201010539 四、指定代表圖： (一） 本案指定代表圖為：第（5)圖。 (二） 本代表圖之元件符號簡單說明： 1〜表面處理銅箔； 2〜銅層； 3〜表面處理層。 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無。 六、發明說明： 【發明所屬之技術領域】 本發明係關於覆銅層積板、使用於製造該覆銅層積板 之表面處理銅箔以及使用該覆銅層積板製造的印刷電路 板。特別是關於使用於製造印刷電路板的覆銅層積板，且 此印刷電路板包括在含硫酸與過氧化氫之蝕刻液中調製電 路線路製程。 【先前技術】 近年來’不只產業用電子及電子機器，甚至民生用電 子及電子機器等，附加資料處理功能之情形越來越多，前 述產品中當然有中央處理器（CPIO、大規模積體電路（LSI) 等積體電路（1C)元件的搭載。祚 戰作為具則述資料處理功能機 、代表，行動電話、行動音樂播放器等追求小型且高功 201010539 能。此結果組裝於搭載大規模積體電路等封裝基板之前述 機器的印刷電路板，對輕薄短小化的要求變強。因此，關 於印刷電路板的製造’提出有採用各種各樣加工工法的方 案，而開發出適用各種工法的覆銅層積板，特別是作為朝 輕薄短小化對應的印刷電路板，電路板彎曲性致容易收納 至有限且狹窄框體内的可彎折印刷電路板（Flex ible Printed Circuit;以下簡稱「FPC」）被大多數的機器採用。 癱 然而，以進一步輕薄短小化為目的時，因印刷電路板 被小型化、多層化以及印刷電路間距狹小化，無電解電锻 (無電解銅電鍍、無電解金電鍍等）會析出在電路線路間， 而發生人稱所謂之「銅遺漏」或「金遺漏」的「電鍍遺漏 現象」。而且，印刷電路板電路線路間距變得越狹窄，越 易發生此種電鍍遺漏現象’甚至移除電路線路間金屬成分 的修理作業變困難。特別是在帶式包裝電路（Tapecarrier Package，TCP)等印刷電路板製造中，雖然可以在可彎折印 • 刷電路板（FPC)中使用不設置接著劑層的2層可彎折覆銅 印刷電路板（Flexible Copper Clad Laminate;以下簡稱 「FCCL」），但因使用薄絕緣層，致使修理作業大體上是不 可能。在前述中，不能進行修補作業的產品，因成為當作 不良品廢棄對象的機率很高，進而構成資源，的浪費，而為 不佳。作為防止此「電路遺漏現象」發生的對策，在電路 線路形成後的電路間使不殘留金屬成分或離子性無機成 分’過去被認為有效。 還有，也可以使用前述2層FCCL，製造具有多個電路 201010539 線路層的多層m。在此μ州製造程序中，在使用聚 亞醯胺等絕緣樹脂基材的舰上職電路線路，經由結合 薄板組合成多層化’再形成介層窗等層間導通方式以 夕個電路線路層間電連接υ，構成Fpc絕緣樹脂層的 聚亞醯胺樹脂、芳㈣聚酿胺樹脂等，—般而言耐熱性佳， 但因缺乏耐藥品性特別是對鹼性藥品之耐藥品性，而致印 刷電路板加工製程受到限制。為此，在用以多層化層積的 前處理，介層窗形成前的軟蝕刻+，大多使用包含硫酸或 過氧化氫且不含氯等強酸離子的水溶液。 、為此，用以解決上述FPC問題的方式是從作為構成材 料之銅泊、絕緣樹脂層構成材料的雙方向上，必須提出有 用以解決前述問題的進路。從銅箔領域來看，欲使金屬成 分等不殘留，需對蝕刻特性的改善、絕緣樹脂層貼合面的 低稜線化、粗化處理粒子的微細化、防錄成分等進行研究。 口例如，專利文獻U曰本專利申請：特開平1〇_138394 號公報）中，將上述FPC製造引入視野，而揭示關於銅落的 亦即’剛述技術之目的是提供一種銅箔，以在銅羯 被接著面層積樹脂基材作為覆銅層積板時，可以在保持高 銅箔與樹脂基材間剝離強度之同時，具有較佳之耐熱性、 耐化學藥品性、耐濕性，且在無電解電鍍時，藉由蝕刻進 行去除時銅箔上不會引起朝樹脂基材面之電鍵金屬析出， 而有較佳之無電解電鍍處理性。此技術是揭示了在銅箔被 接著面上具有由矽烷耦合劑、矽酸鹽及硫撐二乙酸所構成 混合物披復層的印刷電路板用銅箔製造方法。還有，依據 201010539 專利文獻1所揭示之銅落製造方法，是揭示被接著面設置 粗化處理層及防錢層之同時，防銹層是由錄-銷-銘合金層 或銦辞α金層與鉻酸鹽層所構成之層形成。 二 使用貼合此專利文獻1揭示技術所製造之「經 防銹層中含錮等複合金屬層形成粗化處理粒子的銅羯J的 FCCL時也會如第2圖所示，有發生異常底切現象（符號2 箭頭所指處為底切部）的傾向。此現象發生時，即使外觀上 0 為良好線路寬度的電路線路，也會因此電路線路與樹脂絕 緣層間密著性大幅劣化’而容易引起線路剝離並易因反 覆彎曲應力而增加線路脫離之危險性。 由上述可知，在FPC業界，為了有在含硫酸及過氧化 氫之蝕刻液處理下，不會在電路線路底部發生底切現象的 FCCL ’而要求有對可防止前述現象發生之銅箔。 【發明内容】 φ 為此’本發明者深入研究的結果，想到使用具有下述 特性覆銅層積板作成印刷電路板，不僅可以使微細線路形 成變可能，還可以在被含硫酸及過氧化氫蝕刻液處理時， 不會在電路線路底部發生底切現象。 本發明覆銅層積板：本發明覆銅層積板是使用於包括 在含硫酸與過氧化氫之蝕刻液中調製電路線路製程之印刷 電路板製造的覆銅層積板，此覆銅層積板不僅銅層與絕緣 樹脂層為相互貼合之結構’甚至在此銅層與此絕緣樹脂層 間界面上具有包括辞成分與取得3種類以下離子價數之辞 201010539 以外過渡金屬成分的表面處理層，且此銅層與此絕緣樹脂 層間界面表面粗度（Rzj is)在2. 5微米以下。 本發明覆銅層積板中，前述表面處理層之鋅與前述過 渡金屬成分合計質量厚度較佳為4〇毫克/平方公尺(jng/m2) 以上。 本發明覆銅層積板中，前述銅層之與絕緣樹脂基材的 貼合面上較佳是設有粗化處理。 本發明覆銅層積板較佳是使用在前述絕緣樹脂基材上 具可撓性樹脂膜而成之可彎折覆銅層積板。 本發明表面處理銅笛：本發明表面處理銅荡為使用於 上述覆銅層積板製造的表面處理銅箔，在與絕緣樹脂基材 間貼合面上具有包括鋅成分與取得3種類以下離子價數之 鋅以外過渡金屬成分的表面處理&，且與此絕緣樹脂基材 間貼合面表面粗度（Rzj is)在2. 5微米以下。 本發明表面處理銅箔中，前述表面處理銅箱之與絕緣 樹脂基材的貼合面上較佳是設有粗化處理。 本發明印刷電路板：本發明印刷電路板是使用上述覆 銅層積板進行钱刻加工等而得。 還有，本發明印刷電路板中，將前述電路線路浸潰於 硫酸濃度10%至30%、過氧化氫濃度1〇%至2〇%之液溫攝氏 30度水溶液中30料’於前述電路與前述絕緣樹脂基材 間界面形成之底切深度為自前述電路端面起3〇微米（#瓜） 以下的特性。 [發明效果] 201010539 本發明覆銅層積板為用於在含硫酸與過氧化氫蝕刻液 中調製電路線路製程的印刷電路板製造。此覆銅層積板在 此銅層與此絕緣樹脂層間界面上具有包括鋅成分與取得3 種類以下離子價數之辞以外過渡金屬成分的表面處理層， 且此銅層與此絕緣樹脂層間界面表面粗度（Rzjis)在2.5 微米以下。此結果顯示，由於在於含硫酸與過氧化氫之蝕 刻液中進行處理時不會發生底切現象’故可在印刷電路板 製造程序所得電路線路與絕緣樹脂層間發揮良好的密著 性。而且，由於前述銅層與前述絕緣樹脂層間界面表面粗 度（Rz jis)較低’故FPC所要求之微細電路形成變容易。因 此’可以得到較適於印刷電路板製造的覆銅層積板以及對 前述覆銅層積板加工而得的印刷電路板。還有，本發明中 覆銅層積板所具層結構可以使用本發明表面處理銅羯輕易 製造得到。 【實施方式】 本發明覆銅層積板實施例：本發明覆銅層積板是使用 於包括在含硫酸與過氧化氫之蝕刻液中調製電路線路製程 之印刷電路板製造的覆銅層積板。本發明覆銅層積板基本 上有銅層與絕緣樹脂層為相互貼合之層結構，且第丨特徵 是在此銅層與此絕緣樹脂層間界面上具有包括鋅成分與取 得3種類以下離子價數之鋅以外過渡金屬成分的表面處理 層。還有’本發明覆銅層積板第2特徵是此銅層與此絕緣 樹脂層間界面表面粗度（Rzj is)在2.5微米以下。 201010539 首先對第1特徵進行說明。第i特徵是在此鋼層與 絕緣樹脂層間界面上，具有包括「鋅成分」與「取得3種 類以下離子價數之鋅以外過渡金屬成分」的表面處理層。 在此，表面處理層中「鋅成分」為必須成分。此外，例如 有鋅以外其他金屬成分是「取得3種類以下離子價數之鋅 以外過渡金屬成分」，即使係與銅的合金化為困難的金屬 成分，具有易使鋅與銅合金化的性質，因此在包括有含「鋅 成分」與「取得3種類以下離子價數之鋅以外過渡金屬成 分」的表面處理層與銅層間得到良好密著性。而且，鋅成 分因可以提升作為印刷電路板之耐熱特性，而成為必要成 分。 而且，辞以外成分是「取得3種類以下離子價數之鋅 以外過渡金屬成分」。一般而言，在水溶液中金屬與金屬 離子間的舉動，從離子化傾向可以有特定推測。然而，將 覆銅層積板加工成印刷電路板之際所接觸之各種溶液大 多具有溶解金屬成分的氧化力。覆銅層積板接觸前述溶液 (稀硫酸、稀鹽酸等）接觸之際，金屬銅會一邊被氧化，一 邊被溶解成銅離子。 對前述溶解反應模型而言’表面處理層包括「可取得 超過3種類離子價數之鋅以外過渡金屬成分（以下簡稱為 「多價金屬」）」’對此使用含硫酸與過氧化氫之蝕刻液時， 因存在有作為氧供給源之過氧化氫水，故在多價金屬本身 及其多個氧化物之間，容易引起伴隨著離子價數變化的不 可逆反應。此結果是對應使用於電路線路處理的蝕刻液氧 201010539 化還原電位變化，不僅表面處理層内多價金屬成分之氧化 還原狀態會變化，甚至辞或銅溶解析出前氧化狀態也會受 到影響。此結果，表面處理層與鋼層間電位差變動變大， 會產生銅層優先溶解的現象，而可能出現底切現象。 對此，只要表面處理層所含金屬可取得離子價數是3 種類以内（例如溶解析出之金屬離子為〗價、2價、3價任 一之情形），即使使用含硫酸與過氧化氫之蝕刻液時，也不 攀 i引起伴隨著此金屬成分與其氧化物間離子價數變化的不 可逆反應，不呈現上述現象，而顯現為與使用氣化鐵（hi) 銅蝕刻液或氯化銅（m)蝕刻液等之一般銅蝕刻之際相同 的舉動，故可以在得到穩定電路線路形狀之同時，不會引 起底切現象。在此所謂之「可取得3種類以下離子價數之 鋅乂外過渡金屬成分」是指錄、絡、鐵、麵、短、銅等。 則述中較佳是使用「可取得2種類以下離子價數之辞以外 過渡金屬成分」。此取得2種類以下離子價數之鋅以外過 • 渡金屬成分具體而言是形成1價離子或2價離子的銅、形 成2價離子或3價離子的鐵、僅形成2價離子的鎳。還有， 以上所述之「取得3種類以下離子價數之鋅以外過渡金屬 成分」即使以溶解析出方式共存於蝕刻液中，對形成電路 線路時的銅钱刻也沒有不良影響。 在此’第1圖所示為在以下所述本發明製造使用於表 面處理銅箔的覆銅層積板及使用前述覆銅層積板之印刷電 路板製造中，於電路線路形成後使用含硫酸與過氧化氫之 餘刻液進行微蝕刻的結果。此結果是電路線路底部沒有發 201010539 生底切現象時，從銅層2、表面處理層3、絕緣樹脂基材5 剖面所得之層結構。前述情形是使用本發明表面處理銅溶 製造覆銅層積板及使用前述覆銅層積板之印刷電路板製 造。還有’第2圖所示為使用含硫酸與過氧化氮之钱刻液 進打微蝕刻的結果。此結果是從電路線路（銅層底部發 生底切現象時之剖面所得之底切部6樣子。此是使用具含 翻表面處理層的表面處理銅羯製造覆銅層積板，且使用此 覆銅層積板進行印刷電路板製造之情況’鉬是取得超過3 種類離子價數之過渡金屬成分。比對第i圖與第2圖可知，❹ 表面處理層所含金屬取得離子價數在3種類以内（例如溶 解析出之金屬離子為1價、2價、3餘-情形）時，使用 含硫酸與過氧化氫之㈣液進行微㈣之情形下，不會發 生底切現象。 