201139730 六、發明說明： 【發明所屬之技術頜域】 本發明係關於2層可撓性基板及其製造方法，更具體而 言，係關於當在絕緣體薄膜上依乾式鍍敷法形成底層金屬層 (以下有時亦稱「種子層」），接著再形成銅層時，針孔與凹 缺陷較少的2層可撓性基板及其製造方法。 【先前技術】 現今對LCD、行動電話、數位相機及各種電氣機器等係 要求薄型、小型、輕量化，在其上所搭載的電子零件有朝小 型化的動向，且供形成電子電路用的基板有：堅硬板狀的「剛 性印刷配線板」、以及薄膜狀且具柔軟性並可自由彎曲的「可 撓性印刷配線板（以下有時亦稱「FPC」）」。 特別係FPC應用其柔 』使用於睹如：LCD驅動器 用配線板、HDD(硬碟驅動器）、DVD(數位化多功能光碟）模 組、行動電話的鉸鏈部等之類要求曲折性的地方，因而其 求將會日益增加。 、$ 當作該FPC材料使用者係在聚酿亞胺、聚錯等絕緣薄膜 上，黏貼著銅箔（導體層）的貼銅積層板（以下 、 該CCL大致分類有2種。其一係絕緣薄膜與鋼落（ 利用接著劑進行黏貼的CCL(通常稱「3々ccl」，卩下稱 層CCL」），另-係絕緣薄膜與㈣（導體層）在未使用=著3 100108894 201139730 劑的情況下，利用洗鑄法、層壓法、金屬化法等直接進行複 合的CCL(通常稱「2層CCL」，以下稱「2層c 若將該「3詹CCL」與「2層CCL」進行比較，就製造成 本而言，因為3層CCL在絕緣_、接著劑等的材料費、 處置性等製造上較為容易，因而價格較為低廉。另一方面， 就耐熱性、薄膜化、尺寸安定性等特性而言，則係2層ccl 較為優異，受電路的精細圖案化、高密度安裝化之影響，雖 屬高單價，但可薄型化的2層CCL需求卻逐漸擴大。 再者，在FPC上安裝1C的方法係以在CCL上形成配線 圖案後，再利用會穿透過絕緣體薄膜的光檢測1C位置的 COF安裝為主流，而要求素材自體的薄度與絕緣材料的透 明性。就此點而言亦是2層CCL較為有利。 具有此種特徵的2層CCL之製造方法，大致可歸類為3 種。第1種係在電解鋼箔或軋延銅箔上利用澆鑄法黏貼絕緣 薄膜之方法。第2種係在絕緣薄膜上利用層壓法黏貼電解銅 落或軋延銅箔的方法。第三種係在絕緣薄膜上利用乾式鍍敷 法（此處所謂「乾式鍍敷法」係指濺鍍法、離子鍍覆法、團 簇離子束(cluster i〇n beam)法、真空蒸鍍法、CVD法等）， 在絕緣薄膜上設置薄膜的底層金屬層，再於其上面施行電氣 錢銅而形成銅層的方法。通常將第三種方法稱為「金屬化 法」。 因為該金屬化法係藉由使用乾式鍍敷法及濕式鍍敷法(例 100108894 201139730 如電鍍），而可自由控制其金屬層厚度，因而就金屬層的薄 膜化而言，相較於澆鑄法或層壓法係較為容易。又，因為聚 醯亞胺與金屬層界面的平滑性較高，因而一般認為適用於精 細圖案。 但是，利用金屬化法所獲得的CCL，因為金屬-絕緣薄膜 界面較為平滑，因而金屬與絕緣薄膜間的接著並無法期待一 般所利用的錯定效果，而會有界面的密接強度無法充分顯現 之問題。 即’使用該金屬化法所形成的2層CCL，若施行在121<^ 95%RH、2大氣壓的高溫、高濕、高壓下長時間放置之「 試驗(Pressure Cooker Test，高壓水氣測試）」，相較於初期卢 接強度之下，會出現密接強度大幅降低的傾向。因而，若考 慮在圖案形成步驟的液體光阻塗佈後之乾燥時，會皮 100〜l5〇°C左右的熱，且當在所形成圖案上安裝扣等之力 接合與焊接時亦會施加賊左右的熱，以及 的配線利用阻焊劑等密封樹脂進行密 〜成 化法所製造的2房。ΓΤ… 習知依金屬 化法所製一 2層CCL並不適用於高溫下的精 成、COF讀，導剌熱性、耐_ 〜 或缺的課題。 幵成“要不可 針對此種課題的解決方法係例如專利文獻 以Nl、Cr為主成分的金屬合金層作為絕緣薄1案有声= 間層(種子層）之方法，但當形成更精細圖案時，便 100108894 5 201139730 提尚其財濕性。 再者，專利文獻2記載有下列方法：在塑膠膜基板至少單 面上直接設有由銅或以銅為主成分之合金所構成銅薄膜的 可撓性印刷電路基板，其中，該銅薄膜係具有：具結晶構造 的表面層、以及在該表面層與塑膠膜基板之間設有複晶構造 之底面層的2層構造，且銅薄膜的X射線解析圖案中，晶 格面指數(200)的波峰強度除以晶格面指數（in)的波峰強度 之值X射線相對強度比(2〇〇)/(iil)；(系0.1以下，且底面層係 利用使用含氮之混合氣體的電漿處理而在塑膠膜基板上生 成官能基’而形成由銅或以銅為主成分之合金所構成的金 屬’藉由該金屬與構成塑膠膜基板的原子進行化學鍵結並構 成，而提升耐濕性》然而，該發明係依靠晶格面的控制、與 由電漿處理產生的複合效果而達成’但控制該晶格面在技術 上較為困難，難以安定地進行大量生產。 且，為在絕緣體薄膜上形成薄膜的底層金屬層，一般係使 用真空蒸鍍法、濺鍍法、離子鍍覆法等，但因為依照此種乾 式鍍敷法所獲得的被膜層通常會產生多數個數十μιη〜數百 μπι大小的針孔，因而底層金屬層往往會出現因該針孔所造 成的絕緣體薄膜露出部分。 習知，此種可撓性配線板中，配線所需要的銅導電性被膜 厚度係超過35μιη且至5G/mi為止較為恰#，但因為所形成 配線的寬度亦有數百μιη左右，所以很少會因數十仰針孔 100108894 6 201139730 的存在而導致配線部產生缺陷。 然而’當欲獲得本發明目標之具有窄寬度與窄間距配線部 的可撓性配線板時，如前述，較佳為供配線部形成用的銅被 膜厚度係15μιη以下、較佳係8μηι以下、理想係5gm左右 的極薄厚度’導致配線部產生缺陷的可能性提高。 若針對此種狀況，以使用在形成有底層金屬層的絕緣體薄 膜上形成所需厚度銅被膜層的2層可撓性基板，利用移除法 (subtractive method)進行可撓性配線板製造的情況為例進行 說明，則配線部圖案的形成係依照下述步驟實施。 ⑴在銅導體層上設置具有僅遮蔽配線部但露出非配線部 之銅導體層之所需配線部圖案的光阻層。 (2) 對露出的銅導體層施行化學蝕刻處理而予以除去。 (3) 最後將光阻層予以剝離除去。 所以田使用形成有例如5μιη極薄鋼被膜層厚度的基板， 製以例如配線寬15μηι、配線間距3()卿的窄配線寬、窄配 線間距配線板時，在因乾式鍍敷處理而於基板的底層金屬層 :讀產生的針孔中，較粗大者的大小將達數十阿至數百㈣ :等級，因而當形成一左右厚度的紐鋼被膜時，因針孔 所造成的絕緣體薄膜露㈣分幾乎無法被埋藏，所以該露出 部分(即導體層的缺損部分)會牽涉到配線部，導致配線部在 針孔位置出現缺知而成為配線缺陷，即非如此亦會成為導致 配線部密接不良的原因。 100108894 7 201139730 因此，專利文獻3揭示有：規定金屬聚醯亞胺薄膜積層體 之針孔，的技術。但是，專利文獻3並非揭示蒸鐘膜的針 孔而疋規定電鍍銅後的針孔，關於蒸鍍膜與底層金屬層的 針孔並無任何揭露。 再者，作為解決上述問題的方法，專利文獻4係記載有： 在絕緣體薄膜上湘乾式缝法形成底層金屬層，⑽再施 予利用無電解織的銅被覆層作為中間金屬層，俾將因針孔 所造成的絕緣體薄膜露出部分予以被覆之方法。 但是，該方法雖確實可某程度地消除因針孔所造成的絕緣 體薄膜露出部分’但另__方面，已得知無電賴銅處理時所 使用的鑛敷液與其前處理液等，會從已形成的大小各式各樣 之針孔部分滲透入絕緣體薄膜與底層金屬層之間，此現象有 可旎會成為對底層金屬層的密接性、以及爾後利用所形成電 錢銅達成的導體層密接性構絲礙之㈣，並非為充分的解 決策略。又，即便電脑可喊絕緣體薄膜露出部分， 但因為絕緣薄臈與銅層間之密接力低，因而若底層金屬層有 針孔’便會成為導致密料良與絕緣可#性降低的原因θ。 [先行技術文獻] [專利文獻] 專利文獻1 :曰本專利特開2006-13152號公報 專利文獻2 :日本專利第3563730號 專利文獻3:曰本專利特開平號公報 100108894 8 201139730 專利文獻4:日本專利特開平10-195668號 【發明内容】 (發明所欲解決之問題） 本發明之目的係解決使用乾式鍍敷法的2層可撓性基板 製造時之上述問題，並提供：不會有因在絕緣體薄膜上利用 乾式鑛敷處理形成底層金屬層時所產生的針孔而造成之銅 箔膜層與銅層缺損，底層金屬層的缺損較少，且絕緣體薄膜 與底層金屬層間之密接性、耐蝕性、耐水性均優異之2層可 撓性基板，特別係適用於精細圖案形成、COF安裝的2層 可撓性基板，及其製造方法。 (解決問題之手段） 本發明者等發現藉由使用在絕緣體薄膜至少單面上，於未 經由接著劑的情況下，利用乾式鍍敷法形成底層金屬層，而 在該底層金屬層上形成所需層厚之銅薄膜層及/或銅層的2 層可撓性基板，其中，該絕緣體薄膜係經施行表面處理，且 寡聚物量係表面處理前的寡聚物量之70%以下的2層可撓 性基板，便可獲得不會有因形成底層金屬層時所產生的針孔 而造成的銅薄膜層及銅層缺損，且底層金屬層的缺損亦較 少’且絕緣體薄膜與底層金屬層間之密接性、耐蝕性、及耐 水性均優異的2層可撓性基板，亦可適用於具有窄寬度、窄 間距配線部的可撓性配線板，遂完成本發明。 本發明第1發明係2層可撓性基板，係在絕緣體薄膜至少 100108894 9 201139730 單面上，於未經由接著劑的情況下，利用乾式鍍敷法形成底 層金屬層’並在該底層金屬層上利用乾式鍍敷法形成銅薄膜 層者，其中’絕緣體薄膜係對至少其中一面施行表面處理， 且僅對絕緣體薄膜其十一面施行該表面處理後的寡聚物 量，係表面處理前的寡聚物量之70%以下。 本發明第2發明係第1發明的銅薄膜層具有50nm〜500nm 厚度，且皆無直徑超過30μπι的針孔，且直徑5/xm以上、 30μιη的針孔係每1平方公尺45000個以下。 本發明第3發明係第1及第2發明的2層可撓性基板，其 中，在銅薄膜層上利用濕式鍍敷法形成銅濕式鍍敷層。 本發明第4發明係第3發明的銅濕式鍍敷層具有 0.5/rni〜12μιη厚度，且皆無直徑或最大缺陷長超過2〇/xm的 凹缺陷，且直接或最大缺陷長lO^rn以上、20/xm以下的凹 缺陷係每1平方公尺2200個以下。 本發明第5發明係第1至第4發明的2層可撓性基板，其 中’底層金屬層係具有5nm〜50nm層厚，且由含有以鉻為主 的添加元素6重量％〜22重量％而其餘則為鎳所構成的鎳_ 鉻系合金所形成，且在底層金屬層上所設置之由銅薄膜層與 銅濕式鍍敷層所構成的導體層（銅層）之層厚係恥瓜。 本發明第6發明係第1至第5發明的絕緣體薄膜為從聚醯 亞胺系薄膜、聚醯胺系薄膜、聚酯系薄膜、聚四氟乙烯系薄 膜、聚苯硫醚系薄膜、聚萘二甲酸乙二料、薄膜、液晶聚合 100108894 10 201139730 物系薄膜中選擇的樹脂薄膜。 本發明第7發明係第1至第6發明的表面處理係在壓力 0.8Pa〜4.0Pa的惰性環境下，對絕緣體薄膜的表面，施行利 用1500V〜3000V直流電壓之電漿放電處理。 本發明第8發明係第7發明的表面處理之惰性環境係氮環 境，且表面處理後的PCT剝離強度係初期剝離強度的7〇〇/。 以上。 本發明第9發明係第1至第6發明的表面處理係在壓力 0.8Pa〜4.0Pa的惰性環境下，對絕緣體薄膜的表面施行利用 800V〜2000V高頻電壓之電漿放電處理。 本發明第10發明係第9發明的表面處理之惰性環境為氮 環境，且表面處理後的PCT剝離強度係初期剝離強度的70% 以上。 本發明第11發明係在絕緣體薄膜至少單面上，於未經由 接著劑的情況下，利用乾式鍍敷法形成底層金屬層，並在上 述底層金屬層上利用乾式鍍敷法形成銅薄膜層的2層可撓 性基板之製造方法，其中，對該絕緣體薄膜的表面在壓力 0.8Pa〜4.0Pa的惰性環境下，施行利用對電漿電極的配對放 電電極間施加2〜100秒鐘的電漿放電之表面處理後，形成底 層金屬層。 本發明第12發明為第11發明的利用電漿放電之表面處 理，係對電漿電極的放電電極間施加1500V〜3000V直流電 100108894 11 201139730 壓。 本發明第13發明為第η發明的利用電漿放電之表面處 理，係對電漿電極的放電電極間施加8〇〇V〜2000V高頻電 壓。 本發明第14發明係在絕緣體薄膜至少單面上，於未經由 接著劑的情況下，利用乾式鍍敷法形成底層金屬層，並在該 底層金屬層上利用乾式鍍敷法形成銅薄膜層的第8發明之2 層可撓性基板之製造方法，其中，對絕緣體薄膜的表面在壓 力0.8Pa〜4.0Pa的氮環境下，施行利用對電漿電極的配對放 電電極間施加1500V〜3000V直流電壓2〜1〇〇秒鐘而產生的 電漿之表面處理後，形成底層金屬層。 本發明第15發明係在絕緣體薄膜至少單面上，於未經由 接著劑的情況下，利用乾式鍍敷法形成底層金屬層，並在該 底層金屬層上利用乾式鍍敷法形成銅薄膜層的第1〇發明之 2層可撓性基板之製造方法，其中’對絕緣體薄膜的表面在 壓力0.8Pa〜4.0Pa的氮環境下，施行利用對電漿電極的配對 放電電極間施加800V〜2000V高頻電壓2〜1 〇〇秒鐘而產生的 電漿之表面處理後，形成底層金屬層。 本發明第16發明為第11至第15發明的乾式鍍敷法係真 空蒸鍍法、濺鍍法、及離子鍍覆法中之任一者。 本發明第17發明為第11至第16發明的絕緣體薄膜為從 聚醯亞胺系薄臈、聚醯胺系薄膜、聚酯系薄膜、聚四氟乙烯 100108894 12 201139730 系薄膜、聚苯硫醚系薄膜、聚萘二曱酸乙二酯系薄膜、液晶 聚合物系薄膜中選擇的樹脂薄膜。 (發明效果） 根據本發明，可獲得不會有因形成底層金屬層時所產生的 針孔造成的銅薄膜層及銅濕式鍍敷層缺損，底層金屬層的缺 • 損亦較少，且絕緣體薄膜與底層金屬層間之密接性與耐钮性 • 均優異的2層可撓性基板。該2層可撓性基板亦適用於具窄 寬度、窄間距配線部的可撓性配線板，因而發揮工業上顯著 的效果。 【實施方式】 1. 2層可撓性基板 本發明的2層可撓性基板係構成在絕緣體薄膜至少單面 上，於未經由接著劑的情況下，利用乾式鍍敷法設有底層金 屬層，並在該底層金屬層上設有銅薄膜層的構造，其特徵在 於：該絕緣體薄膜係藉由施行表面處理，而使其寡聚物量成 為在表面處理前之寡聚物量的70%以下寡聚物量，藉由對絕 緣體薄膜施行表面處理’而使得相較於表面處理前的寡聚物 量’成為70%以下募聚物量的表面’便可抑制粗大針孔的產 生。 再者’本發明的2層可撓性基板較佳係具有厚度 50nm〜500nm的銅薄膜層’且皆無直徑3〇μιη的針孔，且直 徑5/xm至30μηι的針孔係每1平方公尺45000個以下。 100108894 13 201139730 1 -1.銅薄膜層 銅薄膜層的厚度較佳係50mn〜500nm。 务該銅vl膜層的厚度未滿5Qnm，當利用後續屬於濕式鐘 敷法之一的電鍍鋼法在鋼薄膜層表面上施行銅濕式鍍敷層 的成膜時’銅_層的電阻值會提高，且會使銅層表面的鑛 敷外觀劣化。另外，當利用電鍍銅法進行銅濕式鍍敷層的成 膜時，銅薄膜層係作為陰極而發揮機能，而銅薄膜層的電阻 值便會構成問題。另一方面，若銅薄膜層的厚度超過5〇〇nm 並予以成膜，則銅薄膜間的針孔雖有減少，但在利用乾式鍍 敷法將銅薄膜層成膜較耗時，經濟性較差。 一般而言’銅薄膜層與鋼濕式鍍敷層係越厚則所成膜的銅 越能成長並埋藏針孔，因而針孔較小，甚至會變少。所以， 相較於乾式錢敷法’利用成膜速度較快速的濕式鑛敷法在銅 薄膜層表面上設置銅濕式鍍敷層，而製造2層可撓性基板。 該2層可撓性基板係利用濕式鍍敷使其表面的針孔數變微 小。但是’即便2層可撓性基板表面的針孔被埋藏，但底層 金屬層與銅薄膜層的針孔卻呈未被埋藏狀態。 所以，若在未抑制底層金屬層與銅薄膜層的針孔大小與數 量之情況下，形成窄配線間距的配線部圖案，配線部無底層 金屬層的地方便會露出，導致成為配線缺陷，即便非如此亦 會成為導致配線部密接不良的原因。 再者’銅薄膜層的針孔雖利用濕式鑛敷而被埋藏，但若有 100108894 14 201139730 銅薄膜層的針孔，職層金屬層錢•敷前便會露出於大 氣中’因而底層金屬層便會變質，導致成為配線二陷、及配 線部密接不良的原因。 因而，本發明的銅薄膜層中，即便具有針孔亦是大小為 直徑5师〜3_的針孔較佳係在每！平方公尺45議個: 下範圍内。另外，直徑未滿_ $針孔因為會導致配線缺 陷、密接不良的情況較少，且檢測亦較為_，因而並未規 定數量。 藉由使社述構造’便可獲得竹有_成底層金屬層時 所產生的針孔而造成的銅㈣部缺損，且底層金屬層的缺損 較少，且絕賴薄膜與底層金制間之密接性、耐錄、及 财水性均優異的2層可撓性基板。 1-2.絕緣體薄膜(基材）之表面處理 對基材之絕緣體薄膜的表面處理，係使用電激處理實施。 表面處理係可對絕緣體薄膜的單面實施，但對雙面實施較具 效果。 處理條件係惰性環境下、0.8Pa〜4.0Pa壓力。在壓力未滿 〇.奶的惰性環境下，電漿放電不易呈找，若在超越壓力 4.〇Pa的惰性環境下，因為處理會變為過強，因而會有處理 時導致絕緣薄膜出現起鮍情況，故較不佳。 在電漿電極的配對放電電極間施加15〇〇v〜3〇〇〇v直流電 壓，而施行直流電漿(DC電漿）處理。若該直流電壓未滿 100108894 15 201139730 15講，關用電祕行的處理，，無法顯現出初期密接 強度的上升，若超W_V，則因為處理會變為過強，因而 處理時容易導致絕緣薄膜出現起皺與變形，反將導致使耐熱 密接強度與PCT剝離強度降低的結果，因而較不佳。 在電聚電極的配對放電電極間施力π 8〇〇v〜2000V高頻電 壓，而施行高頻M(RF f漿）處理。若該高頻電壓未滿 800V，則利用電漿施行的處理過弱，無法顯現出初期密接 強度的上升，若超過2000V，則因為處理會變為過強，因而 處理時容易導致絕緣薄膜出現起皺與變形，因而較不佳。 另外，此處所謂「惰性環境下」係指氮氣、氬等第18族 氣體’亦可為氮與氬的混合氣體，別係若在氮環境下利用 電渡施行表面處理’便可使PCT剝離強度成為初期剝離強 度的70%以上。 利用電漿放電施行的處理時間較佳係2秒〜100秒。若電 漿放電的處理時間未滿2秒，則處理過弱，導致對初期密接 強度的上升不具貢獻，若超過100秒持續施行處理，則影響 會過大，導致絕緣薄膜容易發生起皺與變形，反會導致耐熱 密接強度與PCT密接強度降低的結果，因而較不佳。另一 方面，從生產性的觀點而言，超過100秒的長處理時間亦較 不佳β 基材的絕緣體薄膜係寡聚物量越多，則銅薄膜層的針孔越 增加。 100108894 16 201139730 田對絕緣H膜的單面施行表面處理時’經表面處理後的 絕緣體薄膜寡聚物量’相較於表面處理前的寡聚物量，較佳 係在70 /〇以下又’當對絕緣體薄膜雙面施行表面處理時， 、屢表面處理後的絕緣體薄膜之寡聚物量，相較於表面處理前 的寡聚物量，較佳為35%以下， 利用此項表面處理導致S聚物量減少的理由係寡聚物會 因表面處理而被除去的緣故所致Ob處，所謂「寡聚物」係 分子$ 300〜14000範圍的分子，當製造絕緣體薄膜時，並未 充分進行聚合而會殘留於薄膜内的分子。該寡聚物量的判定 係依如下述測定寡聚物量而求得。從絕緣體薄膜中使用四氫 咬喃等溶劑萃取寡聚物，再將該萃取物使用尺寸排除層析法 (SEC法）測定分子量分佈即可。 1-3.底層金屬層 底層金屬層的層厚較佳係5nm 〜50nm。 若利用乾式鍍敷法所獲得之由主要以鉻為添加元素的鎳_ 鉻系合金所構成底層金屬層之層厚未滿5nm，即便經由後續 的處理步驟’底層金屬層的長期密接性仍會出現問題。且， 若底層金屬層的層厚未滿5 nm ’則在施行配線加工時的蝕刻 液會滲入，導致發生配線部浮起等情形，造成配線剝離強度 明顯降低等問題發生，因而較不佳。 另一方面，若底層金屬層的層厚超過5〇nm，則當施行配 線部的加工時，會導致底層金屬層的除去較為困難，且會有 100108894 17 201139730 發生毛裂三勉曲等而導致密接強度降低的情況，因而較不 佳又右層厚係厚於5〇賊，則因為較難施行银刻，因而 仍係不佳。 該底層金屬層的成分組成從耐熱性與耐餘性的觀點 η 12 f t〇/-22 tt%〇 22重=，造成耐熱性降低，另—方面1鉻比例超過 貝田施仃配線部加工時，底層金屬 困難，因而較不任。n .^ 。且，在該鎳-鉻合金令，於提升耐熱性 與财银性之目的 “'、 的下，可配合目的特性適當添加過渡金屬元 素0 • θ金屬層的情況’就本發明的2層可撓性基板而 ，該底層金屬層的層厚較佳係 15nm〜50nm ° 再者’底廣金屬層較佳係由鉻比例為4 重量％〜22重量％， 且更進^ 3有翻5重量％〜40重量％ ’其餘則為錄的合金 構成。 絡比例為4奮普〇/ Λ、 至夏/〇〜22重量％，係為防止因熱劣化導致耐 ”、、卿強度明顯降低所必要者，若鉻比例低於4重量％，則 Ρ便有I目添力α ’仍無法防止雜剝離強度因熱劣化而明顯降 低因而較不佳°又’若鉻比例多於22重量％，則蝕刻會 因而較不佳°因此，鉻的情況，更佳係4重量 /〇 15重量/〇、特佳係5重量％〜12重量％。 h 4求耐飿性、絕緣可靠性的提升，減例較佳係5 100108894 201139730 重量％〜40重量％。若鉬比例少於5重量％，則不會顯現出 添加效果，無法呈現耐蝕性、絕緣可靠性的提升，因而較不 佳。又’若鉬比例超過40重量％ ’則會有耐熱剝離強度極 端降低的傾向，因而較不佳。 再者’通常鎳基合金靶材的情況，若鎳比例大於93重量 °/〇’則濺鍍乾材本身便會成為強磁性體，當利用磁控藏鍍進 行成膜時，會導致成膜速度降低，因而較不佳，而當利用濺 鍍形成本發明的底層金屬層時，因為濺鍍的乾材組成係成:、 鎳量93重量％以下’因而即便使用磁控錢錢法進行成膜時， 仍可獲得良好的成膜速率。另外，在該鎳_鉻_鉬合金中γ於 提升耐熱性與耐蝕性之目的下，可配合目的特性適當添加、" 渡金屬元素。 * °遇 再者，在該底層金屬層中，除鎳_鉻胃鉬合金之外，尚可疒 在有因靶材製作時被取入等而含有的丨重量％以下之不可子 免的雜質。 避 另外，在底層金屬層及銅薄膜層的形成時係使用乾式鍍數 法，而在乾式鍍敷法中，較佳係使用真空蒸鍍法、濺鍍 或離子鍛覆法中之任*^者。 1_4·絕緣體薄膜（基材） 再者，本發_ 2料撓性基板中，基材的絕緣體薄_ 佳係使用從聚醯亞胺系薄膜、聚醯胺系薄膜、聚酯系薄唭 聚四氟乙烯系薄膜、聚苯硫醚系薄膜、聚萘二甲酸乙二酽系 100108894 19 201139730 薄膜、液晶聚合物系薄膜中選擇的樹脂薄膜。 ❹，較適宜使用薄膜厚度25〜75阳的絕緣體.薄膜。另 外’玻璃纖維等無機質材料，因為會成為雷射加工與化學蚀 刻的障礙，因而較佳不要使用含有無機質材料的基板。 1-5.銅層（導體層） 本發明的2層可撓性基板係在底層金屬層上姻乾式鍍 敷法形成銅賴層後’再於該銅_層上利用濕式鍵敷法設 置銅濕式織層，更積層使含有__與_式鍵敷層的 厚度為1 Onm〜12/im之銅層而形成。 當僅使用乾式鑛敷法形成銅層時，乾式鐘敷法係真空蒸鑛 法、舰法、祕子賴法中之任—者，相胁濕讀敷法， 亦會有成膜速度較慢之情形，而較適於形成較薄銅層的情 況。另-方面’利用乾式II敷法形成鋼薄膜層後，再於銅薄 膜層上利用濕式鍍敷法積層形成銅層，係適用在短時間形成 較厚銅層，有助於生產性提升。 本發明的2層可撓性基板若最表面為銅薄膜層，則將直徑 5Mm〜30/mi的針孔數抑制為每！平方公尺45〇〇〇個以下，若 最表面為銅濕式鍍敷層，則將直徑或最大缺陷長為 10/xm〜20/mi的凹缺陷數量抑制為每】平方公尺22⑼個以 下，便適用於製造窄間距配線的可撓性配線板。 2.2層可撓性基板之製造方法 以下，針對本發明的2層可撓性基板之製造方法進行詳 100108894 20 201139730 述。 *本發明中，對#作基材用之從聚酿亞胺㈣膜、聚酿胺系 薄膜、聚醋系薄膜、聚四氟乙稀系薄膜、聚苯硫_薄膜、 聚萘二甲m㈣膜、液晶聚合物㈣财選擇之樹脂 薄膜的絕緣體顏，於其單面或雙面上，在未經由接著劑的 情況下形成底層金屬層，並在該底層金屬層上形成銅薄膜 層。 基材的絕緣體薄膜通常係含有水分，必須在利用乾式鍛敷 法形成由錄·鉻系合金構成的底層金屬層之前，便施行大氣 乾燥或真m俾將崎體薄财存在的水分去除。若此 項動作不;i，便會導致與底層金屬層間之密接性變差。 ¥利用乾式鑛敷法形成底層金屬層時，例如使用R〇U t〇 Roll的捲取式濺鍍裝置形絲層金屬層時，便將具有底層金 屬層組成的靶材裝設於濺鍍用陰極上。 首先’將已安裝有絕緣體薄膜的濺鍍裝置内施行真空排氣 後，導入氮或氬、或氮與氬的混合氣體，並將裝置内保持於 壓力0.8Pa〜4.0Pa的惰性環境下，對㈣電極的配對放電電 極間施加15〇〇V〜3_v直流電壓、或8〇〇v〜2〇〇〇v高頻電 壓’並依2秒〜_秒的時間细轉施行表面處理。 其次，導入氬氣，將裝置内保持於13pa左右，再一邊將 在裝置内的捲取輥、繞出親上所t設之絕緣體薄膜，依每分 鐘3m左右的速度進行搬送，―邊從陰極所連接的麟用直 100108894 201139730 流電源供應電力而開始進行濺鍍放電’便在絕緣體薄膜上形 成由鎳-鉻系合金、或錄_鉻-翻合金所構成的底層金屬層。 銅薄膜層的形成係與底層金屬層的情況同樣，使用已將銅 靶材裝設於濺鍍用陰極上的濺鍍裝置’將銅薄膜層成膜。此 時，底層金屬層與銅薄膜層較佳係在同一真空室内連續形 成，當形成底層金屬層後’將薄膜取出於大氣中，並使用其 他濺鍍裝置形成銅薄膜層時，必須在成膜以前便預先施行充 分的脫水。 再者，當在利用乾式鍵敷法形成銅薄膜層後，再於銅薄膜 層上利用濕式鍍敷法形成銅濕式鍍敷層時，較佳係施行例如 無電解鍍銅處理。該無電解鍍敷處理係藉由在可撓性基板整 體上形成無電解鍍銅層，即便有存在針孔的情況，仍會覆蓋 該露出面而使可撓性基板面整體呈良導體化’藉此便可抑制 降低針孔的影響。但，當施行無電解鍍銅處理時，必須留意 因無電解鍍敷液與其前處理液所造成的滲透並決定條件。 另外’利用該無電解銅鍍敷液所形成的鍍銅濕式鍍敷層之 層厚’係只要當可修復基板面上因針孔所造成的缺陷，且施 行電鍍銅鍍敷液處理時，不會因電鍍銅鍍敷液而溶解之程度 的層厚便可’較佳係〇 Ogm範圍。 已依此形成無電解鍍銅濕式鍍敷層的基板，係為能形成最 終所需層厚的銅濕式鍍敷層，而施行電鍍銅處理，便可獲得 不會受因底層金屬層形成時所產生的各種大小針孔造成之 100108894 22 201139730 影響而良好’且密接度較高的2層可撓性基板。另外，本發 明中所施行的電鍍銅處理係只要採取依常法施行的電鍍銅 法之諸項條件便可。 依此在底層金屬層與銅薄膜層上所形成銅濕式鍍敷層的 層厚，最厚亦較佳在12μπ1以下。設為此種層厚的理由係為 忐獲得窄配線寬度、窄配線間距的配線板。 另外’是否在銅薄膜層的表面上利用濕式鍍敷法形成銅濕 式鍍敷層’係依照配線部圖案的製造方法適當選擇。 例如，當利用公知移除法形成配線部圖案時，係利用底層 金屬層、銅薄膜層、及銅濕式鍍敷層形成配線部，因而必須 形成銅濕式鍍敷層。以成為配線部所要求的層厚。此處所謂 移除去」，係在2層可撓性基板的銅層表面上設置光阻 層，再於該綠膚上設置具有既定線圖錢料，再從其 上方照射料線而曝光’賴影，便獲制於將不需要的鋼 層等予以則的ϋ刻遮罩，接著將露出的銅層施行_而除 去，接著再將殘存的光阻層予以除去之方法。作為配線部不 需要的地方之底層金屬層亦被钱刻除去，而形成配線部圖幸 的方法。 另方面，當利用半添加法形成配線部圖案時，亦可在鋼 薄膜槽上湘濕讀敷法設置銅濕式綠層，亦可未設置5。 此處所謂「半添加法」，係指在2層可紐基㈣金屬層（由 底層金屬層與銅薄膜㈣成的金屬層、或由底層金屬層、鋼 100108894 23 201139730 薄膜層及鋪式鍍敷層構成的金屬層）之某表面上設置光阻 層’再於該光阻層上設置具有既定配線圖案的遮罩，再從其 上方照射紫外線而曝光，經_影，便獲得用於在金屬層表面 上電鐘銅而形成配線部的錢數用遮罩，將露出於開口部的金 屬層當作陰極，經親㈣—線部，接著再將光阻層予以 除去，再施行軟闕而將除配線部以外的不需要之2層可撓 性基板表面金屬予以除去’便完成配線部而形成配線部圖案 的方法。 [實施例] 以下，利用實施例詳細說明本發明，惟本發明並不僅偈限 於該等實施例。各特性的測定係使用以下所示手段實施。 針孔的測定方法係將利用乾式紐法所獲得之底層金屬 層與銅薄膜層的積層體，利用穿透方式予以定位，再利用光 學顯微鏡測定其大小，並測定直徑一至3〇卿的針孔每丄 平方公尺之個數。 寡聚物量的評估方法係將經電漿處理後的絕緣薄膜利用 四氫吱喊進行萃取，再將萃取物使用尺寸排除層析法(SEC 法），測定380〜13500分子量的寡聚物比例，將電製處理前 的數值設為1GG%，並進行峰且視為「寡聚物量」。 剝離強度的測定方法係依照根據IPC-TM-650、 NUMBER2.4.9的方法實;^，並視為「初期剝離強度」。但， 導線寬係設為lmm，剝離角度係設為9G。。導線係利用移除 100108894 24 201139730 法形成 、土材放置於15GC_箱中⑹小時，取出後放置至成為 9〇°韌離強度而實施，並視為「耐熱剝 才*、、、丨生的指樑係將已形成1mm導線薄獏的薄 考箱中 室溫為止，藉由評估 又 離強度 、。愚11的和;^係將已形成^麵導線薄膜的薄膜基材，在 2大氣^的熱壓產尚中放置96 ]、時，S出後放置至成 為至’皿為止，藉由評估9〇°剝離強度而實施，並視為「PCT 剝離強度」。 、Pt3之測疋方去係針對利用電鍵法所獲得銅濕式錄敷 層表面’使用光學顯微鏡進行觀察，並測定凹缺陷的大小。 #凹缺陷係圓形的情況，測定直徑10叫至20阿者每i 平方A尺的個數’ §凹缺陷係除圓形以外的情況，則將凹缺 陷之缺陷部長度最大值視為「最大缺陷長」，駭ΙΟμιη至 20/mi凹缺陷每1平方公尺的個數。 (比較例1) 首先’比較例1係顯示在未施4亍電聚處理情況下施行膜形 成的2層可撓性基板之特性。 在厚度38/mi聚醯亞胺薄膜(東麗杜邦公司製，註冊商標 「Kapton 150EN」）的單面上形成底層金屬層的第i層，該 底層金屬層的第1層係使用20重量％〇见合金靶材(住友 金屬礦山股份有限公司製），在Ar環境中利用直流濺鍍法， 依成膜速度〇.7nm/sec將20重量％〇_犯合金底層金屬層成 100108894 25 201139730 膜。對3外依照相同條件成膜的其中一部分，使用穿透式電 子顯微鏡(TEM:日立製作所股份有限公司製）測定層厚，結 果為0.02/xm。在上述20重量％(>_见膜上更進一步形成第2 層，該第2層係使用Cu靶材(住友金屬礦山股份有限公司 製），利用濺鍍法形成10〇nm厚度的銅薄膜層，接著再利用 銅電鍍法成膜至8/mi厚度為止。 所獲得2層可撓性基板的初期剝離強度係471N/m，pCT 剝離強度係253N/m，乾式基板的針孔數係76714個/m2，寡 聚物量係100%，並未獲得充分的初期剝離強度。 (實施例1) 以下’例示在絕緣薄膜上施行利用電槳處理之表面處理的 情況β 將厚度38μιη聚醯亞胺薄膜（東麗杜邦公司製，註冊商標 「Kapton 150ΕΝ」）在氮氣壓i.6Pa的環境下，於電漿電極 的配對放電電極間施加2000V直流電壓5〇秒鐘，僅對底層 金屬層成膜面施行電漿處理。接著，在聚醯亞胺經電漿處理 過的面上形成底層金屬層的第1層，該底層金屬層的第i 層係使用20重量％Cr-Ni合金靶材(住友金屬礦山股份有限 公司製），在Ar環境中利用直流濺鍍法，依成膜速度 〇.7nm/sec將20 fi%Cr-Ni合金底層金屬層成膜。 對另外依照相同條件成膜的其中一部分，使用穿透式電子 顯微鏡(TEM :日立製作所股份有限公司製）測定層厚，結果 100108894 26 201139730 為0_02μηι。在該20重量％Ni-Cr膜上更進一步形成第2層， 該第2層係使用Cu靶材(住友金屬礦山股份有限公司製）， 利用濺鍍法形成銅薄膜層l〇〇nm厚度，接著再利用銅電鍍 法成膜至8μιη厚度。 所獲得2層可撓性基板的初期剝離強度係624N/m，PCT 剝離強度係434N/m，乾式鍍敷(底層金屬層與銅薄膜層的積 層體。以下稱「乾式鍍敷」）的針孔數係36443個/m2，且皆 無直徑超過30μηι的針孔，寡聚物量係70%，凹缺陷數係 1951個/m2’且皆無直徑或最大缺陷長超過2〇μιη的凹缺陷。 (實施例2) 將厚度38/mi聚醯亞胺薄膜(東麗杜邦公司製’註冊商標 「Kapton 15〇ΕΝ」）在氮氣壓2.4Pa的環境下，於電聚電極 的配對放電電極間施加2000V直流電壓5〇秒鐘，僅對底層 金屬層成膜面施行電漿處理。接著’在聚醯亞胺經電漿處理 過的面上形成底層金屬層的第1層，該底層金屬層的第1 層係使用20重量％Cr-Ni合金乾材(住友金屬礦山股份有限 公司製）’在Ar環境中利用直流濺鍍法，依成膜速度 0.7nm/seC將20重量％Cr-Ni合金底層金屬層成膜。對另外 依照相同條件成膜的其中一部分，使用穿透式電子顯微鏡 (TEM:曰立製作所股份有限公司製）測定層厚，結果為 0.02μιη。在該20重量％Ni-Cr膜上更進一步形成第2層，該 第2層係使用Cu靶材(住友金屬礦山股份有限公司製），利 100108894 27 201139730 用满:鑛法形成銅薄膜層100nm厚度，接著再利用銅電鐘法 成膜至8μηι厚度。 所獲得2層可撓性基板的初期剝離強度係635N/m，PCT 剝離強度係463N/m，乾式鍍敷的針孔數係15571個/m2，且 皆無直徑超過30μηι的針孔，寡聚物量係56%，凹缺陷數係 1645個/m2’且皆無直徑或最大缺陷長超過20μιη的凹缺陷。 (實施例3) 將厚度38/rni聚醯亞胺薄膜(東麗杜邦公司製，註冊商標 「Kapton 150EN」）在氮氣壓3.1Pa的環境下，於電漿電極 的配對放電電極間施加2000V直流電壓50秒鐘，僅對底層 金屬層成膜面施行電漿處理。接著，在聚醢亞胺經電漿處理 過的面上形成底層金屬層的第1層，該底層金屬層的第1 層係使用20重量％Cr-Ni合金乾材(住友金屬礦山股份有限 公司製），在Ar環境中利用直流濺鍍法，依成膜速度 0.7nm/sec將20重量％Cr-Ni合金底層金屬層成膜。對另外 依照相同條件成膜的其中一部分，使用穿透式電子顯微鏡 (TEM :曰立製作所股份有限公司製）測定層厚，結果為 0·02μιη。在上述20重量％Cr-Ni膜上更進一步形成第2層， 該第2層係使用Cu乾材(住友金屬礦山股份有限公司製）， 利用藏鐘法形成銅薄膜層lOOnm厚度，接著再利用銅電鍍 法成膜至8μηι厚度。201139730 VI. Description of the invention: [Technical jaw region to which the invention pertains] The present invention relates to a two-layer flexible substrate and a method of manufacturing the same, and more particularly to forming an underlying metal layer by dry plating on an insulator film (hereinafter sometimes referred to as "seed layer"), and then a two-layer flexible substrate having less pinholes and concave defects when a copper layer is formed, and a method for producing the same. [Prior Art] Today, LCDs, mobile phones, digital cameras, and various types of electrical equipment are required to be thin, compact, and lightweight. The electronic components mounted thereon are oriented toward miniaturization and are used to form substrates for electronic circuits. There are: a rigid printed wiring board with a rigid plate shape, and a flexible printed wiring board (hereinafter sometimes referred to as "FPC") which is flexible and flexible. In particular, the FPC application is used in places such as LCD driver wiring boards, HDD (hard disk drives), DVD (digital versatile optical disk) modules, hinges of mobile phones, and the like. Therefore, its demand will increase. , as a user of the FPC material, a copper-clad laminate in which a copper foil (conductor layer) is adhered to an insulating film such as a polyimide or a polystyrene (hereinafter, the CCL is roughly classified into two types. Insulating film and steel drop (CCL adhered by adhesive (commonly called "3々ccl", 卩 under layer CCL"), another type of insulating film and (4) (conductor layer) are not used = 3 100108894 201139730 In the case of CCL (usually referred to as "two-layer CCL" by means of a washing method, a lamination method, a metallization method, etc., hereinafter, "two layers of c, if the "3 Zan CCL" and "two layers of CCL" In comparison, in terms of manufacturing cost, the three-layer CCL is relatively easy to manufacture in terms of material cost and handling property such as insulation, adhesive, etc., and is inexpensive. On the other hand, heat resistance, thin film formation, and size In terms of stability and other characteristics, the two-layer ccl is excellent, and it is affected by fine patterning and high-density mounting of the circuit. Although it is a high unit price, the demand for a thin two-layer CCL is gradually expanding. The method of installing 1C on the FPC is to form a wiring pattern on the CCL. The COF that detects the light passing through the insulator film at the 1C position is installed as the mainstream, and the thinness of the material itself and the transparency of the insulating material are required. In this regard, it is also advantageous for the two-layer CCL. The manufacturing method of the two-layer CCL can be roughly classified into three types. The first type is a method of adhering an insulating film to an electrolytic steel foil or a rolled copper foil by a casting method, and the second type is laminated on an insulating film. A method of adhering electrolytic copper or rolling copper foil. The third method uses dry plating on an insulating film (here, "dry plating" means sputtering, ion plating, cluster ions A method of forming a copper layer on an insulating film by providing an underlying metal layer of a thin film and a copper layer on the insulating film, usually in the form of a cluster i〇n beam method, a vacuum deposition method, a CVD method, or the like. This method is called “metallization method.” Because the metallization method is free to control the thickness of the metal layer by using dry plating and wet plating (eg, 100108894 201139730 such as electroplating), the metal layer is Thinning, compared to The casting method or the lamination method is relatively easy. Moreover, since the interface between the polyimide and the metal layer has high smoothness, it is generally considered to be suitable for a fine pattern. However, the CCL obtained by the metallization method is metal-insulated. Since the interface between the metal and the insulating film is relatively smooth, the misalignment effect generally used cannot be expected, and the adhesion strength of the interface cannot be sufficiently exhibited. That is, the 2-layer CCL formed by the metallization method is used. If implemented