200934348 九、發明說明 【發明所屬之技術領域】 本發明係關於一種多層印刷電路板之製造方法，尤其 使用黏著薄膜之多層印刷電路板的製造方法。 【先前技術】 以往，就多層印刷電路板之製造技術而言，已知於芯 〇 基板上交互地重疊絕緣層與導體層之積層（built up)方式 的製造方法。例如，於形成絕緣層係已知一種方法，其係 使用於塑膠膜上形成熱硬化性樹脂層之黏著薄膜，使黏著 薄膜積層於內層電路基板上，使熱硬化性樹脂進行熱硬化 之方法。又，有時於絕緣層含有無機塡充材。 藉由近年之電子機器或電子零件之小型化、高功能化 等之需要，在多層印刷電路板中係有要求薄型化、配線之 高密度化的傾向。認爲於多層印刷電路板之薄型化的要求 〇 中’爲同時維持機械強度，係例如含有許多氧化矽等之無 機塡充材作爲形成層間絕緣層之材料，而提高層間絕緣層 _ 之彈性率乃很有效。 又，在配線被高密度化之多層印刷電路板中係易產生 因銅配線與絕緣層之熱膨脹係數相異的龜裂發生等之問 題’但，藉由使絕緣層含有許多二氧化矽等之無機塡充 材’可有效作爲銅配線與絕緣層之熱膨脹係數相異所造成 的龜裂發生之防止對策。亦即，於層間絕緣層之形成材料 含有許多熱膨脹率低的無機塡充材，可抑制絕緣層之熱膨 -4- 200934348 脹率至很低，並可減少銅配線與絕緣層之熱膨脹係數之 差，而抑制龜裂的發生。 專利文獻1、2係記載使用黏著薄膜之多層印刷電路 板的製造方法，於專利文獻1中係揭示一種方法，其係使 用由具有離型層之支撐基膜與熱硬化性樹脂組成物所構成 的黏著薄膜，於芯基板層合該黏著薄膜，以支撐基膜附著 之狀態熱硬化後，直接以支撐基膜附著，或，於剝離後藉 0 雷射或鑽孔機進行開孔。又，於專利文獻2中係揭示一種 方法，其係於金屬箔的單面層合絕緣層，進一步於其絕緣 層表面層合可剝離之有機薄膜，從有機薄膜面側進行雷射 加工之方法。 [專利文獻1]特開2001-196743號公報 [專利文獻2]特許第3899544號公報 【發明內容】 φ [發明之揭示] [發明欲解決之課題] 於絕緣層含有許多無機塡充材時，於盲孔（Via hole )之形成產生問題。盲孔之形成可想到例如使用UV-YAG雷射之方法’但UV-YAG雷射係無機塡充材之加工 性良好，但從成本或加工速度的觀點，未必滿足者。另 外，二氧化碳氣體雷射係於加工速度或成本的面較UV-YAG雷射更優’但於含有許多無機塡充材之絕緣層照射 二氧化碳氣體雷射而形成肓孔時，加工性降低，孔洞底徑 -5- 200934348 小於頂徑，成爲推拔明顯的形狀，成爲降低盲孔之導通信 賴性的原因。可知使孔底徑形成近似於頂徑之形狀，係只 要以強的能量進行加工即可，但提高二氧化碳氣體雷射之 能量時，施加於絕緣層表面之損傷會增大，孔周邊之凹凸 程度變大，有微細配線化變成不佳等之問題。如此之問題 係於含有無機塡充材35質量％以上之絕緣層，製造肓孔 的孔徑（頂徑）成爲1 〇〇 μιη以下之高密度的印刷電路板 φ 時明顯化。另外，於上述2個文獻記載之雷射加工係形成 孔徑（頂徑）超過100 μιη之孔洞的加工，故不會成爲很 大的問題。 本發明係有鑑於上述之事情而成者，其欲解決之課 題，係提供一種多層印刷電路板之製造方法，其係對於含 有無機塡充材35質量％以上之絕緣層，藉二氧化碳氣體 雷射，可生產性佳地形成頂徑爲ΙΟΟμιη以下之肓孔， 且，於孔洞周邊之絕緣層表面不產生大的凹凸，而形成頂 〇 徑與孔底徑之差小的良好孔形狀之肓孔。 [用以解決課題之手段] 本發明人等係爲解決上述課題，專心硏究之結果，發 現若對於含有無機塡充材35質量％以上之絕緣層，從密 著於絕緣層表面之塑膠膜上照射二氧化碳氣體雷射，爲使 加工性良好而照射充分且高能量的二氧化碳氣體雷射時， 可抑制絕緣層表面之損傷，可形成孔底徑近似頂徑之盲 孔，終完成本發明。亦即，本發明係含有如以下之內容 -6 - 200934348 者。 [1] 一種多層印刷電路板之製造方法，其特徵在於： 包含如下步驟：形成於電路基板之雙面或單面且含有無機 塡充材35質量％以上之絕緣層’從密接於該絕緣層表面 之塑膠薄膜上照射二氧化碳氣體雷射，形成頂徑爲ΙΟΟμηι 以下之肓孔。 [2] 如上述[1]項之多層印刷電路板之製造方法，其中 U 含有無機塡充材35質量％以上之絕緣層爲使含有無機塡 充材3 5質量％以上之熱硬化性樹脂組成物層進行熱硬化 者。 [3] 如上述[2]項之多層印刷電路板之製造方法，其中 於塑膠薄膜上形成含有無機塡充材35質量％以上之熱硬 化性樹脂組成物層之黏著薄膜，以該熱硬化性樹脂組成物 層相接於電路基板之雙面或單面之方式層合於電路基板， 使該熱硬化性樹脂組成物層進行熱硬化而形成含有無機塡 Φ 充材35質量％以上之絕緣層後，從塑膠薄膜上照射二氧 化碳氣體雷射。 [4] 如上述[1]〜[3]項中任一項之多層印刷電路板之製 造方法，其中含有無機塡充材35質量％以上之絕緣層爲 含有無機塡充材35〜70質量％之絕緣層。 [5] 如上述[1]〜[4]項中任一項之多層印刷電路板之製 造方法，其中無機塡充材爲二氧化矽。 [6] 如上述[1]〜[5]項中任一項之多層印刷電路板之製 造方法，其中塑膠薄膜爲聚對苯二甲酸乙二酯薄膜。 200934348 [7] 如上述Π]〜[6]項中任一項之多層印刷電爵 造方法，其中塑膠薄膜之厚度爲2 0~5 0μπι，絕緣芳 爲 ΐ5~1〇〇μιη。 [8] 如上述Π]〜[7]項中任一項之多層印刷電腾 造方法，其中二氧化碳氣體雷射之能量爲lmJ以」 [9] 如上述[1]~[7]項中任一項之多層印刷電腾 造方法，其中二氧化碳氣體雷射之能量爲1〜5m J。 [10] 如上述Π]〜[9]項中任一項之多層印刷電K 造方法，其中二氧化碳氣體雷射之發射數爲1或2 [1 1]如上述Π]〜Π〇]項中任一項之多層印刷· 製造方法，其中孔洞之開口率（底徑/頂徑）爲 上。 [12]如上述[1]~[1 1]項中任一項之多層印刷 製造方法，其中進一步含有從絕緣層剝離塑膠薄 步驟。 ❹ [13]如上述[12]項之多層印刷電路板之製造 中進一步含有如下步驟：使絕緣層粗化處理之粗 於所粗化之絕緣層表面藉電鍍形成導體層之電 及，於導體層形成電路之電路形成步驟。 [發明之效果] 若依本發明之多層印刷電路板的製造方法， 無機塡充材35質量％以上之絕緣層，爲使加工 用充分且高能量的二氧化碳氣體雷射時，亦不對 板之製 之厚度 板之製 〇 板之製 板之製 〇 路板之 7 0 %以 路板之 之剝離 法，其 步驟； 步驟； 於含有 良好使 周邊的 -8- 200934348 絕緣層表面造成很大的損傷’可形成頂徑爲1〇〇Mm以下 之盲孔，可形成信賴性高之高密度的多層配線。 又，使上述頂徑爲100 μπί以下之盲孔形成爲孔洞的 開口率（底徑/頂徑）爲頂徑與孔底徑之差小的良好孔形 狀，故可形成導通信賴性優之肓孔。 【實施方式】 φ [用以實施發明之最佳形態] 以下，依其適宜的實施形態而說明本發明。 本發明之多層印刷電路板的製造方法係，其特徵在於 包含如下步驟：形成於電路基板之雙面或單面且含有無機 塡充材35質量％以上之絕緣層，從密接於該絕緣層表面 之塑膠薄膜上照射二氧化碳氣體雷射，形成頂徑爲ΙΟΟμιη 以下之肓孔。 在本發明中，「含有無機塡充材35質量％以上之絕 〇 緣層」係在使用來作爲多層印刷電路板之絕緣層的樹脂組 成物中，藉由含有無機塡充材35質量％以上之樹脂組成 物所形成的絕緣層。尤宜爲以含有無機塡充材35質量％ 以上之熱硬化性樹脂組成物的硬化物所形成。含有二氧化 矽等之無機塡充材3 5質量％以上之絕緣層係表示高彈性 率與低熱膨脹性，例如可達成彈性率爲4GPa以上及/或熱 膨脹係數（室溫~150°C)爲50ppm/°C以下之絕緣層。因 而，藉由如此之絕緣層的使用，可製造機械強度優，且熱 膨脹係數之差所造成的龜裂發生亦被抑制之多層印刷電路 -9- 200934348 板。 本發明中所謂之「無機塡充材的含量」係以構成絕緣 層之樹脂組成物全體的不揮發成分爲100質量％時之無機 塡充材占有的質量分率。例如藉熱硬化性樹脂組成物的硬 化物形成絕緣層時，採用以硬化前之樹脂組成物全體的不 揮發成分爲100質量％時之無機塡充材占有的質量分率所 算出之値。又，在「含有無機塡充材35質量％以上之絕 φ 緣層」中，若無機塡充材之含量太多，在後步驟中要確保 形成於絕緣層上之導體層的密度強度有變困難之傾向，故 無機塡充材之含量宜爲70質量％以下。亦即，無機塡充 材之含量宜爲35~7 0質量％，更宜爲35~60質量％。又， 在本發明中，「含有無機塡充材35質量％以上之絕緣 層」之厚度係宜爲15~1〇〇μιη，更宜爲20~70μιη。若絕緣 層之厚度不足15 μιη，要平坦地層合於電路基板有變困難 之傾向，若超過ΙΟΟμιη，不適於多層印刷電路板之薄型 化。 在本發明中，無機塡充材係可舉例如二氧化矽、氧化 鋁、雲母、雲母粉、矽酸鹽、硫酸鋇、氫氧化鎂、氧化鈦 等。其中，從高彈性率、低熱膨脹率、低介電正切而言’ 宜爲無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合 成二氧化矽等之二氧化矽。又’二氧化矽宜爲球狀者。無 機塡充材係宜使用以矽烷偶合劑等之表面處理劑表面處理 者。矽烷偶合劑係可使用胺基矽烷、烯丙基矽烷、院基砂 院、院氧基较院、苯基砂院、環氧基砍院等公知者。 -10- 200934348 又，無機塡充材係從絕緣層之絕緣信賴性的觀點，宜 平均粒徑爲3 μιη以下’更宜平均粒徑爲1.5 μιη以下者。 又，平均粒徑之下限無特別限定，但從處理性、成本等之 觀點，宜爲〇.1 μ®以上。 上述之無機塡充材的平均粒徑係可依Mi e散射理論之 雷射繞射、散射法來測定。具體上係藉雷射繞射式粒度分 布測定裝置，以體積基準製成無機塡充材之粒度分布’可 @ 以其中間徑作爲平均粒徑來測定。測定試樣係宜使用藉超 音波使無機塡充材分散於水中者。雷射繞射式粒度分布測 定裝置係可使用股份公司堀場製作所製LA-5 00等。 在本發明中，以含有無機塡充材35質量％以上之熱 硬化性樹脂組成物的硬化物構成「含有無機塡充材3 5質 量％以上之絕緣層」時，成爲基材成分之熱硬化性樹脂組 成物係若爲適於多層印刷電路板之絕緣層者，無特別限 制，可使用於例如環氧樹脂、氰酸酯基酯樹脂、酚樹脂、 φ 雙馬來醯亞胺-三嗪樹脂、聚醯亞胺樹脂、丙烯酸樹脂、 乙烯基苯甲基樹脂等之熱硬化性樹脂中至少調配其硬化劑 之組成物，較佳係含有環氧樹脂作爲熱硬化性樹脂之組成 物，例如，尤宜含有環氧樹脂、熱塑性樹脂及硬化劑之組 成物。 上述環氧樹脂係可舉例如雙酚A型環氧樹脂、聯苯 基型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、雙酚F 型環氧樹脂、含磷之環氧樹脂、雙酚S型環氧樹脂、脂環 式環氧樹脂、脂肪族鏈狀環氧樹脂、酚酚醛清漆型環氧樹 -11 - 200934348 脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧 樹脂、具有丁二烯構造的環氧樹脂、雙酚之二縮水甘油基 醚化物、萘二醇之二縮水甘油基醚化物 '酚類之縮水甘油 基醚化物、及醇類之二縮水甘油基醚化物、以及此等之環 氧樹脂的烷基取代體、鹵化物及氫添加物等。此等之環氧 樹脂係使用任一種，或混合2種以上而使用。 環氧樹脂係此等之中’從耐熱性、絕緣信賴性、與金 U 屬膜之密著性的觀點，宜爲雙酚A型環氧樹脂、萘酚型 環氧樹脂、萘型環氧樹脂、聯苯基型環氧樹脂、具有丁二 烯構造的環氧樹脂。具體上係可舉例如液狀雙酚A型環 氧樹脂（Japan Epoxy Resin (股）製「Epicote 8 2 8EL」）、萘型2官能環氧樹脂（大日本油墨化學工業 (股）製「HP 4032」、「HP 4032D」）、萘型4官能環 氧樹脂（大日本油墨化學工業（股）製「HP 4700」、萘 酚型環氧樹脂（東都化成（股）製「ESN-475V」）、具 ❷ 有丁二烯構造之環氧樹脂（Daicel化學工業（股）製 「PB-3 600」）、具有聯苯基構造之環氧樹脂（日本化藥 (股）製「NC 3000 H」、「NC 3000L」、Japan Epoxy Resin (股）製「YX 4000」）等。 又，上述熱塑性樹脂係對硬化後之組成物賦予適度的 可撓性等之目的所調配者，可舉例如苯氧樹脂、聚乙烯基 乙縮醛樹脂、聚醯亞胺、聚醯胺醯亞胺、聚醚楓、聚碾 等。此等係可單獨使用任一種，或倂用2種以上。該熱塑 性樹脂係以熱硬化性樹脂組成物之不揮發成分作爲1 00質 -12- 200934348 量％時，宜以〇.5~60質量％之比率調配，更宜爲3〜50質 量％。 苯氧基樹脂之具體例可舉例如具有 Japan Epoxy Resin (股）製1256、42 50等之雙酚 A骨架者、具有 Japan Epoxy Resin (股）製YX 8100等之雙酣S骨架者、 具有Japan Epoxy Resin (股）製YX 6954等之雙酚乙醯 苯骨架者、具有東都化成（股）製FX 28 0、FX 293等之 0 雙酣苟骨架者、具有Japan Epoxy Resin (股）製YL 75 53 等之雙甲酌荀骨架者、具有Japan Epoxy Resin (股）製 YL 6794等之蔽嫌骨架者、具有Japan Epoxy Resin (股） 製YL 7213、YL 7290等之三甲基環己烷骨架者等。 聚乙烯乙縮醛樹脂宜爲聚乙烯丁縮醛樹脂，聚乙烯乙 縮醛樹脂之具體例可舉例如電化學工業（股）製、電化丁 縮醛 4000-2、 5000-A、 6000-C、 6000-EP、積水化學工業 (股）製Esulex BH系列、BX系列、KS系列、BL系 φ 列、B Μ系列等。 聚醯亞胺之具體例可舉例如新日本理化（股）製之聚 酿亞胺「Rikacoat SN 20」及「Rikacoat ΡΝ 20」。又，使 2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四鹼酸 酐反應所得到之線狀聚醯亞胺（特開2006-37083號公報 記載者）、含有聚矽氧烷骨架之聚醯亞胺（特開2002-12667號公報、特開2000-3 1 9386號公報等記載者）等之 改性聚醯亞胺。 聚醯胺醯亞胺之具體例可舉例如東洋紡績（股）製之 -13- 200934348 聚醯胺醯亞胺「Vylomax HR 11NN」及「Vylomax HR16NN」。又，可舉例如，日立化成工業（股）製之含 有聚矽氧烷骨架之聚醯胺醯亞胺「KS9100」、「KS 9 3 00」等之改性聚醯胺醯亞胺。 聚醚楓之具體例可舉例如住友化學（股）公司製之聚 醚颯r PES5003P」等° 聚砸之具體例可舉例如 Solvay Advanced Polymers φ (股）公司製之聚楓「P1700」、「P3500」等。 又，上述硬化劑可舉例如胺系硬化劑、胍（guanidine) 系硬化劑、咪唑系硬化劑、酚系硬化劑、萘酚系硬化劑、 酸酐系硬化劑或此等之環氧加成物或微膠囊化者、氰酸酯 樹脂等。其中，宜爲酚系硬化劑、萘酚系硬化劑、氰酸酯 樹脂。又，在本發明中，硬化劑係可爲一種亦可倂用2種 以上。 酚系硬化劑、萘酚系硬化劑之具體例可舉例如MEH-φ 7700、MEH-7810、MEH-7851 (明和化成（股）製）、 NHN、CBN ' GPH (日本化藥（股）製）、SN170、 SN180 、 SN190 、 SN475 、 SN485 、 SN495 、 SN375 、 SN395 (東都化成（股）製）、LA7052、LA7054、LA3018、 LA 1356C大日本油墨化學工業（股）製）等。 又，氰酸酯樹脂之具體例可舉例如雙酚A二氰酸 酯、聚酚氰酸酯（寡（3-亞甲基-1,5·苯撐基氰酸酯）、 4,4’-亞甲基雙（2,6-二甲基苯基氰酸酯）、4,4’-乙烯基二 苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙（4-氰酸 -14- 200934348 酯）苯基丙烷、1，1-雙（4-氰酸酯苯基甲烷）、雙（4-氰 酸酯-3,5-二甲基苯基）甲烷、1,3-雙（4-氰酸酯苯基-1-(甲基乙烯基））苯、雙（4-氰酸酯苯基）硫醚、雙（4-氰酸酯苯基）醚等之2官能氰酸酯樹脂、酚酚醛清漆、甲 酚酚醛清漆等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹 脂一部分三嗪化的預聚物等。所市售之氰酸酯樹脂係可舉 例如酚酚醛清漆型多官能氰酸酯樹脂（Lonza Japan (股）製「PT 30」、氰酸酯當量124)或雙酚A二氰酸 酯之一部分或全部被三嗪化且成爲三聚體之預聚物 (Lonza Japan (股）製「BA 230」、氰酸酯當量232) 等。 熱硬化性樹脂與硬化劑之調配比率係可依熱硬化性樹 脂、硬化劑之種類等而適當選擇，但例如熱硬化性樹脂爲 環氧樹脂時，環氧樹脂與硬化劑之調配比率係酚系硬化劑 或萘酚系硬化劑時，相對於環氧樹脂之環氧當量1宜此等 硬化劑的酚性羥基當量成爲0.4〜2.0的範圍之比率，更宜 爲0.5〜1.0的範圍之比率。氰酸酯樹脂之情形係，相對於 環氧當量1宜氰酸酯當量成爲0.3〜3.3的範圍之比率，更 宜爲0.5〜2的範圍之比率。 又，該熱硬化性樹脂組成物係可加入硬化劑，進一步 可調配硬化促進劑，如此之硬化促進劑可舉例如咪唑系化 合物、有機磷系化合物等，具體上可舉例如 2-甲基咪 唑、三苯基磷等。使用硬化促進劑時，宜相對於環氧樹脂 而以0.1〜3.0質量％之範圍使用。又，於環氧樹脂硬化劑 -15- 200934348 使用氰酸酯樹脂時，係縮短硬化時間之目的，以 用環氧樹脂組成物與氰酸酯化合物之系，亦可添 作爲硬化觸媒之有機金屬化合物。有機金屬化合 例如銅（II)乙醯基丙銅等之有機銅化合物、鋅（ 基丙銅等之有機鋅化合物、鈷（II)乙醯基 (III)乙醯基丙銅等之有機鈷化合物等。有機 物之添加量係相對於氰酸酯樹脂，就金屬換 0 10〜500ppm，宜爲 25~200ppm 的範圍。 在本發明中，含有無機塡充材之熱硬化性樹 係除了無機塡充材以外，依需要而可調配其他之 他之成分可舉例如有機磷系難燃劑、含有機系氮 物、氮化合物、矽酮系難燃劑、金屬氫氧化物 劑、矽粉末、尼龍粉末、氟粉末等之有機夫 Orben、皂土（bentone)等之增黏劑、砂酮系、氟 子系之清泡劑或流平劑、咪唑系、噻唑系、三唑 φ 系偶合劑等之密著性賦予劑、酞菁/藍、酞菁/綠 雙偶氮黃、碳黑等之著色劑等。 在本發明中係於電路基板之雙面或單面，形 機塡充材3 5質量％以上之絕緣層，於該絕緣層 著塑膠膜，對該塑膠膜上照射二氧化碳氣體雷射 孔。於含有無機塡充材3 5質量％以上之絕緣層 膜之手段係可舉例如於電路基板上層合含有無 35質量％以上之熱硬化性樹脂組成物層，其時， 層合塑膠膜，其後，熱硬化熱硬化性樹脂組成物 自以往倂 加使用來 物係可舉 II )乙醯 与銅、鈷 金屬化合 i： 一般爲 脂組成物 成分。其 的磷化合 等之難燃 隊充劑、 系、高分 系、矽烷 、碘綠、 成含有無 之表面密 ，形成肓 密著塑膠 機塡充材 亦同時地 層而形成 -16- 200934348 絕緣層之方法等，但最適於工業上生產的方法係使用塑膠 薄膜作爲支撐薄膜，調製於該塑膠薄膜上形成含有無機塡 充材3 5質量％以上之熱硬化性樹脂組成物層的黏著薄 膜，使該黏著薄膜層合於電路基板上，使熱硬化性樹脂組 成物層進行熱硬化之方法》 於上述塑膠薄膜上形成含有無機塡充材之熱硬化性樹 脂組成物層的黏著薄膜係熟悉此技藝者公知之方法，例如 φ 於有機溶劑中溶解熱硬化性樹脂組成物同時並調製分散有 無機塡充材之樹脂清漆，使用模頭塗佈器等將此樹脂清漆 塗佈於支撐薄膜上，藉由加熱或熱風吹出等乾燥有機溶劑 而形成樹脂組成物層來製造。 本發明所謂「塑膠薄膜」可舉例如聚對苯二甲酸乙二 酯（以下有時稱爲「PET」）、聚萘二甲酸乙二酯（以 下，有時簡稱爲「PEN」）等之聚酯、聚碳酸酯（以下， 有時稱爲「PC」）、聚甲基丙烯酸甲酯（PMMA )等之丙 φ 烯酸系樹脂、環狀聚烯烴、三乙醯基纖維素（TAC )、聚 醚硫醚（PES )、聚醚酮、聚醯亞胺等。