以上所逑本發明覆銅層積板之表面處理層之「鋅成分」 ur3種類以下離子價數之鋅以外過渡金屬成分」 ❿ … 厚度較佳為40毫克/平方公尺（mg/m2)以上。此質 量厚度不足40奎券/ JJ1 Htr /\ 0 + a尺時，依據前述表面處理層界 材門的二不完全部分之傾向變強’且銅層與絕緣樹脂基 =的^性、耐熱性、耐藥品性會依場所產生變化而為 。在此，對質量厚度下限值為4〇毫克，平方公尺的理 :: 說明。此質量厚度是完全平的理想平面上披覆成厚 度為40埃之前述表 覆蓋理”面而且，在4°埃厚度下 在幾乎平滑表面二成分量是以理想平面表面積為基準， 面上存在有形狀變化小且微細之粗化處理粒 10 201010539 子而成的粗化處理面，前述的表面積比只要在2前後包 括具有粗化處理粒子的突出的懸崖部分，都有充足的量進 行幾乎無遺漏地覆蓋。 還有，在此並未設定此質量厚度上限，不過有些構成 表面處理層的金屬種類，因前述金屬成分存在大量時，在 蝕刻下形成電路線路之際，會有難以溶解的成分。在上述 結構中，為了不使所使用合金成分有蝕刻殘留等情形，表 φ 面處理層質量厚度較佳是80毫克/平方公尺以下。 接著，對本發明覆銅層積板第2特徵「此銅層與此絕 緣樹脂層間界面表面粗度〇{2扒5)在2. 5微米以下」進行說 明。此界面表面粗度（Rzj is)超過2. 5微米時，製造多層 FPC時，層間絕緣可靠性及微細電路線路形成會變困難。 相對於此，界面表面粗度（Rzjis)在25微米以下時，不僅 局部形成過大粗化處理粒子之可能性會消失，甚至使用於 絕緣樹脂層薄的多層FPC製造也可以維持層間絕緣可靠 • 性。還有，FPC的線/空間為25微米/25微米之微細電路形 成變容易。 還有’本發明覆銅層積板的銅層與絕緣樹脂基材的貼 合面上較佳是設有粗化處理，以提高銅層與絕緣樹脂層間 密著性。因此’本發明覆銅層積板之設於銅層與絕緣樹脂 基材的粗化處理層是在測量此覆銅層積板剖面展開阻抗 時’附著微細銅粒等所形成之粗化處理層的粗化處理層阻 抗值（Rbi)與銅層之塊狀銅層塊狀層阻抗值（rbz)相異，較佳 是具有RB1 < RBZ的關係。具有前述關係時，對防止底切現象 11 201010539 而言為較佳的。 第3圖係繪示電路線路底部沒有發生底切現象時使 用之覆銅層積板之剖面的展開阻抗測量結果。第4圖係絡 示電路線路底部發生底切現象時，使用之覆銅層積板之^ 面的展開阻抗測量結果。在前述圖面中，顏色越暗表示展 開阻抗測量值越高的部分’各㈣a)是剖面展開阻抗影 像，b)則是以塊狀銅部平均值（約為2千歐姆（kQ))為基準 所得之展開阻抗影像。還有’前述圖面上部是銅層與絕緣 樹脂層構成材料間貼合界面，且表層有經粗化處理的粗& m 處理層。在此，比對第3圖與第4圖可以得知，在第3圖 之情形下，銅層之絕緣樹脂層構成材料貼合面附近（粗化處 理層）色調較明亮，其他塊狀銅層色調則較暗。相對於此， 第4圊之情形下，銅I之絕緣樹脂層構成材料貼合面附近 的粗化處理層色調與其他塊狀銅層色調間的差異呈無法明 顯確認之狀態。還有，僅看此第3圖與第4圖之覆銅層積 板銅層與絕緣樹脂層構成材料間貼合界面最表層，比起第 ❿ 3圖，第4圖高阻抗區域會被顯著地觀察到。在此，處理 千兆赫（GHz)命令高頻信號的電路線路中，鑑於依據表皮效 果’也就是信號會流動於銅箔與絕緣樹脂基材間接著面 側，故為改善高頻傳送特性’覆銅層積板的銅層絕緣樹脂 層構成材料間貼合面阻抗越低越佳。因此，從前述觀點來 看’本發明覆銅層積板較佳是具有粗化處理層阻抗值（Rbi) <塊狀層阻抗值（RB2)的關係。 本發明覆銅層積板較佳是使用在前述絕緣樹脂基材上 12 201010539 具可撓性樹脂膜而成之可㈣覆銅層積板。在此所項之具 可撓性樹脂膜是聚亞酿胺樹脂膜、芳香族聚酿胺樹脂膜、、 聚對苯二甲酸乙二醇醋(PET)樹脂膜、液晶聚合物樹脂膜 等’膜材質、膜厚度等並未特別限定。 本發明表面處理銅羯：本發明表面處理銅落為使用上 述覆銅層積板製造的表面處理銅笛。因此，在與絕緣樹脂 層間貼合面上具有包括鋅成分與可取得3種類以下離子價 數之辞以外過渡金屬成分的表面處理層，且與此絕緣樹脂 層間貼合面表面粗度（Rzjis)在2.5微米以下。此表面處理 銅箱貼合於絕緣樹脂層構成材料上，即得到上述本發明覆 銅層積板。因此，對此表面處理銅箔之說明時，關於「表 面處理層」及「貼合面表面粗度（Rzjis)在25微米以下」 說明為了避免重複，而在此省略說明。此時本發明表面處 理銅泊1係由銅箔（塊狀銅層）2、表面處理層3所構成，此 層結構的模式剖面圖…圖所示。還有，本發明表面處 理鋼落之情形下’進-步提高與絕緣樹脂層構成材料間密 著性的方法是在表面處理層表面上進一步設置矽烷耦合劑 處理層。 而且，本發明表面處理銅羯的表面處理銅箔與絕緣樹 脂基材的貼合面上較佳是設有粗化處理。本發明表面處理 銅荡1之情形下’在銅g 2的貼合面上’形成施加粗化處 理而得之粗化處理面4,再於此粗化處理面4上形成表面 處理層3’通常是如第6圖所示之層結構。在此粗化處理 面4之形成中，使用附著粗化處理粒子方法之情形下使 13 201010539 · 用金屬銅所構成之微細銅粒子，可以在形成電路線路之際 的銅蝕刻下一併進行粗化處理粒子蝕刻去除，又因用以去 除粗化處理粒子的過蝕刻時間不需增加，而仍可以維持良 好的蝕刻因子。藉由覆銅層積板製造程序中所施加之熱履 歷，在銅塊（銅4側）與微細銅粒子（粗化處理粒子）間附著 界面，關於所引起之銅相互擴散，更可以使對銅塊之粗化 處理粒子密著性進一步強化固定。 本發明印刷電路板之形態：本發明印刷電路板是使用 上述覆銅層積板進行蝕刻加工等而得。在前述中，於多層 馨 印刷電路板製造程序中，即使電路線路浸潰於各種藥品 中，電路端面上也不會發生底切，而為電特性及連接可靠 性倶佳的印刷電路板。 還有，本發明印刷電路板中，將前述電路線路浸潰於 硫酸濃度10%至30%、過氧化氫濃度10%至2〇%之液溫攝氏 30度水溶液中30秒後，於前述電路與前述絕緣樹脂基材 間界面形成之底切深度為自前述電路端面起3. 〇微米（#m) 馨 以下的特性。亦即，溢料蝕刻、微蝕刻、銅線路蝕刻之際， 即使用含硫酸與過氧化氫之蝕刻液也不會發生底切現象。 因此，印刷電路板中也適於追求微細線路形成之可彎折印 刷電路板用途。 [產業上可利用性] 本發明覆銅層積板為用於在含硫酸與過氧化氫蝕刻液 中調製電路線路製程的印刷電路板製造。使用此覆銅層積 14 201010539 板在溢料蝕刻、微餘刻、銅線路蚀刻中’即使用含硫酸與 過氧化氫之姓刻液也不會發生底切現象。而且’由於前迷 銅層與前述絕緣樹脂層間界面表面粗度（Rzj is)較低，& FPC所要求之微細電路形成變容易。特別是本發明覆銅$ 積板可以滿足可彎折印刷電路板所要求之要求特性。選 有’本發明覆銅層積板使用本發明表面處理銅箔時，藉由 構成絕緣樹脂層之樹脂薄板、預浸潰體等進行層積加工等 可以容易製造。 【圖式簡單說明】 第1圖係繪示電路線路底部沒有發生底切現象時，從 剖面所見樣子的光學顯微鏡觀察圖。 第2圖係繪示電路線路底部發生底切現象時，從剖面 所見樣子的光學顯微鏡觀察圖。201010539 IV. Designated representative map: (1) The representative representative of the case is: (5). (b) The symbol of the symbol of this representative figure is briefly described: 1~ surface treated copper foil; 2~ copper layer; 3~ surface treated layer. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. [Technical Field] The present invention relates to a copper clad laminate, a surface-treated copper foil used for producing the copper clad laminate, and a printed circuit board produced using the copper clad laminate. In particular, it relates to a copper clad laminate for use in the manufacture of printed circuit boards, and the printed circuit board includes a process for modulating a circuit line in an etching solution containing sulfuric acid and hydrogen peroxide. [Prior Art] In recent years, there have been more and more additional data processing functions, not only industrial electronic and electronic equipment, but also electronic and electronic equipment for people's livelihood. Of course, there are central processing units (CPIO, large-scale integrated products). In the case of the integrated circuit (1C), such as the circuit (LSI), the company is pursuing a large-scale and high-powered 201010539, which is a data processing function, representative, mobile phone, and mobile music player. In the printed circuit board of the above-mentioned machine, such as a large-scale integrated circuit, the requirements for thinness and thinness have become stronger. Therefore, regarding the manufacture of printed circuit boards, various methods of processing methods have been proposed, and various methods have been developed. A copper-clad laminated board, in particular, a printed circuit board corresponding to a light and thin short, and a flexible printed circuit board (hereinafter referred to as "Flexible Printed Circuit" (hereinafter referred