at 121 <^ 95% RH, "Pressure Cooker Test" at a high temperature of 2 atm, high humidity, and high pressure for a long time. Compared with the initial strength of the joint, there is a large bond strength. The tendency to decrease. Therefore, in consideration of drying after application of the liquid photoresist in the pattern forming step, heat of about 100 to 15 ° C is applied to the skin, and is also applied when force is applied to the formed pattern by bonding or the like. The heat of the thief and the wiring are sealed by a sealing resin such as a solder resist to make the 2 bedrooms manufactured by the dense method. ΓΤ... The two-layer CCL made by the metallization method is not suitable for the high temperature synthesis, COF reading, heat conduction, resistance _ ~ or lack of problems. For example, a method for solving such a problem is a method in which a metal alloy layer containing Nl and Cr as a main component in the patent document is used as an insulating thin film case with an acoustic layer (seed layer), but when a finer pattern is formed Further, Patent Document 2 discloses a method in which a copper film composed of copper or an alloy containing copper as a main component is directly provided on at least one surface of a plastic film substrate. A flexible printed circuit board comprising: a surface layer having a crystal structure; and a two-layer structure in which a bottom layer of a polycrystalline structure is provided between the surface layer and the plastic film substrate, and the copper film X In the ray analysis pattern, the peak intensity of the lattice plane index (200) is divided by the peak intensity of the lattice plane index (in). The relative intensity ratio of the X-rays is (2〇〇)/(iil); 1 or less, and the bottom layer is formed by using a plasma containing a mixed gas containing nitrogen to form a functional group on the plastic film substrate to form a metal composed of copper or an alloy containing copper as a main component. The atoms constituting the plastic film substrate are chemically bonded and formed to enhance moisture resistance. However, the invention relies on the control of the lattice surface and the composite effect produced by the plasma treatment to achieve 'but control the lattice surface in the technology. It is difficult to carry out mass production. Further, in order to form a thin film on the insulating film, a vacuum deposition method, a sputtering method, an ion plating method, or the like is generally used, but a film layer obtained by such a dry plating method usually has a majority. A pinhole having a size of several tens of μm to several hundreds of μm, and thus the underlying metal layer tends to have an exposed portion of the insulator film due to the pinhole. Conventionally, in such a flexible wiring board, the thickness of the copper conductive film required for wiring is more than 35 μm and is more than 5 G/mi. However, since the width of the formed wiring is also about several hundred μm, it is very The presence of a small factor of ten pinholes 100108894 6 201139730 causes defects in the wiring section. However, when the flexible wiring board having the narrow-width and narrow-pitch wiring portions which is the object of the present invention is obtained, as described above, it is preferable that the thickness of the copper film for forming the wiring portion is 15 μm or less, preferably 8 μm or less. The ideal thickness of about 5 gm is extremely thin, which increases the possibility of defects in the wiring portion. In this case, the flexible wiring board is manufactured by a subtractive method using a two-layer flexible substrate in which a copper film layer having a desired thickness is formed on an insulating film on which an underlying metal layer is formed. As an example, the formation of the wiring portion pattern is carried out in accordance with the following procedure. (1) A photoresist layer having a desired wiring portion pattern of a copper conductor layer that shields only the wiring portion but exposes the non-wiring portion is provided on the copper conductor layer. (2) The exposed copper conductor layer is subjected to a chemical etching treatment to be removed. (3) Finally, the photoresist layer is peeled off. Therefore, when a substrate having a thickness of 5 μm of an ultra-thin steel film layer is formed, for example, when a wiring width of 15 μm, a wiring pitch of 3 (N), a narrow wiring width, and a narrow wiring pitch wiring board are used, the substrate is subjected to dry plating treatment. The underlying metal layer: the size of the pinholes produced by the reading, the size of the thicker ones will be several tens to hundreds (four): grade, so when forming a new steel film of thickness, the insulator film exposed by the pinhole (4) The sub-portion is almost impossible to be buried. Therefore, the exposed portion (that is, the defective portion of the conductor layer) may be involved in the wiring portion, causing the wiring portion to be defective at the pinhole position and becoming a wiring defect, which may cause the wiring portion to be closely connected. Bad cause. 100108894 7 201139730 Therefore, Patent Document 3 discloses a technique for defining a pinhole of a metal polyimine film laminate. However, Patent Document 3 does not disclose the pinhole of the vapor film and defines the pinhole after the copper plating, and the pinholes of the vapor deposited film and the underlying metal layer are not exposed. Further, as a method for solving the above problem, Patent Document 4 discloses that: a thin metal layer is formed on a thin film by a dry stitching method, and (10) a copper coating layer using electroless woven is further applied as an intermediate metal layer. A method in which the exposed portion of the insulator film caused by the pinhole is covered. However, although this method can surely eliminate the exposed portion of the insulator film due to the pinhole to some extent, it is known that the ore solution and the pretreatment liquid used in the treatment of the electroless copper ray are from A wide variety of pinhole portions of the formed size penetrate between the insulator film and the underlying metal layer. This phenomenon may result in adhesion to the underlying metal layer and subsequent use of the formed conductive copper layer. The inconsistency is not a sufficient solution. Moreover, even if the computer can scream the exposed portion of the insulating film, since the adhesion between the insulating thin layer and the copper layer is low, if the underlying metal layer has pinholes, it will cause the deterioration of the dense material and the insulating property. . [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The object of the present invention is to solve the above problems in the manufacture of a two-layer flexible substrate using a dry plating method, and to provide: The copper foil film layer and the copper layer are damaged due to the pinholes generated when the underlying metal layer is formed by the dry ore treatment on the insulator film, the underlying metal layer is less damaged, and the adhesion between the insulator film and the underlying metal layer is small. The two-layer flexible substrate excellent in corrosion resistance and water resistance is particularly suitable for a two-layer flexible substrate for fine pattern formation and COF mounting, and a method for producing the same. (Means for Solving the Problem) The present inventors have found that the underlying metal layer is formed by dry plating on at least one side of the insulating film without using an adhesive, and the underlying metal layer is formed on the underlying metal layer. A two-layer flexible substrate requiring a thick copper film layer and/or a copper layer, wherein the insulator film is subjected to surface treatment, and the amount of the oligomer is 2 layers of 70% or less of the amount of the oligomer before surface treatment. The flexible substrate can obtain defects in the copper film layer and the copper layer without pinholes generated when the underlying metal layer is formed, and the underlying metal layer is less defective' and between the insulator film and the underlying metal layer The two-layer flexible substrate excellent in adhesion, corrosion resistance, and water resistance can also be applied to a flexible wiring board having a narrow width and a narrow pitch wiring portion, and the present invention has been completed. According to a first aspect of the present invention, a two-layer flexible substrate is formed on a single surface of an insulator film of at least 100108894 9 201139730, and an underlying metal layer is formed by dry plating without passing through an adhesive. The method of forming a copper thin film layer by dry plating, wherein the 'insulating thin film is subjected to surface treatment on at least one side thereof, and only the surface of the insulating thin film is subjected to the surface treatment of the oligomer, and the surface is treated before the surface treatment The amount of the polymer is 70% or less. According to a second aspect of the invention, the copper thin film layer of the first invention has a thickness of 50 nm to 500 nm, and has no pinholes having a diameter exceeding 30 μm, and a pinhole having a diameter of 5/xm or more and 30 μm is 45,000 or less per square meter. According to a third aspect of the present invention, in the two-layer flexible substrate of the first and second aspects of the invention, the copper wet plating layer is formed on the copper thin film layer by wet plating. According to a fourth aspect of the present invention, the copper wet plating layer of the third invention has 0. 