其中，宜爲聚酯 (聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜 等），尤宜爲廉價之聚對苯二甲酸乙二酯薄膜。塑膠薄膜 係亦可使用含有碳黑等之雷射吸收性成分者。又，使用於 黏著薄膜之支撐薄膜之塑膠薄膜係可於熱硬化性樹脂組成 物層之加熱硬化後剝離塑膠薄膜，故宜使用於其熱硬化性 樹脂組成物層之被形成面設有離型層之附離型層的塑膠薄 膜。使用於離型層之離型劑係使熱硬化性樹脂組成物層熱 -17- 200934348 硬化後，可剝離塑膠薄膜即可，並無特別限定，而可舉例 如矽酮系離型劑、醇酸樹脂系離型劑等。又，亦可使用所 市售之附離型層的塑膠薄膜，較佳者係具有以醇酸樹脂系 離型劑作爲主成分之離型層的 PET薄膜，可舉例如 Lintech (股）製SK-1、AL-5、AL-7等。又，亦可於塑膠 薄膜之熱硬化性樹脂組成物層之被形成面實施霧化處理、 電暈處理，具有離型層時，於該處理面形成離型層。 φ 在本發明中，塑膠薄膜之厚度（附離型層之塑膠薄膜 時係亦含有離型層的總厚度）係宜爲20〜50μπι的範圍， 更宜爲2 0 ~ 4 5 μ m之範圍，最宜爲2 3 ~ 4 0 μ m的範圍。塑膠 薄膜之厚度不足20μηι時，係絕緣層之電路上的平坦性有 降低之傾向，若超過50 μιη，成本有變高之傾向，不佳。 又，若塑膠薄膜之厚度爲此範圍內，孔洞周邊的絕緣層表 面之損傷抑制等本發明的效果可被更顯著地發揮。又，附 離型層之塑膠薄膜中的離型層厚度一般爲 〇·〇5~2μηι左 ❿ 右。 在本發明所使用的黏著薄膜係至於電路基板進行層 合，宜具有用以保護含無機塡充材之熱硬化性樹脂組成物 層的保護薄膜。保護薄膜係使含無機塡充材之熱硬化性樹 脂組成物層之表面免受物理性損傷，又，有防止塵埃等之 異物附著等的優點。如此之保護薄膜係可舉例如聚乙烯、 聚丙烯、聚氯化乙烯等之聚烯烴、PET、PEN等的聚酯、 PC、聚醯亞胺等之薄膜。又’保護薄膜，亦與使用於支 撐薄膜之塑膠薄膜同樣，亦可實施霧面處理、電暈處理之 -18- 200934348 外，亦可實施離型處理。保護薄膜之厚度宜爲5〜3 Ομιη之 範圍。 在本發明中，使黏著薄膜層合於電路基板，使黏著薄 膜之熱硬化性樹脂組成物層進行熱硬化以形成絕緣層之作 業係可依據習知之方法來實施。例如，於電路基板之單面 或雙面重疊黏著薄膜，使用SUS鏡板等之金屬板，進行 加熱及加壓，再層合沖壓。此時之壓力係宜以5〜40kgf/ cm2 ( 49xl04~392xl04 N/m2)，溫度係宜以 120~180°C， 沖壓時間宜以20~ 1 00分鐘實施。加熱及加壓係使被加熱 之SUS鏡板等的金屬板從塑膠薄膜側進行沖壓來實施， 但宜不直接沖壓金屬板，於電路基板之電路凹凸充分追隨 黏著片，介由耐熱橡膠等之彈性材而進行沖壓。又，亦可 使用真空積層機來製造。此時，使黏著薄膜在減壓下進行 加熱及加壓，於電路基板積層黏著薄膜。積層係溫度宜以 70〜140 °C ，壓力宜以 1~11 kgf/cm2 ( 9·8 X 1 04~1 07.9 X 1 04 N/m2)的範圍來進行。空氣壓宜以 20mmHg(26.7hPa) 以下之減壓下進行。於積層步驟之後，較佳係藉由以金屬 板進行熱沖壓，俾被積層之黏著薄膜進行平滑化。該平滑 化步驟係以常壓下（大氣壓下），藉使被加熱之SUS鏡 板等的金屬板使黏著片進行加熱及加壓。加熱及加壓條件 係可使用與上述積層步驟相同的條件。上述積層步驟及平 滑化步驟係可藉由所市售之真空積層機來連續地進行。所 市售之真空積層機係可舉例如（股）名機製作所製真空 加壓式積層機、Nichigo-Morton (股）製 Vacuum -19- 200934348BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a multilayer printed circuit board, and more particularly to a method of manufacturing a multilayer printed circuit board using an adhesive film. [Prior Art] Conventionally, in the manufacturing technique of a multilayer printed wiring board, a manufacturing method of a built-up method in which an insulating layer and a conductor layer are alternately overlapped on a core substrate is known. For example, a method is known in which an insulating layer is formed, which is an adhesive film formed on a plastic film to form a thermosetting resin layer, and an adhesive film is laminated on an inner layer circuit substrate to thermally harden the thermosetting resin. . Further, the insulating layer may contain an inorganic ruthenium. In the multilayer printed circuit board, the thickness of the multilayer printed circuit board is required to be reduced in size and the density of the wiring is increased. It is considered that the requirement for thinning of a multilayer printed circuit board is to maintain the mechanical strength at the same time, for example, an inorganic ruthenium containing a large amount of ruthenium oxide or the like as a material for forming an interlayer insulating layer, and to improve the elastic modulus of the interlayer insulating layer _ It is very effective. In addition, in a multilayer printed wiring board in which wiring is increased in density, problems such as occurrence of cracks due to thermal expansion coefficients of the copper wiring and the insulating layer are likely to occur. However, the insulating layer contains a large amount of cerium oxide or the like. The inorganic ruthenium material can effectively prevent the occurrence of cracks caused by the difference in thermal expansion coefficient between the copper wiring and the insulating layer. That is, the material for forming the interlayer insulating layer contains a plurality of inorganic germanium filling materials having a low coefficient of thermal expansion, which can suppress the thermal expansion of the insulating layer to a low degree, and can reduce the thermal expansion coefficient of the copper wiring and the insulating layer. Poor, and inhibit the occurrence of cracks. Patent Documents 1 and 2 describe a method for producing a multilayer printed wiring board using an adhesive film, and Patent Document 1 discloses a method in which a support base film having a release layer and a thermosetting resin composition are used. The adhesive film is laminated on the core substrate, and after being thermally hardened to support the adhesion of the base film, it is directly adhered to the support base film, or is opened by a 0 laser or a drill after peeling. Further, Patent Document 2 discloses a method of laminating an insulating film on one side of a metal foil, further laminating a peelable organic film on the surface of the insulating layer, and performing laser processing from the surface side of the organic film. . [Patent Document 1] JP-A-2001-196743 [Patent Document 2] Japanese Patent Application No. 3899544 [Disclosed] [Disclosed by the Invention] [Problems to be Solved by the Invention] When the insulating layer contains a plurality of inorganic ruthenium materials, The formation of a Via hole creates problems. For example, a method of using a UV-YAG laser is considered for the formation of a blind hole. However, the processing property of the UV-YAG laser-based inorganic cerium material is good, but it is not necessarily satisfied from the viewpoint of cost or processing speed. In addition, carbon dioxide gas lasers are superior to UV-YAG lasers in terms of processing speed or cost. However, when an insulating layer containing many inorganic germanium materials is irradiated with a carbon dioxide gas laser to form a pupil, the workability is lowered, and the hole is reduced. The bottom diameter -5 - 200934348 is smaller than the top diameter, which becomes a significant shape for pushing and pushing, which is the reason for reducing the communication communication of blind holes. It can be seen that the shape of the bottom diameter of the hole is approximately the shape of the top diameter, and it is only required to process with a strong energy. However, when the energy of the carbon dioxide gas is increased, the damage applied to the surface of the insulating layer is increased, and the degree of unevenness around the hole is increased. It becomes larger, and there is a problem that fine wiring becomes unsatisfactory. The problem is that the insulating layer containing 35 mass% or more of the inorganic cerium material is formed, and the high-density printed circuit board φ having a pore diameter (top diameter) of 1 〇〇 μη or less is formed. Further, since the laser processing system described in the above two documents forms a hole having a hole diameter (top diameter) of more than 100 μm, it does not become a serious problem. The present invention has been made in view of the above-mentioned problems, and a method for producing a multilayer printed wiring board is disclosed in which a carbon dioxide gas laser is used for an insulating layer containing 35 mass% or more of an inorganic cerium material. The pupil having a top diameter of ΙΟΟμηη or less can be formed with good productivity, and no large unevenness is formed on the surface of the insulating layer around the hole, and a good hole shape having a small difference between the top diameter and the bottom diameter is formed. . [Means for Solving the Problem] The inventors of the present invention have found that the insulating layer containing 35 mass% or more of the inorganic ceramium material is a plastic film adhered to the surface of the insulating layer in order to solve the above problems. When a carbon dioxide gas laser is irradiated upward, and a sufficient and high-energy carbon dioxide gas laser is irradiated for good workability, damage of the surface of the insulating layer can be suppressed, and a blind hole having a hole bottom diameter of approximately the top diameter can be formed, and the present invention has been completed. That is, the present invention contains the following contents -6 - 200934348. [1] A method of manufacturing a multilayer printed wiring board, comprising: forming an insulating layer formed on a double-sided or single-sided surface of a circuit board and containing an inorganic cerium material of 35 mass% or more from the insulating layer The surface of the plastic film is irradiated with a carbon dioxide gas laser to form a pupil having a top diameter of ΙΟΟμηι or less. [2] The method for producing a multilayer printed wiring board according to the above [1], wherein the insulating layer containing 55% by mass or more of the inorganic cerium material is composed of a thermosetting resin containing at least 35 mass% of the inorganic cerium material. The layer is thermally hardened. [3] The method for producing a