to as "flexible printed circuit board" which is easily accommodated in a limited and narrow frame. FPC") is used by most machines. However, for the purpose of further thinning and thinning, due to printed circuit boards Miniaturization, multi-layering, and narrow printed circuit spacing, electroless forging (electroless copper plating, electroless gold plating, etc.) will be deposited between circuit lines, and the so-called "copper omission" or "golden omission" "Electroplating omission phenomenon." Moreover, the narrower the wiring pitch of the printed circuit board becomes, the more likely this kind of plating omission occurs. It is even difficult to remove the metal component between the circuit lines, especially in the tape packaging circuit ( In the manufacture of printed circuit boards such as Tape carrier Package (TCP), it is possible to use a flexible copper clad laminate (Flexible Copper Clad Laminate) in a bendable printed circuit board (FPC) without an adhesive layer. Hereinafter referred to as "FCCL"), but the use of a thin insulating layer makes repair work substantially impossible. In the above, products that cannot be repaired are highly likely to be discarded as defective products, and thus constitute a resource. The waste is not good. As a countermeasure to prevent this "circuit leakage phenomenon", the circuit between the circuit lines is formed. The residual metal component or the ionic inorganic component 'has been considered to be effective in the past. Further, it is also possible to manufacture the multilayer m having a plurality of circuit layers 201010539 using the above two layers of FCCL. In this μ state manufacturing process, polyaluminium is used. A ship's upper circuit circuit of an insulating resin substrate such as an amine is combined with a thin layer to form a multilayered 're-formation layer-to-layer window, and the interlayer connection mode of the interlayer circuit is electrically connected to each other to form a polyacrylamide of the Fpc insulating resin layer. Resin, aromatic (tetra) polyamine resin, etc., generally have good heat resistance, but due to lack of chemical resistance, especially to the chemical resistance of alkaline drugs, the processing process of printed circuit boards is limited. In the pretreatment of the multilayer lamination, the soft etching + before the formation of the via window is mostly an aqueous solution containing sulfuric acid or hydrogen peroxide and containing no strong acid ions such as chlorine. For this reason, in order to solve the above-mentioned FPC problem, it is necessary to propose an approach for solving the above problems from both sides of the material constituting the copper poking and insulating resin layers constituting the material. In the field of the copper foil, in order to prevent the metal component from remaining, it is necessary to improve the etching characteristics, the low ridge line of the insulating resin layer bonding surface, the miniaturization of the roughened particles, and the anti-recording component. In the above-mentioned FPC manufacturing, the above-mentioned FPC manufacturing is introduced into the field of view, and it is revealed that the purpose of the technology is to provide a copper foil, for example, in the patent application U.S. Patent Application No. Hei. When the copper enamel is laminated on the resin substrate as the copper-clad laminate, it is possible to maintain the high peeling strength between the copper foil and the resin substrate, and to have better heat resistance, chemical resistance, and moisture resistance. Further, in the electroless plating, when the etching is performed by etching, the copper foil is not caused to precipitate on the surface of the resin substrate, and the electroless plating treatment property is preferable. This technique discloses a method for producing a copper foil for a printed circuit board having a coating layer of a mixture of a decane coupling agent, a ceric acid salt and a sulfuric acid diacetic acid on a subsequent surface of a copper foil. Further, according to the copper drop manufacturing method disclosed in Patent Document 1 of 201010539, it is disclosed that the roughening treatment layer and the anti-money layer are provided on the joint surface, and the rustproof layer is composed of a recording-pin-ing alloy layer or an indium-based alpha gold. The layer is formed with a layer of chromate layer. In the case of the FCCL of the copper 羯J which forms the roughened particles by the composite metal layer containing ruthenium or the like in the rust-preventive layer, as shown in Fig. 2, an abnormal bottom occurs. The tendency of the phenomenon (the symbol 2 indicates that the arrow is the undercut). When this phenomenon occurs, even if the circuit line whose appearance is 0 is a good line width, the adhesion between the circuit line and the resin