the resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less, and is dried. Drying conditions allow suitable and suitable drying conditions to be set by simple experimentation. Although it varies depending on the amount of the organic solvent in the varnish, for example, the varnish containing 30 to 60% by mass of the organic solvent may be dried at 50 to 150 ° C for about 3 to 10 minutes. The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer having the wiring substrate is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 1 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 in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, and polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate, and the like. A plastic film of polyester, polycarbonate, or polyimide. As a plastic film, it is especially good for PET. A metal foil such as copper foil or aluminum foil is used as a support, and it can also be an adhesive film with a metal foil. The protective film is preferably made of the same plastic film. Further, the support -22-201031707 body and protective film 'can be subjected to mold release treatment in addition to matting treatment and corona treatment. Further, a release agent such as a polyoxyxylene resin release agent, an alkyd resin release agent, or a fluororesin release agent may be applied to the release treatment. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 150 μm, more preferably 25 to 50 μm. Further, the thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 40 μm, and more preferably in the range of 1 〇 to 3 Ο μη. φ The support in the present invention is peeled off after being laminated on the inner layer wiring substrate or after forming an insulating layer by heat curing. After the adhesive film is heat-cured, if the support is peeled off, adhesion of dust or the like can be prevented in the hardening step, and the surface smoothness of the insulating layer after curing can be improved. When peeling after hardening, it is preferred to apply a release treatment to the support in advance. Further, the resin composition layer formed on the support 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. [Manufacturing Method of Multilayer Printed Circuit Board or the Like Using Adhesive Film] Next, a method of manufacturing a wiring board such as a multilayer printed wiring 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,' one layer or both sides of the inner layer wiring substrate are laminated so that the resin composition layer directly contacts the inner layer wiring substrate. In the adhesive film of the present invention, a method of laminating an inner layer wiring substrate under reduced pressure by vacuum lamination is suitably used. The lamination method can be batchwise or continuous by rolls. Further, before lamination, it is necessary to preheat (preheat) the adhesive film and the inner wiring substrate as -23-201031707. 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) that has been patterned. Further, when a conductor layer and an insulating layer are formed in an alternating formation, and a multilayer printed circuit board in which one or both sides of a patterned conductor layer (line) are formed, an intermediate product for forming an insulating layer and a conductor layer is also It is included in the inner layer wiring substrate of the present invention. In the inner layer @ circuit substrate, the surface of the conductor wiring layer is subjected to a roughening treatment in advance by blackening treatment or the like, and is preferably from the viewpoint of the adhesion of the insulating layer to the inner layer wiring substrate. The lamination conditions are preferably 70 to 140 ° C in terms of the pressure bonding temperature (laminating temperature), and preferably 1 to ukgf/cm 2 (9.8 χ 104 to 107 _ 9 x 10 4 N/m 2 ) in terms of the pressure-bonding pressure, preferably. Lamination was carried out under reduced pressure of air pressure of 20 mmHg (26.7 hPa) or less. The vacuum lamination system can be carried out using a commercially available vacuum laminator. For example, a vacuum laminator manufactured 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. Further, the step of laminating heating and pressurizing under reduced pressure can also be carried out by using a general vacuum hot pressing. For example, a metal plate such as a heated SUS plate can be pressurized from the side of the support layer. The pressure reducing condition is preferably 1 x l 〇 2 MPa or less, more preferably -24 to 201031707 is lxl (T3 MPa or less. Heating and pressurization can also be carried out in the i stage, but from the viewpoint of suppressing the bleeding of the resin. It is preferable to carry out the separation conditions of two stages or more. For example, the pressurization of the first stage is preferably carried out at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf/cm 2 , and the second stage of the pressure is higher. Preferably, it is carried out at a temperature of 150 to 2001: and a pressure of 1 to 40 kgf/cm2. The time of each stage is preferably 30 to 120 minutes. In a commercially available vacuum hot press, for example, MNPC is mentioned. -V-750-5 — 200 (share φ) manufactured by Nihon Seiki Co., Ltd.), VH 1 - 1 603 (Beichuan Seiki Co., Ltd.). When the adhesive film is laminated on the inner layer wiring substrate in this manner, the support film is peeled off. The insulating layer can be formed on the inner wiring substrate by thermally curing the resin composition. The conditions for heat hardening can be selected from the range of 150 ° C to 2 2 (TC, 20 minutes to 180 minutes, more preferably 160 ° C to 200 ° C, 30 to 1 20 minutes. After forming the insulating layer, The case where the support film is not peeled off before hardening is peeled off here. Next, the insulating layer φ formed on the inner layer circuit substrate is opened to form a through hole and a through hole. The opening may be, for example, by drilling, Well-known methods such as laser and plasma, and can be combined as needed, and the most common method of laser opening such as carbon dioxide laser, YAG laser, etc. 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.) and dichromate. Ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. It is preferably an oxidizing agent commonly used for the roughening of an insulating layer in the manufacture of a multilayer printed circuit board of a build-up method, that is, -25- 201031707 using an alkaline permanganic acid solution (for example) Sodium permanganate, sodium permanganate, sodium hydroxide water It is preferable that the solution is roughened. The roughness of the roughened surface on which the surface of the insulating layer is roughened is preferably 〇5 μm η to 0.5 μιη when forming fine wiring. Further, Ra 値 indicates One of the numerical values of the surface roughness is called an arithmetic mean roughness, and specifically, from the surface of the average line, the absolute height of the height changed within the measurement range is measured, and arithmetic average is performed. For example, VEECO Instruments can be used. WYKO NT3300 is obtained by a VSI contact mode and a 50-fold lens, and is obtained by measuring the number 値 of a range of 121 μηι> < 92 μπι. Next, a resin composition layer of an anchor having irregularities formed by roughening treatment On the surface, a conductor layer is formed by a combination of electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. Further, after the conductor layer is formed, the annealing strength of the conductor layer can be further