multilayer printed wiring board according to the above [2], wherein an adhesive film containing a thermosetting resin composition layer of 35 mass% or more of an inorganic cerium material is formed on the plastic film, and the thermosetting property is obtained. The resin composition layer is laminated on the circuit board so as to be in contact with the double-sided or single-sided surface of the circuit board, and the thermosetting resin composition layer is thermally cured to form an insulating layer containing 35 mass% or more of the inorganic 塡Φ filling material. Thereafter, a carbon dioxide gas laser is irradiated from the plastic film. [4] The method for producing a multilayer printed wiring board according to any one of the above [1], wherein the insulating layer containing the inorganic cerium material in an amount of 35 mass% or more is contained in an inorganic cerium material of 35 to 70% by mass. Insulation layer. [5] The method of producing a multilayer printed wiring board according to any one of the above [1] to [4] wherein the inorganic cerium material is cerium oxide. [6] The method of producing a multilayer printed wiring board according to any one of the above [1] to [5] wherein the plastic film is a polyethylene terephthalate film. The method for manufacturing a multilayer printed electric power according to any one of the above items, wherein the thickness of the plastic film is 20 to 50 μm and the insulating granule is ΐ5 to 1 〇〇μιη. [8] The multilayer printed electro-tap method according to any one of the above items, wherein the energy of the carbon dioxide gas laser is lmJ" [9] as in the above [1] to [7] A multi-layer printed electroplating method in which the energy of a carbon dioxide gas laser is 1 to 5 mJ. [10] The method of manufacturing a multilayer printed circuit according to any one of the above items, wherein the number of emission of the carbon dioxide gas laser is 1 or 2 [1 1] as in the above Π]~Π〇] In the multilayer printing and manufacturing method according to any one of the aspects, the aperture ratio (bottom diameter/top diameter) of the hole is upper. [12] The multilayer printing manufacturing method according to any one of the above [1] to [1], further comprising the step of peeling the plastic thin from the insulating layer. [13] The manufacturing of the multilayer printed circuit board according to the above [12], further comprising the steps of: roughening the insulating layer to be thicker than the surface of the roughened insulating layer by electroplating to form a conductor layer, and conducting the conductor The circuit forming step of the layer forming circuit. [Effects of the Invention] According to the method for producing a multilayer printed wiring board of the present invention, the insulating layer of 35 mass% or more of the inorganic ceramium material is not made of a plate for making a sufficient and high-energy carbon dioxide gas for processing. The thickness of the slab of the slab is made of 70% of the slab of the slab, the step of the slab, the steps; the step; the damage of the surface of the insulating layer containing the good -8-200934348 'A blind hole with a top diameter of 1 〇〇Mm or less can be formed, and a high-density multilayer wiring with high reliability can be formed. Further, the blind hole having the top diameter of 100 μπ or less is formed such that the aperture ratio (bottom diameter/top diameter) of the hole is a good hole shape having a small difference between the top diameter and the bottom diameter of the hole, so that the communication communication property can be excellent. hole. [Embodiment] φ [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in accordance with an appropriate embodiment. A method of manufacturing a multilayer printed wiring board according to the present invention, comprising the steps of: forming an insulating layer formed on a double-sided or single-sided surface of a circuit board and containing an inorganic filler of 35% by mass or more from the surface of the insulating layer; The plastic film is irradiated with a carbon dioxide gas laser to form a pupil having a top diameter of ΙΟΟμηη or less. In the present invention, the "insulating edge layer containing 35 mass% or more of the inorganic ceramium material" is used in the resin composition used as the insulating layer of the multilayer printed wiring board, and the inorganic ceramium-containing material is contained in an amount of 35 mass% or more. An insulating layer formed of the resin composition. In particular, it is preferably a cured product of a thermosetting resin composition containing 35 mass% or more of an inorganic cerium filler. The insulating layer containing not less than 5% by mass of the inorganic cerium material such as cerium oxide exhibits high modulus of elasticity and low thermal expansion property, and for example, an elastic modulus of 4 GPa or more and/or a coefficient of thermal expansion (room temperature to 150 ° C) can be achieved. Insulation layer below 50ppm/°C. Therefore, with the use of such an insulating layer, it is possible to manufacture a multilayer printed circuit board which is excellent in mechanical strength and which is caused by a difference in thermal expansion coefficient. In the present invention, the "content of the inorganic ruthenium material" is a mass fraction of the inorganic ruthenium material when the non-volatile component of the entire resin composition constituting the insulating layer is 100% by mass. For example, when the insulating layer is formed of a cured product of a thermosetting resin composition, the mass fraction which is obtained by the inorganic cerium filler when the nonvolatile content of the entire resin composition before curing is 100% by mass is used. In addition, in the "extreme φ edge layer containing 35 mass% or more of the inorganic cerium material", if the content of the inorganic cerium material is too large, the density of the conductor layer formed on the insulating layer is changed in the subsequent step. Since the tendency is difficult, the content of the inorganic cerium filler is preferably 70% by mass or less. That is, the content of the inorganic cerium filler is preferably 35 to 70% by mass, more preferably 35 to 60% by mass. In the present invention, the thickness of the "insulating layer containing 35 mass% or more of the inorganic cerium material" is preferably 15 to 1 μm, more preferably 20 to 70 μm. If the thickness of the insulating layer is less than 15 μm, it tends to be difficult to laminate flatly on the circuit board, and if it exceeds ΙΟΟμη, it is not suitable for thinning of a multilayer printed wiring board. In the present invention, the inorganic cerium filling material may, for example, be cerium oxide, aluminum oxide, mica, mica powder, cerium salt, barium sulfate, magnesium hydroxide or titanium oxide. Among them, from the viewpoint of high modulus of elasticity, low coefficient of thermal expansion, and low dielectric tangent, it is preferable to form cerium oxide such as amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic cerium oxide. Further, the cerium oxide is preferably spherical. It is preferable to use a surface treatment agent such as a decane coupling agent for the surface treatment of the enamel-free filling material. As the decane coupling agent, those known to use an amino decane, an allyl decane, a gymnasium, a hospital, a phenyl sand, and an epoxy base can be used. -10-200934348 In addition, from the viewpoint of insulation reliability of the insulating layer, the inorganic ceramium filling material should have an average particle diameter of 3 μm or less, and more preferably have an average particle diameter of 1.5 μm or less. Further, the lower limit of the average particle diameter is not particularly limited, but is preferably 〇.1 μ® or more from the viewpoints of handleability, cost, and the like. The above average particle size of the inorganic cerium can be measured by the laser diffraction or scattering method of the Mi e scattering theory. Specifically, the laser diffraction type particle size distribution measuring apparatus is used to determine the particle size distribution of the inorganic cerium material by volume basis, which can be measured by using the intermediate diameter as the average particle diameter. It is preferable to use a supersonic wave to disperse the inorganic cerium filling material in water. For the laser diffraction type particle size distribution measuring