insulating layer is greatly deteriorated. It is easy to cause the line to peel off and it is easy to increase the risk of line detachment due to the repeated bending stress. It can be seen from the above that in the FPC industry, in order to have an etching solution containing sulfuric acid and hydrogen peroxide, no undercut occurs at the bottom of the circuit line. In the case of the FCCL of the phenomenon, it is required to have a copper foil which can prevent the occurrence of the above-mentioned phenomenon. [Explanation] For the result of intensive study by the present inventors, it is thought to use a copper-clad laminate having the following characteristics to form a printed circuit board, not only It is possible to make the formation of fine lines possible, and it is also possible to prevent undercutting at the bottom of the circuit line when it is treated with a sulfuric acid-containing and hydrogen peroxide etching solution. Copper laminated board: The copper-clad laminated board of the present invention is a copper-clad laminated board manufactured using a printed circuit board including a process for modulating a circuit line in an etching liquid containing sulfuric acid and hydrogen peroxide, and the copper-clad laminated board is not only The copper layer and the insulating resin layer are bonded to each other', and even at the interface between the copper layer and the insulating resin layer, there is a surface treatment layer including a composition component and a transition metal component other than 201010539, which is obtained from the ionic value of three types or less. The thickness of the interface between the copper layer and the insulating resin layer is less than 2.5 μm. In the copper clad laminate of the present invention, the total thickness of the zinc of the surface treatment layer and the transition metal component is preferably 4 In the copper-clad laminate of the present invention, it is preferable to provide a roughening treatment on the bonding surface of the copper layer and the insulating resin substrate. Preferably, the laminate is a bendable copper clad laminate having a flexible resin film on the insulating resin substrate. The surface treated copper flute of the present invention: the surface treated copper of the present invention is used for the above copper clad Laminated panel The surface-treated copper foil has a surface treatment & a zinc-containing component and a transition metal component other than zinc having three or less kinds of ion valences on the surface to be bonded to the insulating resin substrate, and is bonded to the insulating resin substrate. The surface roughness (Rzj is) is 2.5 μm or less. In the surface-treated copper foil of the present invention, the surface of the surface-treated copper box and the insulating resin substrate are preferably provided with a roughening treatment. Printed circuit board: The printed circuit board of the present invention is obtained by performing the etching process using the above copper-clad laminate. Further, in the printed circuit board of the present invention, the circuit line is immersed in a sulfuric acid concentration of 10% to 30%, The hydrogen peroxide concentration of 1% to 2% of the liquid temperature in 30 degree Celsius aqueous solution of 30 materials 'the undercut depth formed at the interface between the aforementioned circuit and the aforementioned insulating resin substrate is 3 〇 micron from the end face of the aforementioned circuit (# melon The following characteristics. [Effect of the Invention] 201010539 The copper clad laminate of the present invention is a printed circuit board for modulating a circuit line process in a sulfuric acid-containing and hydrogen peroxide etching solution. The copper clad laminate has a surface treatment layer including a zinc component and a transition metal component other than the ion valence of 3 types or less at the interface between the copper layer and the insulating resin layer, and the interface between the copper layer and the insulating resin layer The surface roughness (Rzjis) is below 2.5 microns. This result shows that the undercut phenomenon does not occur when the treatment is carried out in the etching solution containing sulfuric acid and hydrogen peroxide, so that good adhesion can be obtained between the circuit line obtained by the printed circuit board manufacturing process and the insulating resin layer. Further, since the interface surface roughness (Rz jis) between the copper layer and the insulating resin layer is low, the formation of a fine circuit required by the FPC becomes easy. Therefore, a copper clad laminate suitable for the manufacture of a printed circuit board and a printed circuit board obtained by processing the above copper clad laminate can be obtained. Further, the layered structure of the copper clad laminate of the present