improved by annealing at 150 to 200 ° C for 20 to 90 minutes, and the peeling strength of the conductor layer is preferably 〇.6 Kgf/cm or more. Further, as a method of patterning the conductor layer to form a line, for example, a subtractive method, a semi-additive method, etc., which are well known to those skilled in the art, can be used. [Prepreg] The prepreg of the present invention The resin composition of the present invention can be produced by semi-curing by heating by a hot melt method or a solvent method in a sheet-like fibrous base material made of fibers. That is, it can be a prepreg, which is The sheet-like fibrous base material made of the fiber is impregnated with the resin composition of the present invention in the state of -26-201031707. As the flaky fibrous base material formed of the fiber, for example, glass cloth or aromatic polyamide can be used. Fibers and the like are commonly used as fibers for prepregs. The hot melt method does not dissolve the resin in an organic solvent, but after coating the resin on a coated paper having good peelability from the resin, it is laminated on the sheet-like fibrous substrate, or by the mouth. A method in which a pattern coater is directly coated or the like to produce a prepreg. Further, in the same manner as the adhesive film, the solvent method is a method in which a flaky fiber substrate is immersed in a resin varnish in which a resin is dissolved in an organic solvent, and a flaky fiber substrate is impregnated with a resin varnish and then dried. [Manufacturing Method of Multilayer Printed Circuit Board or the Like Using Prepreg] Next, a method of manufacturing a wiring board such as a multilayer printed wiring board of the present invention using the prepreg of the present invention will be described. On the inner layer substrate, a plurality of sheets of the prepreg of the present invention are stacked one on top of the other, and a pressure release lamination is performed under pressure* heating conditions with a release film interposed therebetween. The pressure is preferably 5 to 40 kgf/cm2 (49 x 10 4 to 392 x 10 4 N/m 2 ), and the temperature is preferably 120 to 200 ° C. Preferably, it is molded in the range of 20 to 100 minutes. Further, similarly to the adhesive film, it can be produced by laminating the inner layer wiring substrate by vacuum lamination, and then heat-hardening. Then, the wiring layer of the multilayer printed wiring board can be manufactured by roughening the surface of the prepreg cured by the oxidizing agent and then forming the conductor layer by plating in the same manner as the above-described method. [Examples] -27- 201031707 The present invention will be described in more detail below by way of Examples and Comparative Examples, but the present invention is not limited thereto in any sense. In addition, in the following description, "parts" means "parts by mass". (Example 1) 35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, manufactured by Nippon Epoxy Resin Co., Ltd.) was dissolved in 10 parts of MEK and 3 parts of cyclohexanone while stirring. "jER828EL") 35 parts of biphenyl type epoxy resin (epoxy equivalent 269, "Noked Chemical Co., Ltd." "NC3000H"), 40 parts of phenoxy resin (weight average molecular weight 3 8 000, Japanese epoxy resin) "YX6954" is a non-volatile portion of 30% by mass of methyl ethyl ketone (hereinafter referred to as "MEK") and a 1:1 solution of cyclohexanone). Among them, 45 parts of a phenol novolac-based hardener ("ME-7 solution" of "LA-7054" non-volatiles, phenolic hydroxyl equivalent 1 24), and 2 parts of grade 4 scale hardening were mixed. (4_Methylphenyl)triphenyl sulfonate ("TPTP-SCN", a non-volatile matter of 1% by mass of dimethylformamide (hereinafter referred to as "Properger") Abbreviated as "DMF") solution), 7 parts of spherical vermiculite (average particle size of 0. 