5/rni~12μιη thickness, and no concave defects with a diameter or maximum defect length exceeding 2〇/xm, and the direct or maximum defect length lO^rn or more, 20/xm or less concave defect is 2200 or less per 1 square meter . According to a fifth aspect of the present invention, in the two-layer flexible substrate of the first to fourth aspects, the 'underlying metal layer has a layer thickness of 5 nm to 50 nm and contains 6% by weight to 22% by weight of an additive element mainly composed of chromium. The rest is formed of a nickel-chromium alloy composed of nickel, and the layer thickness of the conductor layer (copper layer) composed of the copper thin film layer and the copper wet plating layer provided on the underlying metal layer is shameful. melon. According to a sixth aspect of the invention, the insulator film of the first to fifth inventions is a polyimide film, a polyamide film, a polyester film, a polytetrafluoroethylene film, a polyphenylene sulfide film, or a poly Naphthalene dicarboxylate, film, liquid crystal polymerization 100108894 10 201139730 A resin film selected from the film of the system. According to a seventh aspect of the present invention, in the first to sixth aspects of the invention, the surface treatment is at a pressure of 0. 8Pa~4. In the inert environment of 0 Pa, the surface of the insulator film is subjected to plasma discharge treatment using a DC voltage of 1500 V to 3000 V. According to an eighth aspect of the present invention, in the inert environment of the surface treatment according to the seventh aspect of the invention, the PCT peel strength after the surface treatment is 7 〇〇/ of the initial peel strength. the above. According to a ninth invention of the present invention, the surface treatment of the first to sixth inventions is at a pressure of 0. 8Pa~4. In the inert environment of 0 Pa, the surface of the insulator film was subjected to plasma discharge treatment using a high frequency voltage of 800 V to 2000 V. According to a tenth aspect of the present invention, the surface treatment inert environment of the ninth invention is a nitrogen atmosphere, and the PCT peel strength after the surface treatment is 70% or more of the initial peel strength. According to an eleventh aspect of the present invention, in the at least one surface of the insulating film, the underlying metal layer is formed by dry plating without passing through the adhesive, and the copper thin film layer is formed by dry plating on the underlying metal layer. A method for manufacturing a two-layer flexible substrate, wherein the surface of the insulator film is at a pressure of 0. 8Pa~4. In an inert environment of 0 Pa, a surface metal layer is formed by applying a surface treatment of a plasma discharge between the paired discharge electrodes of the plasma electrode for 2 to 100 seconds. According to a twelfth aspect of the present invention, in the surface treatment by the plasma discharge of the eleventh aspect of the invention, a voltage of 1500 V to 3000 V is applied between the discharge electrodes of the plasma electrode, 100108894 11 201139730. According to a thirteenth aspect of the present invention, in the surface treatment by the plasma discharge of the ηth aspect, a high frequency voltage of 8 〇〇 V to 2000 V is applied between the discharge electrodes of the plasma electrode. According to a fourteenth aspect of the present invention, in the at least one surface of the insulating film, the underlying metal layer is formed by dry plating without passing through the adhesive, and the copper thin film layer is formed by dry plating on the underlying metal layer. The method for producing a two-layer flexible substrate according to the eighth aspect of the invention, wherein the surface of the insulator film is at a pressure of 0. 8Pa~4. In the nitrogen atmosphere of 0 Pa, the surface treatment of the plasma generated by applying a DC voltage of 1500 V to 3000 V between the paired discharge electrodes of the plasma electrode for 2 to 1 Torr is performed to form an underlying metal layer. According to a fifteenth aspect of the present invention, in the at least one surface of the insulating film, the underlying metal layer is formed by dry plating without passing through the adhesive, and the copper thin film layer is formed by dry plating on the underlying metal layer. A method of manufacturing a two-layer flexible substrate according to the first invention, wherein 'the surface of the insulator film is at a pressure of 0. 8Pa~4. In the nitrogen atmosphere of 0 Pa, the surface treatment of the plasma generated by applying a high-frequency voltage of 800 V to 2000 V between the paired discharge electrodes of the plasma electrode for 2 to 1 〇〇 is applied to form an underlying metal layer. According to a sixteenth aspect of the invention, the dry plating method of the eleventh to fifteenth invention is any one of a vacuum deposition method, a sputtering method, and an ion plating method. According to a seventeenth aspect of the present invention, the insulator film of the eleventh to sixteenth aspects of the invention is a polyimide film, a polyamide film, a polyester film, a polytetrafluoroethylene 100108894 12 201139730 film, a polyphenylene sulfide. A resin film selected from the group consisting of a film, a polyethylene naphthalate film, and a liquid crystal polymer film. (Effect of the Invention) According to the present invention, it is possible to obtain a defect in the copper thin film layer and the copper wet plating layer caused by pinholes generated when the underlying metal layer is formed, and the underlying metal layer is less defective, and A two-layer flexible substrate excellent in adhesion between the insulator film and the underlying metal layer and resistance to the button. The two-layer flexible substrate is also suitable for a flexible wiring board having a narrow width and a narrow pitch wiring portion, and thus exhibits an industrially remarkable effect. [Embodiment] 1. Two-layer flexible substrate The two-layer flexible substrate of the present invention is formed on at least one surface of the insulating film, and when the adhesive is not passed, the underlying metal layer is provided by dry plating, and the underlying metal is provided. A structure in which a copper thin film layer is provided on a layer, wherein the insulating thin film is subjected to surface treatment to make the amount of oligomers less than 70% of the amount of oligomers before surface treatment, by The surface treatment of the insulator film is such that the generation of coarse pinholes can be suppressed as compared with the amount of the oligomer before the surface treatment is '70% or less of the surface amount of the polymer. Furthermore, the two-layer flexible substrate of the present invention preferably has a copper thin film layer having a thickness of 50 nm to 500 nm and has no pinholes having a diameter of 3 μm, and a pinhole per diameter of 5/xm to 30 μm is 1 square inch. 45,000 or less. 100108894 13 201139730 1 -1. Copper film layer The thickness of the copper film layer is preferably 50 nm to 500 nm. The thickness of the copper vl film layer is less than 5Qnm. When the copper wet plating layer is formed on the surface of the steel film layer by the galvanizing steel method which is one of the wet bell coating methods, the resistance of the copper layer is The value will increase and the appearance of the mineral deposit on the surface of the copper layer will deteriorate. Further, when the copper wet plating layer is formed by the electroplating copper method, the copper thin film layer functions as a cathode, and the electric resistance value of the copper thin film layer poses a problem. On the other hand, when the thickness of the copper thin film layer exceeds 5 〇〇 nm and the film is formed, the pinholes between the copper thin films are reduced, but it is time-consuming and economical to form the copper thin film layer by dry plating. Poor. In general, the thicker the copper film layer and the steel wet plating layer are, the more copper can be grown and the pinholes are buried, so that the pinholes are small and even less. Therefore, a two-layer flexible substrate is produced by providing a copper wet plating layer on the surface of the copper thin film layer by a wet deposition method in which the film formation speed is relatively fast. The two-layer flexible substrate has a small number of pinholes on the surface by wet plating. However, even if the pinholes on the surface of the two-layer flexible substrate are buried, the pinholes of the underlying metal layer and the copper thin film layer are not buried. Therefore, when the size and number of pinholes of the underlying metal layer and the copper thin film layer are not suppressed, the wiring portion pattern having a narrow wiring pitch is formed, and the wiring portion without the underlying metal layer is easily exposed, resulting in wiring defects, even if This is not the reason why the wiring part is poorly connected. Furthermore, the pinholes of the 'copper film layer are buried by wet ore. However, if there is a pinhole of the copper film layer of 100108894 14 201139730, the metal layer of the service layer will be exposed to the atmosphere before application. The layer is deteriorated, which causes the wiring to be trapped and the wiring portion to be poorly connected. Therefore, in the copper thin film layer of the present invention, even if it has a pinhole, it is preferably a pinhole having a diameter of 5 divisions to 3 mm. 45 square meters square: Within the range. In addition, the diameter is less than _ $ pinhole because it will lead to wiring defects, poor adhesion, and the detection is also relatively _, so there is no specified quantity. By making the structure of the society, it is possible to obtain the copper (four) defect caused by the pinholes generated when the bamboo has the underlying metal layer, and the underlying metal layer has fewer defects, and the film and the underlying gold are between the film and the underlying gold. A two-layer flexible substrate excellent in adhesion, recording resistance, and water quality. 