invention can be easily produced by using the surface treated copper crucible of the present invention. [Embodiment] The present invention relates to a copper clad laminate. The copper clad laminate of the present invention is a copper clad laminate used for a printed circuit board comprising a process for modulating a circuit line in an etching solution containing sulfuric acid and hydrogen peroxide. board. The copper-clad laminate of the present invention basically has a layer structure in which a copper layer and an insulating resin layer are bonded to each other, and the second feature is that the interface between the copper layer and the insulating resin layer has a zinc component and three or less ions are obtained. A surface treatment layer of a transition metal component other than the valence of zinc. Further, the second feature of the copper clad laminate of the present invention is that the interface surface roughness (Rzj is) between the copper layer and the insulating resin layer is 2.5 μm or less. 201010539 First, the first feature will be described. The i-th feature is a surface treatment layer including a "zinc component" and a "transition metal component other than zinc having three kinds of ion valences" at the interface between the steel layer and the insulating resin layer. Here, the "zinc component" in the surface treatment layer is an essential component. In addition, for example, a metal component other than zinc is a transition metal component other than zinc having three or more kinds of ion valences, and even if it is a metal component which is difficult to alloy with copper, it has a property of easily alloying zinc with copper. Therefore, good adhesion is obtained between the surface treatment layer including the "zinc component" and the "transition metal component other than zinc having three types of ion valence" and the copper layer. Moreover, the zinc component is an essential component because it can be improved as a heat resistant property of a printed circuit board. In addition, the component other than the vocabulary is "a transition metal component other than zinc having three types of ion valences". In general, the behavior between metal and metal ions in an aqueous solution can be specifically estimated from the ionization tendency. However, the various solutions contacted when the copper clad laminate is processed into a printed circuit board have an oxidizing power which dissolves the metal component. When the copper clad laminate contacts the solution (dilute sulfuric acid, dilute hydrochloric acid, etc.), the metallic copper is oxidized and dissolved into copper ions. For the dissolution reaction model described above, the surface treatment layer includes "a transition metal component other than zinc which can obtain more than three kinds of ion valences (hereinafter referred to as "polyvalent metal")", which is etched using sulfuric acid and hydrogen peroxide. In the case of liquid, since hydrogen peroxide water is provided as an oxygen supply source, an irreversible reaction accompanying a change in the valence of ions is likely to occur between the polyvalent metal itself and a plurality of oxides thereof. This result is a change in the reduction potential of the etching liquid oxygen used in the circuit line treatment. Not only the oxidation-reduction state of the polyvalent metal component in the surface treatment layer changes, but also the oxidation state before the dissolution or precipitation of copper is affected. As a result, the fluctuation of the potential difference between the surface treatment layer and the steel layer becomes large, and the copper layer is preferentially dissolved, and undercutting may occur. In this case, as long as the metal contained in the surface treatment layer can obtain an ion valence of 3 or less (for example, the metal ion dissolved and precipitated is a valence, a divalent or a trivalent valence), even if sulfuric acid and hydrogen peroxide are used. When etching the liquid, it does not cause an irreversible reaction accompanied by a change in the valence of the ions between the metal component and its oxide, and does not exhibit the above phenomenon, but appears to be in contact with the use of vaporized iron (hi) copper etching solution or copper chloride ( m) The same behavior as the general copper etching of an etching solution, etc., so that the shape of the stable circuit line can be obtained without causing undercut. Here, the "external zinc-transition transition metal component which can obtain three or more kinds of ion valences" refers to a recording, a complex, an iron, a surface, a short, a copper, and the like. In the above description, it is preferable to use "a transition metal component other than the ionic value of two types or less." In addition to the zinc having two or more kinds of ion valences, the metal component