device, LA-5 00, etc., manufactured by the company, Horiba, Ltd., can be used. In the present invention, when the cured product containing the thermosetting resin composition of 35 mass% or more of the inorganic cerium material is composed of the "insulating layer containing 35 mass% or more of the inorganic cerium material", the hardening of the substrate component is performed. The resin composition is not particularly limited as long as it is suitable for the insulating layer of the multilayer printed circuit board, and can be used, for example, for an epoxy resin, a cyanate ester resin, a phenol resin, or a bis-bismimide-triazine. The thermosetting resin such as a resin, a polyimide resin, an acrylic resin, or a vinyl benzyl resin is blended with at least a composition of a curing agent, and preferably contains an epoxy resin as a composition of a thermosetting resin, for example, It is particularly preferable to contain a composition of an epoxy resin, a thermoplastic resin, and a hardener. The epoxy resin may, for example, be a bisphenol A epoxy resin, a biphenyl epoxy resin, a naphthol epoxy resin, a naphthalene epoxy resin, a bisphenol F epoxy resin, or a phosphorus-containing epoxy resin. Resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak type epoxy tree-11 - 200934348 Grease, cresol novolak type epoxy resin, bisphenol A A novolak type epoxy resin, an epoxy resin having a butadiene structure, a diglycidyl etherate of bisphenol, a diglycidyl ether of naphthalenediol, a glycidyl etherate of a phenol, and an alcohol A bisglycidyl etherate, an alkyl substituent of such an epoxy resin, a halide, a hydrogen additive, and the like. Any of these epoxy resins may be used alone or in combination of two or more. Among the epoxy resins, from the viewpoints of heat resistance, insulation reliability, and adhesion to a gold U-based film, it is preferably a bisphenol A type epoxy resin, a naphthol type epoxy resin, or a naphthalene type epoxy. Resin, biphenyl type epoxy resin, epoxy resin having a butadiene structure. Specifically, for example, liquid bisphenol A type epoxy resin ("Epicote 8 2 8EL" manufactured by Japan Epoxy Resin Co., Ltd.) or naphthalene type bifunctional epoxy resin (HP manufactured by Dainippon Ink Chemical Industry Co., Ltd.) 4032", "HP 4032D"), naphthalene type 4-functional epoxy resin (HP 4700, manufactured by Dainippon Ink Chemicals Co., Ltd., and naphthol epoxy resin (ESN-475V, manufactured by Tohto Kasei Co., Ltd.) Epoxy resin having a butadiene structure ("PB-3 600" manufactured by Daicel Chemical Industry Co., Ltd.) and epoxy resin having a biphenyl structure ("NC 3000 H" manufactured by Nippon Kayaku Co., Ltd." "NC 3000L", "YX 4000" manufactured by Japan Epoxy Resin Co., Ltd.), etc. Further, the thermoplastic resin is blended for the purpose of imparting appropriate flexibility to the cured composition, and examples thereof include phenoxy Resin, polyvinyl acetal resin, polyimine, polyamidimide, polyether maple, poly-rolling, etc. These may be used singly or in combination of two or more. When the non-volatile content of the thermosetting resin composition is taken as 100%-12-200934348% It is preferably formulated in a ratio of from 5 to 60% by mass, more preferably from 3 to 50% by mass. Specific examples of the phenoxy resin include, for example, bisphenol A having 1,256, 42 50, etc., manufactured by Japan Epoxy Resin Co., Ltd. Skeleton, bismuth S skeleton with Japan Epoxy Resin YX 8100, etc., bisphenol acetonitrile skeleton with Japan Epoxy Resin YX 6954, etc., FX 28 manufactured by Tohto Kasei Co., Ltd. 0, FX 293, etc. 0 double skeleton skeleton, Japan Epoxy Resin (share) YL 75 53 and other double-armor skeleton, Japan Epoxy Resin (share) YL 6794 and other masks, It has a trimethylcyclohexane skeleton such as YL 7213 or YL 7290 manufactured by Japan Epoxy Resin Co., Ltd., etc. The polyethylene acetal resin is preferably a polyvinyl butyral resin, and a specific example of a polyvinyl acetal resin. For example, the electrochemical industry (stock) system, electro-chemical butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Industry Co., Ltd. Esulex BH series, BX series, KS series, BL system φ Column, B Μ series, etc. Specific examples of polyimine may be, for example, a new Japanese physicochemical (share) system Imine "Rikacoat SN 20" and "Rikacoat ΡΝ 20". Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (Specially Opened 2006-37083) The modified polyimine, such as those described in the above-mentioned publications, which are described in the Japanese Patent Publication No. 2002-12667, and the like. Specific examples of the polyamidoximine may be, for example, Toyobo Co., Ltd. -13-200934348 Polyamidamine "Vylomax HR 11NN" and "Vylomax HR16NN". Further, for example, modified polyamidoquinone imines such as polyacrylamide-based polyamines "KS9100" and "KS 9 3 00", which are manufactured by Hitachi Chemical Co., Ltd., are available. Specific examples of the polyether maple include, for example, a polyether 飒r PES5003P manufactured by Sumitomo Chemical Co., Ltd., and the like. For example, a polyfluorene "P1700" manufactured by Solvay Advanced Polymers φ Co., Ltd., " P3500" and so on. Further, examples of the curing agent include an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, a naphthol curing agent, an acid anhydride curing agent, or an epoxy addition product thereof. Or microencapsulated, cyanate resin, and the like. Among them, a phenolic curing agent, a naphthol curing agent, and a cyanate resin are preferable. Further, in the present invention, the curing agent may be used alone or in combination of two or more. Specific examples of the phenolic curing agent and the naphthol-based curing agent include, for example, MEH-φ 7700, MEH-7810, MEH-7851 (made by Megumi Kasei Co., Ltd.), NHN, and CBN 'GPH (Nippon Chemical Co., Ltd.). ), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (made by Tohto Kasei Co., Ltd.), LA7052, LA7054, LA3018, LA 1356C, Dainippon Ink Chemical Industry Co., Ltd., etc. Further, specific examples of the cyanate resin include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'. -methylenebis(2,6-dimethylphenyl cyanate), 4,4'-vinyldiphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-double (4-cyanate-14- 200934348 ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane , 1,3-bis(4-cyanate phenyl-1-(methylvinyl))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether A polyfunctional cyanate resin derived from a bifunctional cyanate resin, a phenol novolac, a cresol novolak or the like, a pre-polymerized triazine group of these cyanate resins, etc. Commercially available cyanic acid. The ester resin may be, for example, a phenol novolac type polyfunctional cyanate resin ("30" manufactured by Lonza Japan Co., Ltd., cyanate equivalent 124) or a part or all of bisphenol A dicyanate may be triazineized. Further, it is a trimer prepolymer ("BA 230" manufactured by Lonza Japan Co., Ltd., cyanate equivalent 232), etc. The blending ratio of the resin and the curing agent can be appropriately selected depending on the type of the thermosetting resin or the curing agent, etc. However, when the thermosetting resin is an epoxy resin, the blending ratio of the epoxy resin to the hardener is a phenolic hardener. In the case of a naphthol-based curing agent, the epoxy equivalent of the epoxy resin is preferably a ratio of a phenolic hydroxyl equivalent of the curing agent of 0.4 to 2.0, more preferably a ratio of 0.5 to 1.0. In the case of the ester resin, the ratio of the range of the epoxy equivalent 1 isocyanate equivalent to 0.3 to 3.3 is more preferably in the range of 0.5 to 2. Further, the thermosetting resin composition may be added to the hardening. Further, a hardening accelerator may be further added, and examples of such a curing accelerator include an imidazole compound and an organic phosphorus compound, and specific examples thereof include 2-methylimidazole and triphenylphosphorus. When a curing accelerator is used, It is preferably used in the range of 0.1 to 3.0% by mass relative to the epoxy resin. Also, when the cyanate resin is used in the epoxy resin hardener -15-200934348, the curing time is shortened to use the epoxy resin group. The compound and the cyanate ester compound may also be added as an organometallic compound of a hardening catalyst. The organometallic compound may be an organic copper compound such as copper (II) ethenylpropyl copper or the like, or an organic zinc such as zinc or