5 μm, manufactured by "Actual decane-treated "SOC2" ADMATECHS), uniformly dispersed by a high-speed rotary mixer to produce a resin Varnish. Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as "PET") by a die coater so that the thickness of the resin after drying became 40 μm. ~120. (: (average 1 〇〇. (:) drying for 6 minutes (residual solvent amount is about 2% by weight). Next, on the surface of the resin composition, 28-201031707, the polypropylene film is rolled up to a thickness of 15 μm. The light-adhesive film was slit into a width of 507 mm, thereby obtaining a sheet-like adhesive film having a size of 5 07 x 336 mm. (Example 2) In addition to the four-stage scale of Example 1 (4. Methylphenyl) triphenyl rust thiocyanate of the hardening accelerator ("DMTP-SCN" nonvolatiles DMF solution of Beixing Chemical Industry Co., Ltd.) was changed to 4 parts In addition to the tetraphenyl thiocyanate of the same four-stage scale-hardening accelerator (manufactured by Behind Chemical Industry Co., Ltd., "TPP-SCN" non-volatile 5% by mass D MF solution), it is completely adhered in the same manner. Then, using the resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Example 3) In 8 parts of MEK '8 parts of cyclohexanone, 18 parts of liquid was dissolved by heating while stirring. Bisphenol A type epoxy resin (epoxy equivalent 180, Japan epoxy resin company) "jER828EL "), 20 parts of biphenyl type epoxy resin (epoxy equivalent 269 'Nippon Chemical Co., Ltd. "NC3000L"), 6 parts of naphthalene type 4-functional epoxy resin (epoxy equivalent 162, DIC (share) "HP-4700"), 12 parts of phenoxy resin (weight average molecular weight 380 0, "YL75 5 3" made of Nippon Epoxy Resin Co., Ltd., nonvolatiles, 3 % by mass of MEK and cyclohexanone :1 solution), in which 13 parts of a phenol novolac-based curing agent (MEK solution of "LA-7054" non-volatile content of 60% by mass, phenolic hydroxyl equivalent 124), 20 parts - 29 was mixed. - 201031707 Active ester-based curing agent (EXB-9460, a non-volatile portion of DIC (EXB-9460), a toluene solution of 65% by mass, active ester equivalent of 223), and 0.2 parts of a tetrabutyl scale of a 4-stage scaly hardening accelerator癸 ( ( (Beixing Chemical Industry Co., Ltd., "TBP-DA"), 75 parts of spherical vermiculite (average particle size 0.5μιη, "SOC2" ADMATECHS company with amine decane treatment), 18 parts of poly Vinyl butyral resin solution (glass transition temperature 1 〇 5 °C, Sekisui Chemical Industry Co., Ltd. "KS-1" non-volatile 15 mass The 1:1 solution of ethanol and toluene was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Then, using the resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Example 4) Into 5 parts of MEK and 5 parts of cyclohexanone, 25 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "JER828EL" made by Nippon Epoxy Co., Ltd.) was heated and dissolved while stirring. 25 parts of biphenyl type epoxy resin (epoxy equivalent 269, "Nippon Chemical Co., Ltd." "NC3000L"), 6 Q parts of naphthalene type 4-functional epoxy resin (epoxy equivalent 162, DIC) "HP-4700"), 12 parts of phenoxy resin (weight average molecular weight 38,000, "YL7553" made by Nippon Epoxy Resin Co., Ltd., non-volatile content of 30% by mass of a 1:1 solution of MEK and cyclohexanone). Among them, 36 parts of a phenol novolac-based curing agent ("LA-7054" manufactured by DIC Co., Ltd., a 60% by mass MEK solution, a phenolic hydroxyl equivalent of 124), and 2 parts were mixed.