1-2. Surface treatment of insulator film (substrate) The surface treatment of the insulator film of the substrate was carried out by electroporation. The surface treatment can be applied to one side of the insulator film, but it is more effective for double-sided implementation. The processing conditions are in an inert environment, 0. 8Pa~4. 0Pa pressure. Under pressure is not enough. In the inert environment of milk, the plasma discharge is not easy to find, if the pressure is exceeded. In the inert environment of 〇Pa, since the treatment becomes too strong, there is a case where the insulating film is creased during processing, which is not preferable. A DC voltage of 15 〇〇 v 〜 3 〇〇〇 v was applied between the paired discharge electrodes of the plasma electrode, and DC plasma (DC plasma) treatment was performed. If the DC voltage is less than 100108894 15 201139730 15 and the treatment of the secret electricity is used, the initial adhesion strength cannot be increased. If W_V is exceeded, the treatment will become too strong, so the insulation film is easily caused during the treatment. Wrinkling and deformation occur, which in turn leads to a decrease in heat-resistant adhesion strength and PCT peel strength, which is less preferable. A high frequency voltage of π 8 〇〇 v to 2000 V is applied between the paired discharge electrodes of the electropolymer electrode, and a high frequency M (RF f slurry) treatment is performed. If the high-frequency voltage is less than 800 V, the treatment by the plasma is too weak, and the initial adhesion strength does not rise. If it exceeds 2000 V, the treatment becomes too strong, so that the insulating film tends to occur during the treatment. Wrinkles and deformations are therefore less preferred. In addition, the term "inert atmosphere" means "a gas of Group 18 such as nitrogen or argon", which may be a mixed gas of nitrogen and argon, and the PCT may be stripped if it is subjected to surface treatment by electric ferrolysis in a nitrogen atmosphere. The strength is 70% or more of the initial peel strength. The processing time by plasma discharge is preferably from 2 seconds to 100 seconds. If the treatment time of the plasma discharge is less than 2 seconds, the treatment is too weak, which does not contribute to the increase of the initial adhesion strength. If the treatment is continued for more than 100 seconds, the influence is excessive, and the insulating film is likely to wrinkle and deform. The result is that the heat-resistant adhesion strength and the PCT adhesion strength are lowered, which is less preferable. On the other hand, from the viewpoint of productivity, the longer the treatment time of more than 100 seconds, the more the amount of the insulator film-based oligomer of the β substrate is, the more the pinhole of the copper film layer is increased. 100108894 16 201139730 When the surface treatment of one side of the insulating H film is performed, the 'the amount of the insulator film oligomer after the surface treatment' is preferably 70/〇 or less compared with the amount of the oligomer before the surface treatment. When the surface of the insulator film is subjected to surface treatment on both sides, the amount of the oligomer of the insulator film after the surface treatment is preferably 35% or less compared with the amount of the oligomer before the surface treatment, and the amount of the S polymer is reduced by the surface treatment. The reason is that the oligomer is removed by surface treatment, and the "oligomer" molecule is in the range of $300 to 14000. When the insulator film is produced, it is not sufficiently polymerized and remains. The molecules in the film. The amount of the oligomer was determined by measuring the amount of the oligomer as follows. The oligomer is extracted from the insulator film by using a solvent such as tetrahydroanthracene, and the molecular weight distribution can be measured by size exclusion chromatography (SEC method). 1-3. The underlying metal layer preferably has a layer thickness of 5 nm to 50 nm. If the thickness of the underlying metal layer formed by the nickel-chromium-based alloy mainly composed of chromium as an additive element obtained by the dry plating method is less than 5 nm, the long-term adhesion of the underlying metal layer will still be obtained through the subsequent processing steps. problem appear. In addition, if the thickness of the underlying metal layer is less than 5 nm, the etching solution may be infiltrated during wiring processing, which may cause problems such as floating of the wiring portion, and the wiring peeling strength may be significantly lowered, which is undesirable. On the other hand, if the layer thickness of the underlying metal layer exceeds 5 〇 nm, it is difficult to remove the underlying metal layer when the wiring portion is processed, and there is a three-curvature such as a crack in 100108894 17 201139730. The case where the adhesion strength is lowered is poor, and the thickness of the right layer is thicker than that of the 5 thief, which is still poor because it is difficult to perform silver engraving. The composition of the underlying metal layer is from the viewpoint of heat resistance and durability η 12 ft 〇 / -22 tt% 〇 22 weight = which causes a decrease in heat resistance, and the other aspect 1 chrome ratio exceeds that of the processing of the wiring portion of the field. The underlying metal is difficult and therefore less suitable. n . ^. In addition, in the nickel-chromium alloy, in the case of improving the heat resistance and the silver property, the case where the transition metal element 0 • θ metal layer can be appropriately added in accordance with the purpose of the characteristics can be used. For the flexible substrate, the thickness of the underlying metal layer is preferably 15 nm to 50 nm. Further, the bottom metal layer preferably has a chromium ratio of 4% by weight to 22% by weight, and further has 3 turns of 5 weights. %~40% by weight 'The rest is composed of recorded alloys. The ratio of the network is 4 奋 〇 Λ / Λ, to summer / 〇 ~ 22% by weight, is to prevent the resistance due to thermal deterioration", and the strength of the Qing is significantly reduced If the chromium ratio is less than 4% by weight, then the I-eye addition force α' still does not prevent the miscible strength from being significantly lowered due to thermal degradation, and thus is less preferred. If the chromium ratio is more than 22% by weight, then The etching may be less preferred. Therefore, in the case of chromium, it is more preferably 4 wt/〇15 wt/〇, particularly preferably 5% by weight to 12% by weight. h 4 is to improve the durability and the reliability of the insulation, and the reduction is preferably 5 100108894 201139730% by weight to 40% by weight. If the proportion of molybdenum is less than 5% by weight, the effect of addition is not exhibited, and corrosion resistance and insulation reliability are not improved, which is not preferable. Further, if the proportion of molybdenum exceeds 40% by weight, the heat-resistant peel strength tends to decrease extremely, which is not preferable. Furthermore, in the case of the usual nickel-based alloy target, if the nickel ratio is more than 93% by weight, the dry material itself becomes a ferromagnetic body, and when the film is formed by magnetron plating, film formation is caused. The speed is lowered, and thus it is less preferable, and when the underlying metal layer of the present invention is formed by sputtering, since the composition of the dry material of the sputtering is:: the amount of nickel is 93% by weight or less, and thus even if the magnetic control method is used, At the time of filming, a good film formation rate can still be obtained. Further, in the nickel-chromium-molybdenum alloy, γ can be appropriately added to the purpose of improving heat resistance and corrosion resistance, and a metal element can be added. In addition to the nickel-chromium-molybdenum alloy, in addition to the nickel-chromium-molybdenum-molybdenum alloy, it is possible to have impurities which are less than 5% by weight of the niobium contained in the target material. . In addition, in the formation of the underlying metal layer and the copper thin film layer, the dry plating method is used, and in the dry plating method, it is preferable to use any of the vacuum evaporation method, the sputtering method, or the ion forging method. By. 1_4·Insulator film (substrate) In addition, in the flexible substrate of the present invention, the insulator of the substrate is thin. The film is made of a polyimide film, a polyamide film, or a polyester film. A vinyl film, a polyphenylene sulfide film, and a polyethylene naphthalate system 100108894 19 201139730 A resin film selected from a film or a liquid crystal polymer film. ❹, it is more suitable to use an insulator with a film thickness of 25 to 75 yang. film. In addition, since inorganic materials such as glass fibers are an obstacle to laser processing and chemical etching, it is preferable not to use a substrate containing an inorganic material. 