copper. a compound, an organic cobalt compound such as cobalt (II) ethenyl (III) etidinylpropyl copper, etc. The amount of the organic substance added is 0 to 500 ppm, preferably 25 to 200 ppm, with respect to the cyanate resin. In the present invention, the thermosetting tree containing the inorganic cerium material may be other than the inorganic cerium material, and other components may be added as needed. For example, an organic phosphorus-based flame retardant or a mechanical nitrogen-containing material may be used. , a nitrogen compound, an anthrone-based flame retardant, a metal hydroxide agent, a strontium powder, a nylon powder, a fluorine powder, etc., such as a thickener, a sulphonone, or a fluorosis. A tackifier such as a foaming agent or a leveling agent, an imidazole-based, a thiazole-based or a triazole φ-based coupling agent, a coloring agent such as phthalocyanine/blue, phthalocyanine/green disazo yellow, or carbon black. In the present invention, on the double-sided or single-sided side of the circuit board, the mold is filled with an insulating layer of 35 mass% or more, and a plastic film is applied to the insulating layer, and the plastic film is irradiated with a carbon dioxide gas laser hole. The means for containing an insulating layer film of 35 mass% or more of the inorganic ceramium material is, for example, a layer containing a thermosetting resin composition of not more than 35 mass% or more laminated on a circuit board, and a laminated plastic film. Then, the thermosetting thermosetting resin composition is used in the past, and II) is combined with copper and cobalt metal. i: It is generally a fat composition component. Its phosphating and other non-combustible team fillings, systems, high-scoring systems, decane, iodine green, and the surface of the densely formed, densely formed plastic machine 塡 filling material also formed at the same time to form the insulation layer -16-200934348 The method, which is most suitable for industrial production, uses a plastic film as a support film, and is formed on the plastic film to form an adhesive film containing a thermosetting resin composition layer of 35 mass% or more of the inorganic cerium material. The adhesive film is laminated on a circuit board to thermally cure the thermosetting resin composition layer. The adhesive film forming the thermosetting resin composition layer containing the inorganic chelating material on the plastic film is familiar with the art. A method known in the art, for example, φ dissolves a thermosetting resin composition in an organic solvent and prepares a resin varnish in which an inorganic cerium material is dispersed, and applies the resin varnish to the support film using a die coater or the like. It is produced by drying a organic solvent such as by heating or hot air to form a resin composition layer. The "plastic film" of the present invention may, for example, be a polyethylene terephthalate (hereinafter sometimes referred to as "PET") or polyethylene naphthalate (hereinafter sometimes referred to as "PEN"). An ester, a polycarbonate (hereinafter sometimes referred to as "PC"), a polyacrylic acid methyl ester (PMMA) or the like, a propylene olefinic resin, a cyclic polyolefin, a triethyl fluorenyl cellulose (TAC), Polyether sulfide (PES), polyether ketone, polyimine, and the like. Among them, polyester (polyethylene terephthalate film, polyethylene naphthalate film, etc.) is preferable, and an inexpensive polyethylene terephthalate film is particularly preferable. For the plastic film, a laser absorbing component containing carbon black or the like can also be used. Further, the plastic film used for the support film of the adhesive film can be peeled off from the plastic film after heat curing of the thermosetting resin composition layer, and therefore it is preferable to use a release film on the formed surface of the thermosetting resin composition layer. A plastic film with a release layer attached to the layer. The release agent to be used in the release layer is not particularly limited as long as the thermosetting resin composition layer is cured, and the plastic film can be peeled off, and may be, for example, an anthrone-based release agent or an alcohol. An acid resin is a release agent or the like. Further, a commercially available release film of a release layer may be used, and a PET film having a release layer containing an alkyd resin release agent as a main component is preferable, and for example, SK manufactured by Lintech Co., Ltd. may be used. -1, AL-5, AL-7, etc. Further, the surface to be formed of the thermosetting resin composition layer of the plastic film may be subjected to atomization treatment or corona treatment, and when the release layer is provided, a release layer may be formed on the treated surface. φ In the present invention, the thickness of the plastic film (the total thickness of the release layer of the plastic film attached to the release layer) is preferably in the range of 20 to 50 μm, more preferably in the range of 20 to 45 μm. It is most preferably in the range of 2 3 to 40 μm. When the thickness of the plastic film is less than 20 μm, the flatness of the circuit of the insulating layer tends to be lowered, and if it exceeds 50 μm, the cost tends to be high, which is not preferable. Further, if the thickness of the plastic film is within this range, the effects of the present invention such as the damage of the surface of the insulating layer around the hole can be more prominently exhibited. Further, the thickness of the release layer in the plastic film of the release layer is generally 〇·〇5~2μηι left ❿ right. In the adhesive film used in the present invention, it is preferable to have a protective film for protecting the thermosetting resin composition layer containing the inorganic cerium material for lamination on the circuit board. The protective film is advantageous in that the surface of the thermosetting resin composition layer containing the inorganic cerium filler is protected from physical damage, and the foreign matter such as dust is prevented from adhering. Examples of such a protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, and films such as PC and polyimide. Further, the protective film can be subjected to a matte treatment as well as a plastic film for supporting a film, and can be subjected to matte treatment or corona treatment -18-200934348. The thickness of the protective film is preferably in the range of 5 to 3 Ο μιη. In the present invention, the work for laminating the adhesive film to the circuit board and thermally hardening the thermosetting resin composition layer of the adhesive film to form the insulating layer can be carried out according to a conventional method. For example, a film is laminated on one side or both sides of a circuit board, and a metal plate such as a SUS mirror plate is used for heating and pressurization, and then laminated. The pressure at this time should be 5~40kgf/cm2 (49xl04~392xl04 N/m2), the temperature should be 120~180°C, and the pressing time should be 20~100 minutes. Heating and pressurization are performed by pressing a metal plate such as a heated SUS mirror plate from the side of the plastic film. However, it is preferable not to directly press the metal plate, and the unevenness of the circuit on the circuit board sufficiently follows the adhesive sheet, and the elasticity is imparted by heat-resistant rubber or the like. Pressing the material. Alternatively, it can be manufactured using a vacuum laminator. At this time, the adhesive film was heated and pressurized under reduced pressure to deposit a film on the circuit board. The temperature of the laminate system should be 70~140 °C, and the pressure should be in the range of 1~11 kgf/cm2 (9·8 X 1 04~1 07.9 X 1 04 N/m2). The air pressure is preferably carried out under a reduced pressure of 20 mmHg (26.7 hPa) or less. After the lamination step, it is preferred that the laminated film is smoothed by hot stamping with a metal plate. In the smoothing step, the adhesive sheet is heated and pressurized by a metal plate such as a heated SUS mirror under normal pressure (at atmospheric pressure). Heating and pressurizing conditions The same conditions as those of the above laminating step can be used. The above lamination step and smoothing step can be carried out continuously by a commercially available vacuum laminator. The commercially available vacuum laminator is, for example, a vacuum pressurizing laminator manufactured by Nippon Machine Co., Ltd., and Nichigo-Morton Co., Ltd. Vacuum -19- 200934348