4級銕系硬化促進劑之丁基三苯基鱗硫氰酸酯（北興化學 工業（股）製、「TPPB-SCN」不揮發份1〇質量％的DMF -30- 201031707 溶液）、：190份的球形矽石（平均粒徑〇·5 μιη，附胺基砂 烷處理的「SOC2」ADMATECHS公司製）、12份的聚乙 烯縮丁醛樹脂溶液（玻璃轉移溫度1 05 °C，積水化學工業 (股）製「KS-1」不揮發份15質量％的乙醇與甲苯之ι:1 溶液），藉由高速旋轉混合機進行均勻分散，以製作樹脂 清漆。接著’使用該樹脂清漆’與實施例1全完同樣地得 到黏著薄膜。 參 (比較例1 ) 除了不添加實施例1的4級鳞系硬化促進劑以外，完 全同樣地得到黏著薄膜。接著，使用該樹脂清漆，與實施 例1全完同樣地得到黏著薄膜。 (比較例2 ) 除了將實施例1之2份的4級鳞系硬化促進劑之（4_ • 甲基苯基）三苯基銹硫氰酸酯（北興化學工業（股）製， 「TPTP-SCN」不揮發份1〇質量％的DMF溶液）變更爲2 份的同樣4級鍈系硬化促進劑之d B U系四苯基硼酸鹽（ SUNAPRO株式會社製，「U-CAT 5002」不揮發份1〇質量 %的MEK溶液）以外，完全同樣地得到黏著薄膜。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3 ) 除了將實施例3之0.2份的4級鱗系硬化促進劑之四 -31 - 201031707 丁基銹癸酸鹽（北興化學工業（股）製，「TBP-DA」） 變更爲2份的同樣4級鍈系硬化促進劑之三苯基膦三苯基 硼烷（北興化學工業（股）製，「Tpp-s」不揮發份10質 量％的DMF溶液）以外，完全同樣地得到黏著薄膜。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 全0 (比較例4 ) φ 除了將實施例1之2份的4級錢系硬化促進劑之（4-甲基苯基）三苯基錢硫氰酸酯（北興化學工業（股）製’ 「TPTP-SCN」不揮發份10質量°/。的DMF溶液）變更爲 0.2份同樣4級鋳系硬化促進劑之四苯基銹四苯基硼酸酯 (北興化學工業（股）製，「TPP-K」）以外，完全同樣 地得到黏著薄膜。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全。 <剝離強度及Ra値測定用樣品之調製> (1) 內層線路基板的基底處理 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-5 00 (名機（股） -32- 201031707 製商品名），將實施例及比較例所作成的黏著薄膜層合在 內層線路基板的兩面。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，以形成絕緣層。 φ ( 4 )粗化處理 於60°C將形成有絕緣層的內層線路基板浸漬在膨潤液 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 80°C 浸漬在 作爲粗化液的 ATOTECH 日本（股）之 Concentrate Compact P(KMn〇4: 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。使 • 用此基板，進行粗化處理後的絕緣層表面之表面粗糙度（ Ra値）的測定。 (5 )半加成法的鍍敷 爲了在絕緣層表面上形成線路，將內層線路基板浸漬 含PdCl2的無電解鍍敷用溶液中，接著浸漬在無電解鍍銅 液中。於1 5(TC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 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。對於此線路基板，進行所鍍敷的銅之剝離 -33- 201031707 強度的測定。 <鍍敷導體層的拉剝強度（剝離強度）之測定及評價 >Butyl triphenyl scaly thiocyanate of grade 4 lanthanide hardening accelerator (made by Beixing Chemical Industry Co., Ltd., "TPPB-SCN" nonvolatile matter 1% by mass of DMF -30- 201031707 solution), 190 Part of spherical vermiculite (average particle size 〇·5 μιη, "SOC2" ADMATECHS company with amine-based sandane treatment), 12 parts of polyvinyl butyral resin solution (glass transition temperature 1 05 °C, hydrophobic chemistry) Industrial Co., Ltd. "KS-1" non-volatile portion of 15% by mass of ethanol and toluene (1:1 solution) was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Then, using the resin varnish, an adhesive film was obtained in the same manner as in Example 1. Reference (Comparative Example 1) An adhesive film was obtained in the same manner except that the fourth-order scale hardening accelerator of Example 1 was not added. Then, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1. (Comparative Example 2) In addition to the 4 parts of the scaly hardening accelerator of the first embodiment, (4_ • methylphenyl) triphenyl rust thiocyanate (Beixing Chemical Industry Co., Ltd., "TPTP- "SCN" non-volatile content of 1% by mass of DMF solution) changed to 2 parts of d BU-based tetraphenylborate of the same grade 4 lanthanum hardening accelerator ("U-CAT 5002" non-volatiles manufactured by SUNAPRO Co., Ltd. An adhesive film was obtained in the same manner except for 1% by mass of the MEK solution. Then, an adhesive film was obtained in the same manner as in Example 1 using this resin varnish. (Comparative Example 3) In addition to 0.2 parts of the fourth-order scale hardening accelerator of Example 3, four-31 - 201031707 butyl rust citrate ("TBP-DA", manufactured by Kitai Chemical Industry Co., Ltd.) was changed to Two parts of the same four-stage lanthanide hardening accelerator, triphenylphosphine triphenylborane ("Tpp-s" non-volatile 10% by mass DMF solution), completely identically An adhesive film is obtained. Then, using the resin varnish, the adhesive film was obtained in the same manner as in Example 1 (Comparative Example 4) φ In addition to the (4-methylphenyl) group of the four-stage hardening accelerator of Example 1 Triphenylphenol thiocyanate ("TPTP-SCN" non-volatile content of 10 mass% / DMF solution) was changed to 0.2 parts of the same 4-stage lanthanide hardening accelerator tetraphenyl An adhesive film was obtained in the same manner except for the