is specifically copper which forms a monovalent ion or a divalent ion, iron which forms a divalent ion or a trivalent ion, and nickel which forms only a divalent ion. In addition, the above-mentioned "transition metal component other than zinc having three or more kinds of ion valences" does not adversely affect the copper alloy when forming a circuit line even if it is coexisted in the etching liquid by dissolution and precipitation. Here, FIG. 1 is a view showing the production of a copper-clad laminate for use in a surface-treated copper foil and a printed circuit board using the copper-clad laminate according to the present invention described below. The result of microetching of the residual solution of sulfuric acid and hydrogen peroxide. This result is a layer structure obtained from the copper layer 2, the surface treatment layer 3, and the insulating resin substrate 5 when the bottom of the circuit line is not subjected to the undercut phenomenon of 201010539. The foregoing case is produced by using the surface-treated copper-soluble copper-clad laminate of the present invention and a printed circuit board using the copper-clad laminate. Also, Fig. 2 shows the results of microetching using a solvent containing sulfuric acid and nitrogen peroxide. The result is the undercut portion 6 obtained from the circuit line (the cross section at the bottom of the copper layer when the undercut phenomenon occurs. This is to use a surface treated copper enamel with a surface treatment layer to produce a copper clad laminate, and use this overlay The case where a copper laminate is used for the manufacture of a printed circuit board. 'Molybdenum is a transition metal component that obtains more than three types of ion valence. Comparing the first and second figures, the metal contained in the surface treatment layer has an ion valence of 3 When the type (for example, in the case where the metal ions dissolved and precipitated are in the form of monovalent, divalent or trivalent), when the (four) liquid containing sulfuric acid and hydrogen peroxide is used, the undercut phenomenon does not occur. The "zinc component" of the surface-treated layer of the copper-clad laminate of the present invention has a transition metal component other than the ur 3 type ion valence number 」 ... The thickness is preferably 40 mg / m 2 (mg / m 2 ) or more. When the thickness is less than 40 vouchers / JJ1 Htr / \ 0 + a ruler, the tendency of the two incomplete parts of the surface treatment layer is increased according to the surface treatment layer, and the copper layer and the insulating resin base = heat resistance, heat resistance, resistance Drug properties will change depending on the location Here, the lower limit of the mass thickness is 4 〇 millimeters, and the square meter is:: This mass thickness is completely flat and the ideal plane is covered with a thickness of 40 angstroms. At a thickness of 4° angstrom, the amount of the two components on the almost smooth surface is based on the ideal plane surface area, and there is a roughened surface having a small shape change and a fine roughened grain 10 201010539. As long as the protruding cliff portion with roughened particles is included before and after 2, there is a sufficient amount for almost complete coverage. Also, the upper limit of the mass thickness is not set here, but some metal types constituting the surface treatment layer When there is a large amount of the above-mentioned metal component, a component which is difficult to dissolve is formed when a circuit line is formed by etching. In the above configuration, in order to prevent the alloy component used from being etched, the mass thickness of the surface φ surface treatment layer is Preferably, it is 80 mg/m 2 or less. Next, the second feature of the copper clad laminate of the present invention "the thickness of the interface surface between the copper layer and the insulating resin layer" 2 {5 Pa) "in 2.5 micron or less will be described. When the interface surface roughness (Rzj is) exceeds 2.5 μm, the interlayer insulation reliability and the formation of the fine circuit wiring become difficult when the multilayer FPC is manufactured. On the other hand, when the interface surface roughness (Rzjis) is 25 μm or less, the possibility of not only partially forming excessively roughened particles is lost, and even the multilayer FPC manufactured by using a thin insulating resin layer can maintain interlayer insulation reliability. . Also, the fine circuit of the FPC line/space of 25 μm / 25 μm is made easy. Further, it is preferable that the bonding surface of the copper layer of the copper-clad laminate of the present invention and the insulating resin substrate is provided with a roughening treatment to improve the adhesion between the copper layer and the insulating resin layer. Therefore, the roughened layer