Applicator 等 ° 積層步驟之後，或平滑化步驟之後，進行熱硬化步 驟。在熱硬化步驟中係使樹脂組成物熱硬化，形成絕緣 層。熱硬化條件係依熱硬化性樹脂組成物之種類等而異， 但一般硬化溫度爲170〜19(TC，硬化時間爲15〜60分鐘。 在本發明中係對密著於絕緣層表面之塑膠薄膜上照射 二氧化碳氣體雷射，形成頂徑ΙΟΟμιη以下之盲孔。爲對 應於多層印刷電路板之薄型化、配線的高密度化，盲孔之 頂徑爲1 〇 〇 μ m以下，宜爲9 0 μ m以下，更宜爲8 0 μ m以 下。 所照射之二氧化碳氣體雷射係一般可使用9.3〜10.6 μπι的波長之雷射。又，發射數係依爲形成之盲孔的深 度、孔徑而異，但一般於1〜5發射數之間選擇。從加速肓 孔之加工速度，提昇多層印刷電路板之生產性的觀點，發 射數宜爲少者，發射數宜爲1或2。爲減少發射數，宜使 φ 二氧化碳氣體雷射之能量高高地設定於一定値以上，尤 其，在絕緣層中含有無機塡充材35質量％以上之本發明 中有加工性降低之傾向，故二氧化碳氣體雷射之能量宜設 定於lmJ以上，更宜設定於2mJ以上。 若二氧化碳氣體雷射之能量降低，因加工性降低，孔 底之徑小於頂徑，成爲推拔明顯的形狀，成爲降低導通信 賴性之原因。尤其在頂徑小的盲孔中係若孔底徑太小於頂 徑，導通信賴性之降低變成明顯的問題，故宜減少頂徑與 孔底徑之差。亦即，在頂徑爲100 μηι以下之盲孔中宜其 -20- 200934348 開口徑（底徑/頂徑）爲70%以上。 另外，若二氧化碳氣體雷射之能量太高，肓 導體層易受到損傷。因此，亦依發射數或爲形成 深度等而定，但二氧化碳氣體雷射之能量的上限 以下，更宜爲 4_5mJ以下，最宜爲 4mJ以下 3 . 5 m J以下。 又，以複數之發射數進行加工時，連續之發 @ 佳模式係於孔內籠罩加工熱，故於無機塡充材與 樹脂組成物的加工性易產生差，孔洞之推拔有 向，故宜爲具有時間間隔之複數發射數即循環模 二氧化碳氣體雷射之脈沖寬係無特別限定 28μ8之中範圍至4μ8左右的短脈沖廣範圍選擇 高能量的情形，短脈沖者形成孔洞加工形狀優者 又，所謂二氧化碳氣體雷射之能量係在每一 絕緣層表面之雷射能量値，可依二氧化碳氣體雷 φ 之振盪機的輸出、準直透鏡（能量調整用透鏡） 而進行調整。光罩徑係實際上可依加工之盲孔 擇。能量値係於進行雷射加工之座台上放置測定 感測器），而實測被加工之電路基板的絕緣層表 之能量來測定。又，所市售之二氧化碳氣體雷射 備測定裝置，可容易地測定照射對象表面的能量 之二氧化碳氣體雷射裝置可舉例如三菱電機I 605GTWII ' 日立 Via mechanics (股）LC-G 系 焊接System (股）基板開孔雷射加工機等。 孔之基底 之肓孔的 宜爲5mJ ，尤宜爲 射數的最 熱硬化性 變大之傾 式。 ，而可從 ，但一般 〇 發射數的 射裝置中 、光罩徑 的徑而選 器（功率 面高度中 裝置係裝 。所市售 :股）ML 列、松下 200934348 於本發明製造之多層印刷電路板中係依需要亦可於形 成絕緣層之電路基板上形成貫通孔（through hole )。貫 通孔形成係可使用以往公知的方法。在多層印刷電路板中 係貫通孔的形成一般在芯基板中進行，被積層之絕緣層一 般係藉肓孔進行導通。又，貫通孔形成一般係可使用機械 鑽孔機。以雷射於芯基板形成貫通孔之方法亦已爲人知， 但，其情形，銅箔會反射雷射，故一般可使用化學性加工 ^ 銅箔表面之後，照射雷射之方法。又，含有可提高雷射能 量吸收之成分的開孔用補助片設置於銅箔表面以照射雷射 之方法亦已爲人知。以二氧化碳氣體雷射形成貫通孔時， 必須爲更大的能量，亦依銅箔或芯基板之厚度而定，但可 採用例如10〜60m J之能量。在薄型之電路基板中例如本 發明之盲孔的形成，從密著於絕緣層表面之塑膠薄膜上照 射二氧化碳氣體雷射，而形成貫通孔等，從被積層之絕緣 層上藉雷射形成貫通孔。 Q 本發明之多層印刷電路板的製造方法中係肓孔形成後 從絕緣層剝離塑膠薄膜。塑膠薄膜之剝離係可以手動剝 離，亦可藉自動剝離裝置機械性剝離。又，形成貫通孔時 係於盲孔與貫通孔之形成後剝離塑膠薄膜。 在本發明之多層印刷電路板的製造方法中係亦可進一 步包括：粗化處理絕緣層表面之粗化步驟、於被粗化之絕 緣層表面藉電鍍形成導體層之電鍍步驟、及於導體層形成 電路之電路形成步驟。此等之步驟係可依據於多層印刷電 路板之製造所使用的以往公知之各種方法來進行。 -22- 200934348After the applicator is equal to the lamination step, or after the smoothing step, the thermal hardening step is performed. In the thermosetting step, the resin composition is thermally hardened to form an insulating layer. The thermosetting conditions vary depending on the type of the thermosetting resin composition, etc., but generally the curing temperature is 170 to 19 (TC, and the curing time is 15 to 60 minutes. In the present invention, the plastic is adhered to the surface of the insulating layer. The carbon dioxide gas is irradiated on the film to form a blind hole having a top diameter of ιμηη or less. In order to reduce the thickness of the multilayer printed circuit board and increase the density of the wiring, the top diameter of the blind hole is 1 〇〇μm or less, preferably 9 0 μ m or less, more preferably 80 μm or less. The carbon dioxide gas laser system to be irradiated generally uses a laser of a wavelength of 9.3 to 10.6 μπι. Further, the number of emission systems depends on the depth and aperture of the blind hole formed. However, it is generally selected between the number of shots of 1 to 5. From the viewpoint of speeding up the processing speed of the pupil and improving the productivity of the multilayer printed circuit board, the number of shots should be less, and the number of shots should be 1 or 2. In order to reduce the number of shots, it is preferable to set the energy of the φ carbon dioxide gas laser to a certain level or more. In particular, the insulating layer contains 35 mass% or more of the inorganic cerium material, and the workability is lowered in the present invention. Oxidation The energy of the gas laser should be set to lmJ or higher, and more preferably set to 2 mJ or more. If the energy of the carbon dioxide gas laser is lowered, the processability is lowered, and the diameter of the bottom of the hole is smaller than the top diameter, which becomes a highly obvious shape and reduces the conduction. The reason for the reliability. Especially in the blind hole with small top diameter, if the bottom diameter of the hole is too smaller than the top diameter, the decrease of the communication communication becomes a significant problem, so the difference between the top diameter and the bottom diameter should be reduced. In the blind hole with a top diameter of 100 μηι or less, the opening diameter (bottom diameter/top diameter) of the -20-200934348 is 70% or more. In addition, if the energy of the carbon dioxide gas laser is too high, the conductive layer of the crucible is easily damaged. It is also determined by the number of shots or the depth of formation, but the upper limit of the energy of the carbon dioxide gas laser is more preferably 4_5mJ or less, and most preferably 4mJ or less and 3.5m J or less. Also, the number of shots is plural. During processing, the continuous hair @佳 mode is processed in the hole to cover the heat of processing, so the processing property of the inorganic ruthenium filler and the resin composition is likely to be poor, and the hole is pushed and pulled, so it is suitable to have a complex emission with time interval. That is, the pulse width of the cyclic mode carbon dioxide gas laser is not particularly limited to a range of 28 μ8 to a short pulse of about 4 μ8, and a wide range of high energy is selected. The short pulse shape forms a hole shape and the energy of the so-called carbon dioxide gas laser The laser energy 系 on the surface of each insulating layer can be adjusted according to the output of the oscillating machine of the carbon dioxide gas ray φ and the collimating lens (the lens for energy adjustment). The reticle diameter can actually be processed according to the blind hole. The energy is measured by placing the measurement sensor on the stage where the laser processing is performed, and measuring the energy of the insulating layer of the circuit substrate to be processed. Further, a carbon dioxide gas laser measuring device which is commercially available, and a carbon dioxide gas laser device which can easily measure the energy of the surface to be irradiated can be, for example, Mitsubishi Electric I 605GTWII 'Hitachi Via mechanics (s) LC-G welding system ( Stock) substrate open hole laser processing machine, etc. The pupil of the base of the hole should preferably be 5 mJ, and it is particularly suitable for the most hardening of the number of shots. However, it can be used in the multi-layer printing manufactured by the present invention, but in the ejector of the number of shots, the diameter of the mask diameter, and the ML column of the power unit height (commercially available: stock) ML column, Panasonic 200934348 A through hole may be formed in the circuit board on the circuit substrate on which the insulating layer is formed, as needed. A conventionally known method can be used for the through hole forming system. The formation of the through holes in the multilayer printed circuit board is generally performed in the core substrate, and the laminated insulating layer is generally turned on by the via holes. Further, a through hole is generally formed by using a mechanical drill. A method of forming a through hole by laser irradiation on a core substrate is also known. However, in the case where the copper foil reflects the laser, it is generally possible to use a method of irradiating a laser after chemically processing the surface of the copper foil. Further, a method of providing a hole-providing sheet containing a component for improving the absorption of laser energy on the surface of a copper foil to irradiate a laser is also known. When a through hole is formed by a carbon dioxide gas laser, it is necessary to have a larger energy depending on the thickness of the copper foil or the core substrate, but for example, an energy of 10 to 60 m J can be used. In the thin circuit board, for example, the blind hole of the present invention is formed by irradiating a carbon dioxide gas laser from a plastic film adhered to the surface of the insulating layer to form a through hole or the like, and forming a through-hole from the insulating layer of the laminated layer. hole. Q In the method of manufacturing a multilayer printed wiring board of the present invention, the plastic film is peeled off from the insulating layer after the formation of the pupil. The peeling of the plastic film can be manually peeled off or mechanically peeled off by an automatic peeling device. Further, when the through hole is formed, the plastic film is peeled off after the formation of the blind hole and the through hole. In the method of manufacturing a multilayer printed circuit board of the present invention, the method further includes: a roughening step of roughening the surface of the insulating layer, a plating step of forming a conductor layer by plating on the surface of the roughened insulating layer, and a conductor layer A circuit forming step of forming a circuit. These steps can be carried out in accordance with various conventionally known methods used in the manufacture of multilayer printed circuit boards. -22- 200934348