rust tetraphenyl borate ("TPP-K" manufactured by Kitai Chemical Industry Co., Ltd.). Then, using this resin varnish, the entire adhesive film was obtained in the same manner as in Example 1. <Preparation of peel strength and Ra値 measurement sample> (1) Underlayer treatment of inner layer wiring substrate A glass cloth substrate epoxy resin double-sided copper-clad laminate in which an inner layer is formed [copper foil thickness 18 μπι 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 the adhesive film The adhesive film laminate of the examples and the comparative examples was laminated using a batch vacuum pressure laminator MVLP-5 00 (brand name: 32-201031707) On both sides of the inner layer circuit substrate. 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. The resin composition was cured at 180 ° C for 30 minutes to form an insulating layer. φ ( 4 ) roughening treatment The inner layer wiring substrate on which the insulating layer was formed was immersed in Swelling Dip Securigand P containing diethylene glycol monobutyl ether in ATOTECH Japan (stock) at a temperature of 60 ° C for 5 minutes. Then, it was immersed in ATOTECH Japan's Concentrate Compact P (KMn〇4: 60 g/L, NaOH: 40 g/L aqueous solution) as a roughening solution at 80 ° C for 20 minutes, and finally immersed at 40 ° C for 20 minutes. Neutralization solution is 5 minutes in ATOTECH Japan's Reduction Solution Securigand P. Use this substrate to measure the surface roughness (Ra値) of the surface of the insulating layer after roughening. (5) Plating by semi-additive method In order to form a wiring on the surface of the insulating layer, the inner wiring substrate was immersed in a solution for electroless plating containing PdCl 2 and then immersed in an electroless copper plating solution. After annealing for 15 minutes at TC for annealing, a photoresist for etching was formed, and a pattern was formed by etching, and then copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 ± 5 μm. Next, at 180. Annealing treatment was performed for 60 minutes at ° C. The strength of the plated copper peeling-33-201031707 was measured for this circuit board. <Measurement and evaluation of the peeling strength (peeling strength) of the plated conductor layer> ;
使用刀具，在線路基板的導體層中導入寬度l〇mm、 長度lOOinm的切槽，剝離其一端且以夾具（株式會社 TSE Autocom型試驗機AC-50C-SL )夾住，測定在室溫中 以5 Omm/分鐘的速度在垂直方向中拉剝35mm時的荷重。 將荷重爲 〇.75kgf/cm以上時評價爲「◎」，將未達 0.75kgf/cm 且 0.62kgf/cn t!以上時評價爲 「〇」 ，將未達 0.62kgf/cm 且 0.40kgf/cr η以上時評價爲 「△」 ，將未達 0.40kgf/cm 時評價爲^ x」 〇 <粗化後的表面粗糙度（Ra値）之測定及評價> 使用非接觸型表面粗糙度計（VEECO儀器公司製 WYKO NT3300 )，藉由VSI接觸模式、50倍透鏡，測定 @ 以測定範圍當作121 μιηχ 92 μιη所得之數値。又，藉由求得 10點的平均粗糙度而測定，當作Ra値。將Ra値500nm 以上時評價爲「xxj ，將未達500nm且420nm以上時評 價「X」，將未達420nm且3 80nm以上時評價爲「△」， 將未達3 8 0nm且300nm以上時評價爲「〇」，將未達 300nm且200nm以上時評價爲「◎」，將未達200nm時評 價爲「◎ ◎ j 。 下述表1中記載使用實施例及比較例所得之清漆的評 -34- 201031707 價樣品之鍍敷導體層的剝離強度及粗化後的表面粗糙度（ Ra値）之結果。如由表1可明知，於實施例的樹脂組成 物中，儘管絕緣層的表面粗糙度低，卻形成具有高剝離強 度的導體層。如此地可知在本發明中，由於達成低的表面 粗糙度，而有利於微細配線化。於不加有4級鱗系硬化促 進劑的比較例1中，爲了得到同等的剝離強度，粗糙度增 大。於比較例2中，雖然使用胺系硬化劑，但還是成爲粗 φ 糙度增大的結果。於比較例3、4中，雖然使用同樣的三 苯基膦系硬化促進劑當作硬化促進劑，但是與實施例比較 下，無法達成低粗糙度且高剝離的並存。 [表1] | ®合成分(不揮發份換》κ質量份〉 實施例 1 IT施例 2 *施钿 3 實施例 4 比較例 1 比較例 2 比較例 3 比較例 4 (Α)多官能環氧樹脂 NC3000H 35 35 35 35 35 NC3000L 20 25 20 HP-4700 6 6 6 iER828EL 35 35 18 25 35 35 18 35 (Β)硬化劑 LA-7054 27 27 ΊΑ 21 27 27 7Λ 27 EXB9460 13 13 (C)熱塑性樹脂 YX6954 12 12 12 12 12 YL7553 3.6 3.6 3.6 KS-1 2.7 1.8 2.7 nyi無機塡尭材 SOC2 70 70 75 190 70 70 75 70 硬化促進劑 TPTP-SCN 0.2 TPP-SCN 0.2 TBP-DA 0*2 TPPB-SCN 0.2 U-CAT 5002 02 TPP-S 0>2 TPP-K 0·2 0^06 0^06 0.309 0<260 0.000 0206 0.309 0^06 剝離強度(kgf/cm> ◎ (0.75) ◎ (0.75) Ο (0.70) Ο (0.63) j ο (0.70) Ο (0.70) Δ (0.61) Ο (0.70) 表面粗糖度(Ra働(nm) 〇 (350) 〇 (370) @ (200) ◎◎ 1 (150) I XX (650) I XX (680) X (420) XX (700) [產業上的利用可能性] 可提供即使將樹脂組成物硬化所得之絕緣層表面的粗 糙度低，也可形成具有高剝離強度的導體層之樹脂組成物 -35- 201031707 、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。