1-5. Copper layer (conductor layer) The two-layer flexible substrate of the present invention is formed on the underlying metal layer by a wet-coating method to form a copper-laid layer, and then a wet-weave is provided on the copper layer by wet bonding. The layer is further laminated to form a copper layer having a thickness of 1 Onm to 12/im including a __ and _ bond bond layer. When the copper layer is formed by only the dry ore method, the dry bell method is a vacuum distillation method, a ship method, or a secret method, and the phase-wet wet reading method also has a slow film formation rate. In the case, it is more suitable for the case of forming a thinner copper layer. On the other hand, after the steel film layer is formed by the dry type II deposition method, the copper layer is formed by wet plating on the copper film layer, which is suitable for forming a thick copper layer in a short time, which contributes to productivity improvement. When the outermost surface of the two-layer flexible substrate of the present invention is a copper thin film layer, the number of pinholes having a diameter of 5 Mm to 30/mi is suppressed to each! 45 square meters or less, if the outermost surface is a copper wet plating layer, the number of concave defects having a diameter or maximum defect length of 10/xm to 20/mi is suppressed to 22 (9) or less per square meter. It is suitable for the manufacture of flexible wiring boards with narrow pitch wiring. 2. Method for Producing Two-Layer Flexible Substrate Hereinafter, a method for producing a two-layer flexible substrate of the present invention will be described in detail with reference to 100108894 20 201139730. * In the present invention, the base material for the base material is a polyaniline (tetra) film, a polystyrene film, a polyester film, a polytetrafluoroethylene film, a polyphenylene sulfide film, a polyphthalate m (4). The insulating film of the resin film selected from the film and the liquid crystal polymer (4) is formed on one or both sides thereof without forming an underlying metal layer, and a copper thin film layer is formed on the underlying metal layer. The insulator film of the substrate usually contains moisture, and it is necessary to perform atmospheric drying or the removal of the moisture present in the body before the formation of the underlying metal layer composed of the chromium-based alloy by the dry forging method. If this action is not; i, the adhesion to the underlying metal layer will be deteriorated. When the underlying metal layer is formed by the dry ore method, for example, when a wire-type metal layer of a wound-type sputtering apparatus of R〇U t〇Roll is used, the target having the underlying metal layer is mounted on the sputtering. On the cathode. First, after performing vacuum evacuation in a sputtering apparatus equipped with an insulator film, nitrogen or argon or a mixed gas of nitrogen and argon is introduced, and the inside of the apparatus is maintained at a pressure of 0. 8Pa~4. In an inert environment of 0 Pa, apply 15 〇〇V~3_v DC voltage or 8〇〇v~2〇〇〇v high-frequency voltage between the paired discharge electrodes of the (four) electrode and finely rotate for 2 seconds~_second. Perform surface treatment. Next, argon gas is introduced, and the inside of the apparatus is held at about 13 Pa, and the winding film in the apparatus and the insulator film which is wound around the front side are conveyed at a speed of about 3 m per minute. The connected lining straight 100108894 201139730 flow power supply to start the sputtering discharge, and the underlying metal layer composed of a nickel-chromium alloy or a chrome-turn alloy is formed on the insulator film. The formation of the copper thin film layer is the same as in the case of the underlying metal layer, and the copper thin film layer is formed by using a sputtering apparatus ‘where the copper target is mounted on the sputtering cathode. At this time, the underlying metal layer and the copper thin film layer are preferably formed continuously in the same vacuum chamber. After the underlying metal layer is formed, the film is taken out in the atmosphere, and when a copper thin film layer is formed by using another sputtering device, the film must be formed. Adequate dehydration was performed beforehand. Further, when the copper thin film layer is formed by the dry bond method and the copper wet plating layer is formed by wet plating on the copper thin film layer, for example, electroless copper plating is preferably performed. In the electroless plating treatment, an electroless copper plating layer is formed on the entire flexible substrate, and even if there is a pinhole, the exposed surface is covered and the entire flexible substrate surface is formed into a good conductor. Thereby, the influence of the pinhole can be suppressed. However, when electroless copper plating is performed, it is necessary to pay attention to the penetration caused by the electroless plating solution and its pretreatment liquid and determine the conditions. In addition, the layer thickness of the copper-plated wet plating layer formed by the electroless copper plating solution is as long as the defects on the repairable substrate surface due to pinholes are applied and the electroplated copper plating solution is applied. The layer thickness which does not dissolve due to the electroplating copper plating solution can be 'better' in the range of Ogm. The substrate on which the electroless copper plating wet plating layer has been formed is formed as a copper wet plating layer capable of forming a final desired layer thickness, and the electroplated copper treatment is performed to obtain a metal layer which is not affected by the underlying metal layer. The two-layer flexible substrate which is affected by the various sizes of pinholes caused by 100108894 22 201139730 is good and has a high degree of adhesion. Further, the electroplating copper treatment performed in the present invention may be carried out by any of the conditions of the electroplating copper method which is carried out by the usual method. Accordingly, the layer thickness of the copper wet plating layer formed on the underlying metal layer and the copper thin film layer is preferably 12 μπ 1 or less. The reason for setting the layer thickness is to obtain a wiring board having a narrow wiring width and a narrow wiring pitch. Further, whether or not the copper wet plating layer is formed by wet plating on the surface of the copper thin film layer is appropriately selected in accordance with the method for producing the wiring portion pattern. For example, when the wiring portion pattern is formed by a known removal method, the wiring portion is formed by the underlying metal layer, the copper thin film layer, and the copper wet plating layer, and thus it is necessary to form a copper wet plating layer. It is required to be the layer thickness required for the wiring portion. Here, the removal is performed by providing a photoresist layer on the surface of the copper layer of the two-layer flexible substrate, and then providing a predetermined line of money on the green skin, and then exposing the material line from above to expose the ' The film is obtained by subjecting an unnecessary steel layer or the like to an engraved mask, then removing the exposed copper layer, and then removing the remaining photoresist layer. The underlying metal layer, which is not required for the wiring portion, is also removed by the money, and the method of forming the wiring portion is fortunate. On the other hand, when the wiring portion pattern is formed by the semi-additive method, the copper wet green layer may be provided on the steel film groove by the wet-wet reading method, or 5 may not be provided. The term "semi-additive method" as used herein refers to a two-layer Nike (iv) metal layer (a metal layer formed from an underlying metal layer and a copper film (4), or a bottom metal layer, steel 100108894 23 201139730 film layer and plate plating). a photoresist layer is disposed on a surface of the metal layer formed by the cladding layer, and a mask having a predetermined wiring pattern is disposed on the photoresist layer, and then ultraviolet rays are irradiated from above to be exposed, and the image is obtained by using the image. On the surface of the metal layer, the electric clock is formed on the surface of the metal layer to form a wiring portion, and the metal layer exposed in the opening portion is used as a cathode, and the photoresist layer is removed by the parent (four)-line portion, and then the soft layer is removed. On the other hand, a method of forming a wiring portion pattern by completing the wiring portion by removing the unnecessary metal layers on the surface of the two flexible substrates other than the wiring portion. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. The measurement of each characteristic was carried out using the means shown below. The method for measuring pinholes is to use a layered body of a bottom metal layer and a copper film layer obtained by a dry method, which is positioned by a penetrating method, and then measured by an optical microscope, and a pinhole having a diameter of one to three 〇 is measured. The number of square meters per square meter. The method for evaluating the amount of oligomers is to extract the plasma-treated insulating film by tetrahydromanganese, and then use the size exclusion chromatography (SEC method) to determine the proportion of oligomers having a molecular weight of 380 to 13500. The value before the electroforming treatment was set to 1 GG%, and a peak was observed and regarded as "amount of oligomer". The method for determining the peel strength is in accordance with IPC-TM-650, NUMBER2. 4. The method of 9 is ^; and is regarded as "initial peel strength". However, the wire width was set to 1 mm, and the peeling angle was set to 9 G. . The wire is formed by removing 100108894 24 201139730, and the soil is placed in a 15GC_ box for (6) hours. After being taken out, it is placed to a 9〇° toughness strength and is considered as “heat-resistant stripping*,,, twinning. The finger beam system will form a thin test box with a thin wire of 1 mm wire in the room temperature, by evaluating the strength and the strength of the fool, and the film substrate of the film of the wire surface is formed at 2 atmospheres ^ When the hot press production was placed at 96], the S was placed until it became a dish, and was evaluated by evaluating the peel strength of 9°°, and was regarded as “PCT peel strength”. The measurement of the Pt3 is performed on the surface of the copper wet recording layer obtained by the electric key method using an optical microscope, and the size of the concave defect is measured. #凹凹 is a circular case, and the number of diameters is 10 to 20 A squares per square inch. § The concave defect is a circle other than a circle, and the maximum length of the defect of the concave defect is regarded as " The maximum defect length", 骇ΙΟμιη to 20/mi concave defects per 1 square meter. (Comparative Example 1) First, Comparative Example 1 shows the characteristics of a two-layer flexible substrate which was formed by performing a film formation without performing a polymerization treatment. The i-th layer of the underlying metal layer is formed on one surface of a 38/mi polyimide film (Kapton 150EN, manufactured by Toray DuPont Co., Ltd.), and the first layer of the underlying metal layer is 20% by weight. I saw the alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.), using DC sputtering method in the Ar environment, depending on the film formation speed. 7nm/sec will be 20% by weight of the 底层 犯 alloy underlying metal layer into a 100108894 25 201139730 film. The layer thickness was measured using a transmission electron microscope (TEM: manufactured by Hitachi, Ltd.) for a part of the film formed under the same conditions, and the result was 0. 02/xm. Further, a second layer was formed on the film by the above-mentioned 20% by weight (> the film was formed on the film, and a Cu target (manufactured by Sumitomo Metal Mining Co., Ltd.) was used for the second layer, and a copper film having a thickness of 10 〇 nm was formed by sputtering. The layer was then formed by copper plating to a thickness of 8/mi. The initial peel strength of the obtained two-layer flexible substrate was 471 N/m, the pCT peel strength was 253 N/m, and the number of pinholes of the dry substrate was 76714. The amount of oligomer was 100%, and sufficient initial peel strength was not obtained. (Example 1) The following is exemplified by the case where the surface treatment by the electric paddle treatment was performed on the insulating film. β The thickness of the polyimide was adjusted to 38 μm. Film (manufactured by Toray DuPont, registered trademark "Kapton 150") under nitrogen pressure i. In a 6 Pa environment, a DC voltage of 2000 V was applied between the paired discharge electrodes of the plasma electrode for 5 sec seconds, and only the film formation surface of the underlying metal layer was subjected to plasma treatment. Next, a first layer of an underlying metal layer is formed on the plasma-treated surface of the polyimide, and the second layer of the underlying metal layer is a 20% by weight Cr-Ni alloy target (Sumitomo Metal Mining Co., Ltd.) System), using the DC sputtering method in the Ar environment, depending on the film formation speed 〇. A 20 μ% Cr-Ni alloy underlayer metal layer was formed into a film at 7 nm/sec. The layer thickness was measured using a transmission electron microscope (TEM: manufactured by Hitachi, Ltd.) for a part of the film formed under the same conditions, and the result was 100-108894 26 201139730, which was 0_02 μm. Further, a second layer was formed on the 20 wt% Ni-Cr film, and the second layer was formed by using a Cu target (manufactured by Sumitomo Metal Mining Co., Ltd.) to form a thickness of the copper thin film layer by sputtering. Then, a film was formed by copper plating to a thickness of 8 μm. The initial peel strength of the obtained two-layer flexible substrate was 624 N/m, the PCT peel strength was 434 N/m, and the dry plating (layered body of the underlying metal layer and the copper thin film layer. Hereinafter referred to as "dry plating") was used. The number of holes was 36,443 / m2, and there were no pinholes with a diameter exceeding 30 μm, the amount of oligomers was 70%, the number of concave defects was 1951/m2', and there were no concave defects with a diameter or a maximum defect length exceeding 2 μm. (Example 2) A 38/mi polyimide film ("Kapton 15" manufactured by Toray DuPont Co., Ltd.) was placed under a nitrogen pressure of 2. In a 4 Pa environment, a DC voltage of 2000 V was applied between the paired discharge electrodes of the electropolymer electrode for 5 sec seconds, and only the film formation surface of the underlying metal layer was subjected to plasma treatment. Then, the first layer of the underlying metal layer is formed on the plasma-treated surface of the polyimide, and the first layer of the underlying metal layer is made of 20% by weight of Cr-Ni alloy dry material (Sumitomo Metal Mining Co., Ltd.) System) 'Using DC sputtering method in Ar environment, according to film formation speed 0. 7 nm/seC A 20 wt% Cr-Ni alloy underlayer metal layer was formed into a film. The thickness of the layer was measured using a transmission electron microscope (TEM: manufactured by Toray Industries, Inc.) in part of the film formation under the same conditions, and the result was 0. 02μιη. A second layer was further formed on the 20% by weight Ni-Cr film, and the second layer was a Cu target (manufactured by Sumitomo Metal Mining Co., Ltd.), and the product was formed by a method of forming a copper thin film layer 100 nm. The thickness was then filmed to a thickness of 8 μm by a copper electric clock method. The initial peel strength of the obtained two-layer flexible substrate was 635 N/m, the PCT peel strength was 463 N/m, the number of pinholes for dry plating was 15,571 / m 2 , and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomer It is 56%, the number of concave defects is 1645/m2' and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 3) A 38/rni polyimide film (manufactured by Toray DuPont Co., Ltd., registered trademark "Kapton 150EN") was placed under a nitrogen pressure of 3. In a 1 Pa environment, a DC voltage of 2000 V was applied between the paired discharge electrodes of the plasma electrode for 50 seconds, and only the film formation surface of the underlying metal layer was subjected to plasma treatment. Next, a first layer of the underlying metal layer is formed on the plasma-treated surface of the polyimide, and the first layer of the underlying metal layer is made of 20% by weight of Cr-Ni alloy dry material (Sumitomo Metal Mining Co., Ltd.) System), using the DC sputtering method in the Ar environment, according to the film formation speed of 0. A 20 wt% Cr-Ni alloy underlayer metal layer was formed into a film at 7 nm/sec. The thickness of the layer was measured using a transmission electron microscope (TEM: manufactured by Toray Industries, Inc.), and the result was 0·02 μιη. Further, a second layer was formed on the above-mentioned 20% by weight Cr-Ni film, and the second layer was made of Cu dry material (manufactured by Sumitomo Metal Mining Co., Ltd.), and a thickness of 100 nm of the copper thin film layer was formed by the Tibetan clock method, and then reused. The copper plating method was performed to a thickness of 8 μm.