粗化處理絕緣層表面之粗化步驟係例如以鹼性過錳酸 水溶液等之氧化劑處理絕緣層表面來進行。又，該粗化步 驟係有時兼具除去肓孔、貫通孔等之孔內殘渣（Smear ) 的去膠渣步驟。又，以鹼性過錳酸水溶液進行粗化處理 時，宜在粗化處理之前以膨潤液進行膨潤處理。膨潤液係 可舉例如 Atotech Japan股份公司製之 Swelling Dip Securiganth P、Swelling Dip Securiganth SBU 等。膨潤處 理係一般於加熱至 60〜80 °C左右的膨潤液賦予絕緣層 5〜1 0分鐘來進行。鹼性過錳酸水溶液可舉例如於氫氧化 鈉之水溶液中溶解過錳酸鉀或過錳酸鈉之溶液。以鹼性過 錳酸水溶液進行粗化處理係一般於60〜80°C的鹼性過錳酸 水溶液中賦予絕緣層1〇〜3 0分鐘左右。鹼性過錳酸水溶液 係市售品可舉例如Atotech Japan股份公司製之濃縮液小 型 CP、劑量溶液（dosing solution)溶脹劑（Securiganth)P 等。 電鍍步驟係例如藉粗化處理形成凹凸之絕緣層表面組 合無電解電鍍與電解電鍍之方法形成導體層，或只以無電 解電鍍形成導體層。導體層係可以銅、鋁、鎳、銀、金等 之金屬或此等金屬的合金等形成，但尤宜爲銅。鍍銅層係 組合無電解電鍍與電解電鍍之方法，或形成與導體層相反 圖型之電鍍光阻，只以無電解電鍍形成導體層。無電解電 鍍層之厚度宜爲0.1〜3μιη，更宜爲0.3〜2μιη。另外，電解 電鍍層之厚度係與無電解電鍍層之厚度的合計厚度宜爲 3~35μιη，更宜爲5~20μιη之厚度。又，導體層形成後，藉 -23- 200934348 由以15 0-2 00 °C退火處理2 0〜9 0分鐘，俾可進一步提昇導 體層之剝離強度，安定化。 電路形成步驟係可使用例如減去法、半加成法等。微 細線形成宜爲半加成法，於無電解電鍍層上形成圖型光 阻，形成所希望之厚度的電解電鍍層（圖型電鍍層）後， 剝離圖型光阻，以沖洗蝕刻除去無電解電鍍層，俾可形成 電路。 φ 使用於本發明之多層印刷電路板的製造之電路基板係 主要謂玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基 板、ΒΤ樹脂基板、熱硬化型聚苯醚基板等之基板的單面 或雙面形成被圖型加工之導體層（電路）者。又，製造多 層印刷電路板時，進一步爲形成絕緣層及/或導體層之中 間製造物的內層電路基板亦包含於本發明之電路基板。 又，導體層（電路）表面係藉黑化處理等預先實施粗化處 理者，從絕緣層於電路基板的密著性之觀點，佳。 ❹ 以下，顯示實施例及比較例而更具體地說明本發明。 又，在以下之記載中「份」意指「質量份」。 (熱硬化性樹脂組成物清漆之製造例1 ) 使液狀雙酚Α型環氧樹脂（環氧基當量180、Japan Epoxy Resin (股）製「Epicote 828EL」）28 份、萘型 4 官能環氧樹脂（環氧基當量163、大日、本油墨化學工業 (股）製「HP4700」）28份於甲乙酮15份與環己酮15 份之混合溶劑中一邊攪拌一邊加熱溶解。再混合萘酚系硬 -24- 200934348 化劑（東都化成（股）製「SN-485」、酚性羥基當量 215 )的固形分50%之甲乙酮溶液110份、硬化觸媒（四 國化成工業（股）製、「2E4MZ」）0.1份、球形二氧化 砂（平均粒徑 0.5μιη、「SO-C2」Adomatech公司製）70 份、聚乙烯丁縮醛樹脂溶液（積水化學（股）製「KS-lj 的固形分15%之乙醇與甲苯的1: 1溶液）30份，以高速 旋轉混合機均一地分散，製作熱硬化性樹脂組成物清漆。 該清漆每固形分（不揮發成分）全部的二氧化矽含量約爲 3 8質量％。 [實施例1] 使上述清漆，於總厚度爲38μιη之附離型層之PET薄 膜（Lintech (股）製AL5 )的離型面，以乾燥後之樹脂 組成物層的厚度成爲40μιη之方式以模縫塗佈器均一地塗 佈，以80~120°C (平均100°C )乾燥6分鐘（樹脂組成物 〇 層中之殘留溶劑量：約1 · 5質量％)。然後，於樹脂組成 物層之表面一邊貼合厚15 μιη之聚丙烯薄膜一邊捲取成輥 狀。將輥狀之黏著薄膜裁切成寬 507mm，得到 507 X 3 3 6mm大小的片狀之黏著薄膜。其後，於該黏著薄膜上 暫貼於被電路形成（電路導體厚18μηχ)之5 1 0x3 40mm大 小、厚0.2mm之銅箔層合板的雙面，藉（股）各機製作 所製真空積層機，以溫度100°C、壓力7kgf/cm2、氣壓 5mmHg以下之條件積層於雙面，進一步連續地以溫度1〇〇 °C、壓力5kgf/cm2之條件以SUs鏡板進行熱沖壓。然 -25- 200934348 後，以附著附離型層之PET薄膜的狀態以180°C、30分 鐘的條件熱硬化，於電路基板雙面形成絕緣層。 冷卻至室溫後，不剝離附離型層之PET薄膜’而從 其上藉三菱電機（股）製二氧化碳氣體雷射裝置（ML 605GTWII-P)，以記載於下述表1之實施例1的欄之條 件（脈沖寬4ns )進行開孔，形成肓孔（預設頂徑 70μιη )。又，使預設頂徑7 0 μ m與比較例相同，故以本例 φ 之附離型層的PET薄膜黏著的狀態之開孔中的光罩徑， 係略大於後揭示比較例（無附離型層的PET薄膜之開 孔）時的光罩徑（1.0mm)之1.1mm。 其後，以電子顯微鏡（SEM )進行肓孔的觀察，孔洞 的開口率（底徑/頂徑）以縱、橫之平均値計算，評估雷 射加工性。又，兼具去膠渣處理之絕緣層的表面處理之實 施後，以電子顯微鏡進行盲孔的觀察。又，表面處理係使 用 Atotech 公司之粗化液（Swelling Dip Securiganth P ❹ （膨潤）、濃縮液小型P (氧化）、還原溶液Securiganth P (中和）），而以經過膨潤60°C x5分、氧化80°C x20 分、中和40 °C x5分鐘之步驟來進行。 又，上述之「孔洞的開口率（底徑/頂徑）以縱、橫 的平均値計算」意指分別對於孔洞之底徑與頂徑，於與孔 洞之軸徑交叉的相互正交之2個方向（縱方向、橫方向） 而測定孔的直徑，計算其平均値。 又，孔洞之底徑及頂徑之測定係以（股）日立High Technologies製、掃描型電子顯微鏡（型式「SU-1500 -26- 200934348 」）進行。首先，對孔洞頂對準焦點，從以所觀察之倍率 顯示的刻度算出縱、橫之直徑，以其平均作爲頂徑。對孔 底頂對準焦點，從以所觀察之倍率顯示的刻度算出縱、橫 之直徑，以其平均作爲底徑。 [實施例2] 除以記載於表1之實施例2的欄之條件進行開孔以 φ 外，其餘係進行與實施例1同樣之操作，進行與實施例1 同樣之評估。 <比較例1、2 > 冷卻至室溫後，剝離附離型層之PET薄膜，而藉三 菱電機（股）製二氧化碳氣體雷射裝置（ML 605 GTWII-P )，以記載於下述表2之比較例1、2之條件進行開孔 (光罩徑1.0mm)。其以外，係進行與實施例1同樣之操 Ο 作’進行與實施例1同樣之評估。 結果表示於表1及表2。 -27- 200934348 樹脂（東都化成（股）製「ESN-475V」、環氧基當量約 3 40之不揮發成分65質量％的MEK溶液）40質量份、進 —步液狀雙酚A型環氧樹脂（Jap an Epoxy Resin (股）製 「828 EL」）6質量份、苯氧樹脂溶液（東都化成（股） 製「YP-70」、不揮發成分40質量。/❶之MEK與環己酮之 混合溶液）15質量份、作爲硬化觸媒之鈷（Π)乙醯基丙 酮（東京化成（股）製）之1質量％的Ν,Ν-二甲基甲醯胺 (DMF )溶液 4質量份、及球形二氧化矽（（股） Adomatech製「SO-C2」以胺基矽烷進行表面處理者、平 均粒徑0.5 μιη) 75質量份進行混合，以高速旋轉混合機均 一地分散，製作熱硬化性樹脂組成物清漆。該清漆每固形 分（不揮發成分）全部的二氧化矽含量約爲50質量％。 [實施例3] 使上述清漆，於總厚度爲38 μπι之附離型層之PET薄 〇 膜（Lintech (股）製AL5 )的離型面，以乾燥後之樹脂 組成物層的厚度成爲40μιη之方式以模縫塗佈器均一地塗 佈’以80~120°C (平均100°C )乾燥6分鐘（樹脂組成物 層中之殘留溶劑量：約1 .4質量％)。然後，於樹脂組成 物層之表面一邊貼合厚15 μηι之聚丙烯薄膜一邊捲取成輥 狀。將輥狀之黏著薄膜裁切成寬507mm，得到507 χ 336mm大小的片狀之黏著薄膜。其後，進行與實施例1 同樣之操作’進行與實施例1同樣之評估。但，兼具去膨 渣處理之絕緣層的表面處理係經過膨潤8(Tc xl0分、氧化 -29- 200934348 [產業上之利用可能性] 若依本發明，對於含有無機塡充材35質量％以上之 絕緣層，爲使加工性良好使用充分且高能量的二氧化碳氣 體雷射時，亦不對孔周邊的絕緣層表面造成很大的凹凸， 可形成頂徑爲1 00 μπι以下且孔底徑與頂徑之差小的良好 孔形狀之肓孔。因此，可製造導通信賴性高、且適於高密 度配線化之多層印刷電路板，尤其，藉由含有許多無機塡 充材，俾可適宜使用於以絕緣層之機械強度提高或熱膨脹 率降低等爲目的之多層印刷電路板的製造。 本申請案係以日本所申請之特願2007-30283 1爲基 礎，其內容係全部包含於本說明書中。 ❹ -32-The roughening step of roughening the surface of the insulating layer is carried out, for example, by treating the surface of the insulating layer with an oxidizing agent such as an aqueous alkaline permanganate solution. Further, the roughening step may be a step of removing the residue in the pores (Smear) such as a boring hole or a through hole. Further, when the roughening treatment is carried out with an aqueous alkaline permanganic acid solution, it is preferred to carry out a swelling treatment with a swelling liquid before the roughening treatment. The swelling liquid system is, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by Atotech Japan Co., Ltd. The swelling treatment system is generally carried out by applying a swelling liquid heated to about 60 to 80 ° C to the insulating layer for 5 to 10 minutes. The alkaline permanganic acid aqueous solution may, for example, be a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an aqueous solution of alkaline permanganic acid is generally carried out in an aqueous solution of an alkaline permanganic acid at 60 to 80 ° C for about 1 to 30 minutes. The alkaline permanganic acid aqueous solution is, for example, a concentrate small CP manufactured by Atotech Japan Co., Ltd., a dosing solution swelling agent (Securiganth) P, or the like. The electroplating step is, for example, a method of forming a conductor layer by a combination of electroless plating and electrolytic plating by a roughening treatment to form an uneven layer of an insulating layer, or forming a conductor layer by electroless plating only. The conductor layer may be formed of a metal such as copper, aluminum, nickel, silver or gold or an alloy of such metals, but is preferably copper. The copper plating layer is a combination of electroless plating and electrolytic plating, or a plating resist having a pattern opposite to that of the conductor layer, and the conductor layer is formed only by electroless plating. The thickness of the electroless plating layer is preferably from 0.1 to 3 μm, more preferably from 0.3 to 2 μm. Further, the total thickness of the thickness of the electrolytic plating layer and the thickness of the electroless plating layer is preferably from 3 to 35 μm, more preferably from 5 to 20 μm. Further, after the conductor layer is formed, it is annealed at 15 0 to 00 ° C for 20 to 90 minutes by -23-200934348, and the peel strength of the conductor layer can be further improved and stabilized. The circuit forming step can use, for example, subtraction, semi-additive, or the like. The formation of the fine lines is preferably a semi-additive method, forming a pattern resist on the electroless plating layer, forming an electrolytic plating layer (pattern plating layer) of a desired thickness, and then peeling off the pattern photoresist to remove the etching by the etching. Electrolytic plating, 俾 can form a circuit. φ The circuit board used in the manufacture of the multilayer printed wiring board of the present invention is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a resin substrate, or a thermosetting polyphenylene ether substrate. One or both sides form a patterned conductor layer (circuit). Further, in the case of manufacturing a multi-layer printed circuit board, an inner layer circuit board further forming an intermediate layer between the insulating layer and/or the conductor layer is also included in the circuit board of the present invention. Further, the surface of the conductor layer (circuit) is preferably subjected to a roughening treatment by a blackening treatment or the like, and is preferably from the viewpoint of the adhesion of the insulating layer to the circuit board. Hereinafter, the present invention will be more specifically described by showing examples and comparative examples. In the following description, "parts" means "parts by mass". (Production Example 1 of Thermosetting Resin Composition Varnish) 28 parts of liquid bisphenol fluorene type epoxy resin (epoxy equivalent weight 180, "Epicote 