provided on the copper layer and the insulating resin substrate of the copper-clad laminate of the present invention is a roughened layer formed by attaching fine copper particles or the like when measuring the strain of the copper-clad laminate. The roughened layer resistance value (Rbi) is different from the bulk copper layer bulk layer resistance value (rbz) of the copper layer, and preferably has a relationship of RB1 < RBZ. When the above relationship is present, it is preferable to prevent the undercut phenomenon 11 201010539. Fig. 3 is a graph showing the developed impedance measurement of the cross section of the copper clad laminate used when no undercut occurs at the bottom of the circuit. Fig. 4 shows the measured results of the developed impedance of the copper clad laminate used when the undercut occurs at the bottom of the circuit. In the above-mentioned drawings, the darker the color, the higher the portion where the measured impedance value is expanded, the (a) a) is the cross-sectional expansion impedance image, and the b) is the average value of the bulk copper portion (approximately 2 kilo ohms (kQ)). The expanded impedance image obtained from the benchmark. Further, the upper surface portion is a bonding interface between the copper layer and the insulating resin layer constituting material, and the surface layer has a roughened & m treated layer. Here, it can be seen from the comparison between FIG. 3 and FIG. 4 that in the case of FIG. 3, the insulating resin layer of the copper layer constitutes a bright color near the bonding surface of the material (roughening layer), and other bulk copper The layer tones are darker. On the other hand, in the case of the fourth layer, the difference between the color tone of the roughened layer in the vicinity of the bonding surface of the insulating resin layer of the copper I and the color tone of the other bulk copper layer was not clearly confirmed. In addition, only the outermost layer of the bonding interface between the copper-clad laminate and the insulating resin layer of the copper-clad laminate of the third and fourth figures can be seen. Compared with the third graph, the high-impedance region of the fourth graph is marked. Observed. Here, in the circuit circuit for processing the high-frequency signal of the gigahertz (GHz) command, in order to improve the high-frequency transmission characteristics in view of the effect of the skin, that is, the signal flows on the interface side between the copper foil and the insulating resin substrate. The copper layer insulating resin layer of the copper laminated board preferably has a lower bonding surface resistance between the constituent materials. Therefore, from the foregoing point of view, the copper clad laminate of the present invention preferably has a relationship of a roughened layer resistance value (Rbi) < a bulk layer impedance value (RB2). The copper clad laminate of the present invention is preferably a (IV) copper clad laminate which is formed of a flexible resin film on the insulating resin substrate 12 201010539. The flexible resin film referred to herein is a polyacrylamide resin film, an aromatic polyamine resin film, a polyethylene terephthalate (PET) resin film, a liquid crystal polymer resin film, etc. The film material, film thickness, and the like are not particularly limited. The surface treated copper ruthenium of the present invention: the surface treated copper slab of the present invention is a surface treated copper distiller manufactured using the above copper clad laminate. Therefore, a surface treatment layer including a zinc component and a transition metal component other than the ion valence of three types or less is provided on the surface to be bonded to the insulating resin layer, and the surface roughness of the surface of the bonding surface between the insulating resin layers (Rzjis) Below 2.5 microns. This surface-treated copper case is bonded to the insulating resin layer constituting material to obtain the above-described copper-clad laminate of the present invention. Therefore, in the description of the surface-treated copper foil, the description of the "surface treatment layer" and the "surface roughness of the surface of the bonding surface (Rzjis) of 25 μm or less" will be omitted in order to avoid redundancy. At this time, the surface treatment copper plating system of the present invention is composed of a copper foil (block copper layer) 2 and a surface treatment layer 3, and a schematic sectional view of the layer structure is shown in the figure. Further, in the case where the surface of the present invention is treated to have a steel drop, the method of improving the adhesion between the insulating resin layer and the insulating resin layer is further provided by further providing a decane coupling agent treatment layer on the surface of the surface treatment