Using a cutter, a slit having a width of l〇mm and a length of 100 inm was introduced into the conductor layer of the circuit board, and one end thereof was peeled off and clamped by a jig (TSE Autocom type tester AC-50C-SL), and measured at room temperature. The load at the time of pulling 35 mm in the vertical direction at a speed of 5 Omm/min. When the load is 〇.75kgf/cm or more, it is evaluated as "◎", and when it is less than 0.75kgf/cm and 0.62kgf/cn t! or more, it is evaluated as "〇", which will not reach 0.62kgf/cm and 0.40kgf/cr. When η or more, the evaluation was "△", and when it was less than 0.40 kgf/cm, it was evaluated as ^x" 〇 <Measurement and evaluation of surface roughness (Ra値) after roughening> Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by VEECO Instruments Co., Ltd.), measured by the VSI contact mode and a 50-fold lens, with a measurement range of 121 μm χ 92 μιη. Further, it was measured by obtaining an average roughness of 10 points, and it was regarded as Ra値. When Ra 値 500 nm or more, it is evaluated as “xxj, when it is less than 500 nm and 420 nm or more, “X” is evaluated, and when it is less than 420 nm and 380 nm or more, it is evaluated as “Δ”, and when it is less than 380 nm and 300 nm or more, it is evaluated. "〇" is evaluated as "◎" when it is less than 300 nm and 200 nm or more, and "◎ ◎ j when it is less than 200 nm. The varnish obtained by using the examples and the comparative examples is described in Table 1 below - 34 - 201031707 The result of the peel strength of the plated conductor layer of the valence sample and the surface roughness after roughening (Ra 値). As is apparent from Table 1, in the resin composition of the example, although the surface roughness of the insulating layer When it is low, a conductor layer having a high peeling strength is formed. Thus, in the present invention, it is known that a low surface roughness is obtained, which is advantageous for fine wiring. Comparative Example 1 in which no grade 4 scale hardening accelerator is added In order to obtain the same peeling strength, the roughness was increased. In Comparative Example 2, although an amine-based curing agent was used, the roughness of the coarse φ was increased. In Comparative Examples 3 and 4, the same was used. Triphenylphosphine-based hardening accelerator It is regarded as a hardening accelerator, but compared with the examples, it is impossible to achieve low roughness and high peeling. [Table 1] | ® Synthesis (non-volatiles exchange) κ mass parts> Example 1 IT Example 2 *钿 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (Α) Polyfunctional epoxy resin NC3000H 35 35 35 35 35 NC3000L 20 25 20 HP-4700 6 6 6 iER828EL 35 35 18 25 35 35 18 35 (Β) hardener LA-7054 27 27 ΊΑ 21 27 27 7Λ 27 EXB9460 13 13 (C) Thermoplastic resin YX6954 12 12 12 12 12 YL7553 3.6 3.6 3.6 KS-1 2.7 1.8 2.7 nyi inorganic coffin SOC2 70 70 75 190 70 70 75 70 Hardening accelerator TPTP-SCN 0.2 TPP-SCN 0.2 TBP-DA 0*2 TPPB-SCN 0.2 U-CAT 5002 02 TPP-S 0>2 TPP-K 0·2 0^06 0^06 0.309 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Roughness (Ra働(nm) 〇(350) 〇(370) @ (200) ◎◎ 1 (150) I XX (650) I XX (6 80) X (420) XX (700) [Industrial use possibility] A resin composition capable of forming a conductor layer having high peel strength even when the surface roughness of the insulating layer obtained by hardening the resin composition is low -35- 201031707 , Adhesive film, prepreg, multilayer printed circuit board. In addition, it is also possible to provide electric appliances such as computers equipped with such computers, portable telephones, digital cameras, televisions, etc., or vehicles such as automatic two-wheelers, automobiles, trams, ships, and airplanes.
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