828EL" manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type 4 functional ring Oxygen resin (epoxy equivalent 163, Dainippon, "HP4700" manufactured by the Ink Chemical Industry Co., Ltd.) was dissolved in a mixed solvent of 15 parts of methyl ethyl ketone and 15 parts of cyclohexanone while stirring. Further, a naphthol-based hard-24-200934348 chemical agent ("SN-485" manufactured by Tohto Kasei Co., Ltd., phenolic hydroxyl equivalent 215), a solid solution of 50% methyl ethyl ketone solution, and a curing catalyst (Four Nations Chemical Industry) (2E4MZ), 0.1 parts, spherical silica sand (average particle size 0.5μιη, "SO-C2" manufactured by Adomatech) 70 parts, polyvinyl butyral resin solution (made by Sekisui Chemical Co., Ltd.) 30 parts of KS-lj solid solution of 15% ethanol and toluene in 1:1 solution, uniformly dispersed in a high-speed rotary mixer to prepare a thermosetting resin composition varnish. The varnish has a solid content (nonvolatile content) The content of cerium oxide is about 38% by mass. [Example 1] The varnish was dried on a release film of a PET film (AL5 manufactured by Lintech Co., Ltd.) having a total thickness of 38 μm. The thickness of the resin composition layer was 40 μm, and the coating was uniformly applied by a die coater, and dried at 80 to 120 ° C (average 100 ° C) for 6 minutes (the amount of residual solvent in the resin composition layer: about 1 · 5 mass%). Then, paste on the surface of the resin composition layer The polypropylene film having a thickness of 15 μm was taken up in a roll shape, and the roll-shaped adhesive film was cut into a width of 507 mm to obtain a sheet-like adhesive film of 507 X 3 3 6 mm. Thereafter, the adhesive film was temporarily placed on the adhesive film. It is attached to both sides of a copper foil laminate of 5 1 0x3 40 mm and 0.2 mm thick which is formed by a circuit (circuit conductor thickness: 18 μηχ), and a vacuum laminator manufactured by each machine is manufactured at a temperature of 100 ° C and a pressure of 7 kgf. /cm2, air pressure of 5mmHg or less, the conditions are laminated on both sides, and further continuously hot-stamped with a SUs mirror at a temperature of 1 ° C and a pressure of 5 kgf / cm 2 . After -25-200934348, the attached release layer The state of the PET film was thermally cured at 180 ° C for 30 minutes, and an insulating layer was formed on both surfaces of the circuit board. After cooling to room temperature, the PET film of the release layer was not peeled off, and Mitsubishi Electric was borrowed therefrom ( The carbon dioxide gas laser device (ML 605GTWII-P) was opened by a condition (pulse width 4 ns) described in the first embodiment of Table 1 below to form a pupil (predetermined top diameter 70 μm). Moreover, the preset top diameter of 70 μm is the same as that of the comparative example, so The mask diameter in the opening of the PET film attached to the release layer of this example φ is slightly larger than the mask diameter when the comparative example (the opening of the PET film without the release layer) is later disclosed (1.0). 1.1 mm of mm). Thereafter, the pupil was observed by an electron microscope (SEM), and the aperture ratio (bottom diameter/top diameter) of the hole was calculated by the average 纵 of the longitudinal and transverse directions to evaluate the laser processability. After the surface treatment of the desmear-treated insulating layer was carried out, blind holes were observed by an electron microscope. Further, the surface treatment was performed using Atotech's roughening liquid (Swelling Dip Securiganth P ❹ (swelling), concentrate small P (oxidation), reducing solution Securiganth P (neutralization)), and after swelling 60 ° C x 5 minutes, The procedure of oxidizing 80 ° C x 20 minutes, neutralizing 40 ° C x 5 minutes was carried out. In addition, the above-mentioned "opening ratio (bottom diameter/top diameter) of the hole is calculated as the average 纵 of the vertical and horizontal directions" means that the bottom diameter and the top diameter of the hole are orthogonal to each other with respect to the axial diameter of the hole. The diameter of the hole was measured in one direction (longitudinal direction and lateral direction), and the average enthalpy was calculated. In addition, the measurement of the bottom diameter and the top diameter of the hole was carried out by a Hitachi High Technologies product and a scanning electron microscope (type "SU-1500-26-200934348"). First, the top of the hole is aligned with the focus, and the vertical and horizontal diameters are calculated from the scale displayed at the observed magnification, and the average is taken as the top diameter. The bottom of the hole is aligned with the focus, and the vertical and horizontal diameters are calculated from the scale displayed at the observed magnification, and the average is used as the bottom diameter. [Example 2] The same operation as in Example 1 was carried out except that the opening was performed at a condition described in the column of Example 2 of Table 1, and the same evaluation as in Example 1 was carried out. <Comparative Example 1, 2 > After cooling to room temperature, the PET film of the release layer was peeled off, and a carbon dioxide gas laser device (ML 605 GTWII-P) manufactured by Mitsubishi Electric Corporation was described below. The conditions of Comparative Examples 1 and 2 of Table 2 were carried out (opening diameter: 1.0 mm). Other than that, the same operation as in the first embodiment was carried out, and the same evaluation as in the first embodiment was carried out. The results are shown in Tables 1 and 2. -27- 200934348 Resin (MEN-475V, manufactured by Tohto Kasei Co., Ltd., MEK solution of 65 mass% of non-volatile content of epoxy resin equivalent to 3 40) 40 parts by mass, liquid-phase bisphenol A ring Oxygen resin ("828 EL" manufactured by Jap an Epoxy Resin Co., Ltd.), 6 parts by mass, phenoxy resin solution (YP-70, manufactured by Tohto Kasei Co., Ltd., and 40% nonvolatile content. / MEK and Cyclohexane a mixed solution of ketone) 15 parts by mass of a ruthenium, ruthenium-dimethylformamide (DMF) solution of 1% by mass of cobalt (barium) acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing catalyst A mass fraction and a spherical cerium oxide (manufactured by Adomatech "SO-C2", surface-treated with an amino decane, an average particle diameter of 0.5 μm), 75 parts by mass, and uniformly dispersed by a high-speed rotary mixer. Thermosetting resin composition varnish. The varnish has a total cerium oxide content of about 50% by mass per solid content (nonvolatile content). [Example 3] The varnish was applied to a release surface of a PET film (AL5 manufactured by Lintech Co., Ltd.) having a total thickness of 38 μm, and the thickness of the resin composition layer after drying was 40 μm. The method was uniformly applied by a die coater to dry at 80 to 120 ° C (average 100 ° C) for 6 minutes (the amount of residual solvent in the resin composition layer: about 1.4% by mass). Then, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer while being wound into a roll. The roll-shaped adhesive film was cut into a width of 507 mm to obtain a sheet-like adhesive film of 507 χ 336 mm in size. Thereafter, the same operation as in Example 1 was carried out, and the same evaluation as in Example 1 was carried out. However, the surface treatment of the insulating layer which has the de-swelling treatment is swelled 8 (Tc x10, oxidized -29-200934348 [industrial use possibility], according to the present invention, for the inorganic cerium-containing material, 35 mass% In the above insulating layer, in order to make the processability good and use high-energy carbon dioxide gas laser, the surface of the insulating layer around the hole is not greatly uneven, and the top diameter is less than 100 μm and the hole diameter is A hole having a good hole shape with a small difference in the top diameter. Therefore, it is possible to manufacture a multilayer printed circuit board having high conductivity and high wiring density, and in particular, it can be suitably used by containing many inorganic ruthenium materials. The manufacture of a multilayer printed circuit board for the purpose of improving the mechanical strength of the insulating layer or reducing the thermal expansion rate. The present application is based on the Japanese Patent Application No. 2007-30283, the entire contents of which are incorporated herein by reference. ❹ -32-