layer. Further, it is preferable that the surface of the surface-treated copper foil of the surface-treated copper ruthenium of the present invention and the insulating resin substrate are provided with a roughening treatment. In the case where the surface treatment of the copper is 1 in the present invention, the roughened surface 4 is formed by applying a roughening treatment on the bonding surface of the copper g 2, and the surface treated layer 3' is formed on the roughened surface 4 It is usually a layer structure as shown in Fig. 6. In the formation of the roughened surface 4, in the case of the method of attaching the roughened particles, the fine copper particles composed of metallic copper can be used for the copper etching at the time of forming the circuit line. The particle etching is removed, and the overetching time for removing the roughened particles does not need to be increased, and a good etching factor can be maintained. The interface between the copper block (copper 4 side) and the fine copper particles (roughened particles) is adhered to by the heat history applied in the copper-clad laminate manufacturing process, and the copper can be mutually diffused. The roughening of the copper block is further enhanced by the particle adhesion. In the form of the printed circuit board of the present invention, the printed circuit board of the present invention is obtained by etching or the like using the above copper clad laminate. In the above, in the manufacturing process of the multilayer printed circuit board, even if the circuit line is immersed in various chemicals, undercutting does not occur on the end face of the circuit, and the printed circuit board is excellent in electrical characteristics and connection reliability. Further, in the printed circuit board of the present invention, the circuit circuit is immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30%, a hydrogen peroxide concentration of 10% to 2%, and a liquid temperature of 30 degrees Celsius for 30 seconds, after the circuit is The undercut depth formed by the interface with the insulating resin substrate is 3. 〇 micron (#m) below the characteristics of the circuit end face. That is, during the flash etching, the micro etching, and the copper line etching, the undercut phenomenon does not occur even if an etching solution containing sulfuric acid and hydrogen peroxide is used. Therefore, printed circuit boards are also suitable for the use of bendable printed circuit boards for the formation of fine lines. [Industrial Applicability] The copper clad laminate of the present invention is a printed circuit board for modulating a circuit line process in a sulfuric acid-containing and hydrogen peroxide etching solution. The use of this copper-clad laminate 14 201010539 plate in the flash etching, micro-removal, copper line etching, that is, the use of sulfuric acid and hydrogen peroxide surname engraving will not occur undercut. Further, since the interface surface roughness (Rzj is) between the front copper layer and the insulating resin layer is low, the formation of fine circuits required by & FPC becomes easy. In particular, the copper clad laminate of the present invention can meet the required characteristics required for a bendable printed circuit board. When the surface-treated copper foil of the present invention is used in the copper-clad laminate of the present invention, it can be easily produced by laminating a resin sheet or a prepreg or the like constituting the insulating resin layer. [Simple description of the diagram] Figure 1 shows an optical microscope observation of the shape seen from the section when no undercut occurs at the bottom of the circuit. Fig. 2 is a photomicrograph showing the appearance of the undercut when the undercut occurs at the bottom of the circuit.
第3圖係繪示電路線路底部沒有發生底切現象時，使 乍為表面處理銅箱塊狀銅層剖面的展開阻抗測量結果。 目係'繪不電路線路底部發生底切現象時，使用作 為表面處理鋼箔拔, 塊版鋼層剖面的展開阻抗測量結果。 模式剖面：係繪不用以說明本發明表面處理銅箱層結構的 第6圖係輪^ _ 理銅落層結構的模式剖=本發明含粗化處理層之表面處 【主要元件符號說明】 15 201010539 1〜表面處理銅箱； 2〜銅層； 3〜表面處理層； 4〜粗化處理面； 5〜絕緣樹脂基材； 6〜底切部。Fig. 3 is a graph showing the developed impedance measurement of the profile of the surface treated copper box bulk copper layer when no undercut occurs at the bottom of the circuit. When the undercut phenomenon occurs at the bottom of the circuit, the expansion impedance measurement results of the profile of the steel layer are obtained. Mode section: a pattern section of the copper-bearing layer structure which is not used to illustrate the surface treatment copper box layer structure of the present invention. = The surface of the invention containing the roughening layer [Description of main components] 15 201010539 1 ~ surface treatment copper box; 2 ~ copper layer; 3 ~ surface treatment layer; 4 ~ roughened surface; 5 ~ insulating resin substrate; 6 ~ undercut.
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