所獲付2層可挽性基板的初期剝離強度係632N/m , PCT 100108894 28 201139730 剝離強度係467N/m，乾式鍍敷的針孔數係 8236 個/m2，且 白無直徑超過30/mi的針孔，寡聚物量係5〇%，凹缺陷數係 2005個/m2’且皆無直徑或最大缺陷長超過2〇μιη的凹缺陷。 (比較例2) 雖欲將厚度38/xm聚醯亞胺薄膜（東麗杜邦公司製，註冊 商標「Kapton 150EN」）在氮氣壓〇.7pa的環境下，於電漿 電極的配對放電電極間施加500V直流電壓15秒鐘，但放 電呈不安定，而無法處理。 (比較例3) 雖將厚度38μιη聚醯亞胺薄膜(.東麗杜邦公司製，註冊商 標「Kapton 150ΕΝ」）在氮氣壓4.7Pa的環境下，於電漿電 極的配對放電電極間施加3500V直流電壓6秒鐘而施行電 漿處理，但表面有出現起皺，導致後續的特性評估無法進行。 (實施例4) 除設為氬氣壓3.6Pa，並對電漿電極施加直流2800V而施 行6秒鐘電漿處理之外，其餘均與實施例1同樣地製作實施 例4的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係612N/m，乾式 鍍敷的針孔數係7428個/m2’且皆無直徑超過30/an的針 孔，寡聚物量係50%，凹缺陷數係889個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例5) 100108894 29 201139730 除設為氬氣壓1.6Pa，並對電漿電極施加直流2200V而施 行6秒鐘電漿處理之外，其餘均與實施例1同樣地製作實施 例5的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係627N/m，乾式 鐘敷的針孔數係5142個/m2，且皆無直徑超過30/rni的針 孔，寡聚物量係70%。另外，實施例5的2層可撓性基板之 凹缺陷測定並未實施。 (實施例6) 除設為氬氣壓3.6Pa，並對電漿電極施加直流1600V而施 行6秒鐘電漿處理之外，其餘均與實施例1同樣地製作實施 例6的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係626N/m，乾式 鍍敷的針孔數係6428個/m2，且皆無直徑超過30μιη的針 孔，寡聚物量係70%。另外，實施例6的2層可撓性基板之 凹缺陷測定並未實施。 (比較例4) 雖設為氬氣壓0.7Pa，並欲對電漿電極施加6秒鐘的直流 500V，但放電呈不安定，而無法進行處理。 (比較例5) 雖設為氬氣壓4.7Pa，並對電漿電極施加直流3500V而施 行6秒鐘電漿處理，但表面有出現起皺，導致後續的特性評 估無法進行。 100108894 30 201139730 (實施例7) 除設為75體積％氬-25體積％氮~的混合氣壓1.6Pa，並對 電漿電極施加直流1800V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例7的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係608N/m，乾式 鍍敷的針孔數係8571個/m2，且皆無直徑超過30μιη的針 孔，寡聚物量係70%，凹缺陷數係1855個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例8) 除設為75體積％氬-25體積％氮的混合氣壓1.6Pa，並對 電漿電極施加直流2300V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例8的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係599N/m，乾式 鍍敷的針孔數係7143個/m2，且皆無直徑超過30μιη的針 孔，寡聚物量係50%，凹缺陷數係1554個/m2，且皆無直徑 或最大缺陷長超過20/xm的凹缺陷。 (實施例9) 除設為75體積％氬-25體積％氮的混合氣壓3.6Pa，並對 電漿電極施加直流1500V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例9的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係593N/m，乾式 鍍敷的針孔數係24000個/m2，且皆無直徑超過3〇μιη的針 100108894 31 201139730 孔，寡聚物量係60%，凹缺陷數係1762個/m2,且皆無直捏 或最大缺陷長超過20μηι的凹缺陷。 (比較例6) 雖設為75體積％氬-25體積％氮的混合氣壓〇.7Pa，並欲 對電漿電極施加6秒鐘的直流500V，但放電呈不安定，而 無法進行處理。 (比較例7) 雖設為75體積％氬-25體積％氮的混合氣壓4.7Pa，並對 電漿電極施加直流3500V而施行6秒鐘電漿處理，但表面 有出現起皺，導致後續的特性評估無法進行。 (實施例10) 除設為50體積％氬-50體積％氮的混合氣壓1.6Pa，並對 電漿電極施加直流3000V而施行50秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例1〇的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係681Ν/Π1，乾式 鍍敷的針孔數係18276個/m2，且皆無直徑超過30μηι的針 孔，寡聚物量係70%，凹缺陷數係2076個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例11) 除設為50體積％氬_50體積％氮的混合氣壓1.6Pa，並對 電漿電極施加直流1800V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例11的2層可撓性基板。 100108894 32 201139730 所獲得2層可撓性基板的初期制離強度係572N/m，乾式 鑛敷的針孔數係15286個/m2，且皆無直徑超過卿m的針 孔，寡聚物量係30% ’凹缺陷數係、1861個/爪2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例12) 除設為50體積％氬-50體積。/。氮的混合氣壓3 6pa，並對 電漿電極施加直流2000V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例12的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係583N/m，乾式 鍍敷的針孔數係21286個/m2，且皆無直徑超過3〇/im的針 孔，寡聚物量係40%，凹缺陷數係1889個/m2，且皆無直徑 或最大缺陷長超過20/mi的凹缺陷。 (比較例8) 雖設為50體積％氬-50體積％氮的混合氣壓〇 7Pa，並欲 對電漿電極施加6秒鐘的直流500V，但放電呈不安定，而 無法進行處理。 : (比較例9) : 雖設為50體積％氬-50體積％氮的混合氣壓4.7Pa，並對 電漿電極施加直流3500V而施行6秒鐘電漿處理，但表面 有出現起皺，導致後續的特性評估無法進行。 (實施例13) 除設為25體積％氬-75體積％氮的混合氣壓1.6Pa，並對 100108894 33 201139730 電漿電極施加直流1600V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例13的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係586N/m，乾式 鍍敷的針孔數係8857個/m2，且皆無直徑超過30μηι的針 孔，寡聚物量係55%，凹缺陷數係1428個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例14) 除設為25體積％氬-75體積％氮的混合氣壓1.6Pa，並對 電漿電極施加直流1800V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例14的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係567N/m，乾式 鍍敷的針孔數係11569個/m2，且皆無直徑超過30/rni的針 孔，寡聚物量係50%，凹缺陷數係1276個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例15) 除設為25體積％氬-75體積％氮的混合氣壓3.6Pa，並對 電漿電極施加直流2000V而施行6秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例15的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係584N/m，乾式 鍍敷的針孔數係22429個/m2，且皆無直徑超過30/rni的針 孔，寡聚物量係70%，凹缺陷數係1987個/m2,且皆無直徑 或最大缺陷長超過20/ζηι的凹缺陷。 100108894 34 201139730 (比較例10) 雖設為25體積％氬_75體積％氮的混合氣壓〇.7Pa，並欲 對電漿電極施加6秒鐘的直流500V，但放電呈不安定，而 無法進行處理。 (比較例11) 雖設為25體積％氬-75體積％氮的混合氣壓4.7Pa，並對 電漿電極施加直流3500V而施行6秒鐘電漿處理，但表面 有出現起皺，導致後續的特性評估無法進行。 (實施例16) 除設為25體積％氬-75體積％氮的混合氣壓1.6Pa，並對 電漿電極施加高頻600V而施行12秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例16的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係598N/m ’乾式 鍍敷的針孔數係9847個/m2，且皆無直徑超過30μιη的針 孔，寡聚物量係65%，凹缺陷數係1564個/m2,且皆無直徑 或最大缺陷長超過20/mi的凹缺陷。 (實施例Π) 除設為25體積％氬-75體積％氮的混合氣壓1.6Pa，並對 電漿電極施加高頻1000V而施行Π秒鐘電漿處理之外’其 餘均與實施例1同樣地製作實施例17的2層可撓性基板。 所獲得2層可換性基板的初期剝離強度係608N/m，乾式 鍍敷的針孔數係15098個/m2 ’且皆無直徑超過30μπι的針 100108894 35 201139730 孔，寡聚物量係63%，凹缺陷數係2〇 17個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (實施例18) 除設為25體積％氬-75體積。/。氮的混合氣壓2.4Pa，並對 電聚電極施加高頻600V而施行12秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例18的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係6i4N/m，乾式 鍍敷的針孔數係19713個/m2 ’且皆無直徑超過3〇μιη的針 孔’寡聚物量係70%，凹缺陷數係1798個/m2，且皆無直徑 或最大缺陷長超過20μιη的凹缺陷。 (比較例12) 雖設為25體積％氬-75體積％氮的混合氣壓0 3Pa，並欲 對電漿電極施加12秒鐘的高頻600V，但放電呈不安定，而 無法進行處理。 (比較例13) 雖設為25體積％氬-75體積％気的混合氣壓4.7Pa，並對 電衆電極施加高頻600V而碑行12秒鐘電楽:處理，但表面 有出現起敵’導致後續的特性評估無法進行。 (實施例19) 除設為氬氣壓1.6Pa’並對電漿電極施加高頻6〇〇v而施 行12秒鐘電漿處理之外’其餘均與實施例1同樣地製作實 施例19的2層可撓性基板。 100108894 36 201139730 所獲得2層可撓性基板的初期剝離強度係598N/m，乾式 鍍敷的針孔數係25673個/m2，且皆無直徑超過30μιη的針 孔，寡聚物量係56%，凹缺陷數係1897個/m2，且皆無直徑 或最大缺陷長超過20/im的凹缺陷。 (實施例20) 除設為75體積％氬-25體積％氮的混合氣壓1.6Pa，並對 電漿電極施加高頻600V而施行12秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例20的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係587N/m，乾式 鍍敷的針孔數係19476個/m2，且皆無直徑超過30μηι的針 孔，募聚物量係66%，凹缺陷數係1674個/m2，且皆無直徑 或最大缺陷長超過20/mi的凹缺陷。 (實施例21) 除設為50體積％氬-50體積％氮的混合氣壓1.6Pa，並對 電漿電極施加高頻600V而施行12秒鐘電漿處理之外，其 餘均與實施例1同樣地製作實施例21的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係569N/m，乾式 鍍敷的針孔數係24384個/m2 ’且皆無直徑超過30μιη的針 孔，寡聚物量係62%，凹缺陷數係1720個/m2，且皆無直徑 或最大缺陷長超過20/mi的凹缺陷。 (實施例22) 除設為氮氣壓1.6Pa，並對電漿電極施加高頻600V而施 100108894 37 201139730 行12秒鐘電漿處理之外，其餘均與實施例1同樣地製作實 施例22的2層可撓性基板。 所獲得2層可撓性基板的初期剝離強度係601N/m，乾式 鍍敷的針孔數係27846個/m2，且皆無直徑超過30/rni的針 孔，寡聚物量係59%，凹缺陷數係2008個/m2,且皆無直徑 或最大缺陷長超過的凹缺陷。 上述實施例、比較例的結果整理如表1所示。 100108894 38 20 ο 3 97 3 鬥1<〕 3 fli S Γ〇 § 1 K- 叫 柘 € wt.l 鉍 W 0 00 5 κ 僉 vi m.l B? m 00 f-H V*) S 卜 r*H κ- Μ vi fw.l Bv w l_ o § a 00 % H- 鞞 衫 t V? (bJ R) 0 00 CM 2 rs 卜 oo ON ff dhI pBr € s? 鲧 rpBT El S 1 t> oo σ\ r- 1 1 w: mill £^tD W\ j 1 1 1 1 1 ! 1 1 1 1 1 1 1 破 ί! vi m.t 8? 00 v〇 R 卜 00 1 w < 喊搞 iDHg3j 11^ (4giJ Ο ο Ο Ο 8 tn g 8 8 o , 0 1 0 1 o o 0 1 0 1 〇 »r! <Τ) 0 1 o o j o in v〇 〇 o CO VO o o o： Ol 1 1 o V〇 O S 1 o 〇\ 乾式織基板 單面針?_μ數 [個/m2] 3; ν〇 2 Π \T) ώ 00 00 § s 00 ~1 O 8 o cs 00 g ?! o s rs 00 00 O\ v〇 — 〇\ <N CN 卜 ON 00 g ro σ\ Ρ·Η . ~~1 1 Pi s〇' «1 1 VO »—1. A o s f5 毕 初觸CT 〇 P !〇 ?! o 0\ CO CN (N i〇 S in w-) !n ~i u^l 1 *〇 00 »r> PCT [N/m] CN s δ IT) 00 cs !2 cs 00 (S ~·1 § CN s ΓΛ o m ~1 U^) 〇\ (N s m cn —1 (N ro u·) cn 卜 CN cn 00 On CN s CO s 糊 II Os 00 00 « ο s cs 氏 cs g § 氏 ΓΛ rn m S rs 00 σ\ 00 00 cn 〇 to v〇 m l〇 00 ro s〇 ? S g m 初期 [N/m] _ 5 Ό 2 CN s rs o o 'O s 00 s a <n $ rj E S3 vo 00 δ s oo On <n 00 s 寸 w 0 00 〇\ ^T) ss iTi $ \n s 越 ti i ΐ ? ί 1 II μ: 〇〇 __ 00 00 __ 00 oo 00 00 u. 00 L 00 oo 00 00 00 00 00 00 00 00 L 00 00 L_ 00 1 L IOO 00 1 L 乾式鍵敷， 銅薄膜層[nm] ο Ο — o r·^ o r-H o o o B o O o g o o ο o o r·^ i— o o o !〇 i-H 0 j 1 _ 1 'O 1 底層金屬層 S ο S 〇 S o g d (N § CNJ P o o s o s o 1 g d — (N P o s d s o s 〇 s d o d s d g d s o s d 1 iS 1° [_ g d 11 ㈣ li 1 沄 1 Ό 1 Ο Ό Ό 1 Γ <〇 沄 卜 r° o 1 VD SO 1 v〇 CN cs r4 i cs cs is 1 1 (N 8 8 8 S 8 00 pi o CN 8 ο 8 CO 8 22 8 S I ο ΚΓϊ 8 8 s 22 g ο vTi 8 in m IBHIHIIII I 剛 mi 酬 剛 1 1 U P a 卜 U Q 8 δ S S a H δ δ δ δ S -1 氣體壓力 [Pa] 1 vq 卜 〇 co 'O CO 寸· VO NO CO 卜 ο 卜 O so rn 卜 Ο 卜· ^«4 sD r〇 卜 d 卜 寸· v〇 NO s 卜 寸· \q ρ·Η \D vq 混合比例1 1 〇 O 8 o ^H 〇 ° o ° ο ° ~~ ~ in jn JO JQ JO LO 卜 jO r ° o L 1 Ο o o o 〇 o o 一 o »»H ο f—^ s Γ |〇 *n LO jn O t: s CS o 氣體種類 _ truJ Bv m.l Βν ΓΗ.Ι Ε» 1 _. 1 ΙΛ I l % 1 i〇 1 1 0 1 1 ί 1 S? 〇 % g 1 if , Ar-75%N2 i , 1 JO i 1 m L_ 1 I 靈 SIS 1 1 1 1 III lil s£55 1 BESSIE] 1 ill I5S5 ι^ί § - $0 .. 6ε 【％οΛ】υί : Γ sil 201139730 由表1得知，藉由對絕緣體薄膜施行依照本發明指定條件 之電漿處理的表面處理，便可使絕緣體薄膜的寡聚物量成為 表面處理前的寡聚物量之70%以下，且可將乾式鍍敷的針孔 數抑制在45000個/m2以下，並可將銅濕式鍍敷層的凹缺陷 數抑制在2200個/m2以下。 再者，表面處理的電漿處理之環境壓力未滿0.8Pa時，確 認到放電呈不安定，而無法對絕緣體薄膜施行表面處理。 且，亦得知對於電漿電極的施加電壓若過高，則絕緣體薄膜 會出現起皺，導致無法製造2層可撓性基板。 100108894 40The initial peel strength of the two-layer removable substrate was 632 N/m, the peel strength of PCT 100108894 28 201139730 was 467 N/m, the number of pinholes for dry plating was 8236/m2, and the diameter of white no more than 30/mi. The pinholes, the amount of oligomers were 5%, the number of concave defects was 2005/m2' and there were no concave defects with a diameter or a maximum defect length exceeding 2 μm. (Comparative Example 2) It is intended to use a 38/xm polyimide film (trademark "Kapton 150EN", manufactured by Toray DuPont Co., Ltd.) under a nitrogen pressure of .7 Pa in a pair of discharge electrodes of a plasma electrode. A 500V DC voltage was applied for 15 seconds, but the discharge was unstable and could not be processed. (Comparative Example 3) A film of 38 μm thick polyimine film (trademark "Kapton 150", manufactured by Toray DuPont Co., Ltd.) was applied at a nitrogen pressure of 4.7 Pa to apply 3500 V DC between the paired discharge electrodes of the plasma electrode. The plasma was treated for 6 seconds at a voltage, but wrinkles appeared on the surface, which prevented subsequent evaluation of the characteristics. (Example 4) The two-layer flexibility of Example 4 was produced in the same manner as in Example 1 except that the argon gas pressure was 3.6 Pa, and the plasma electrode was subjected to a direct current of 2,800 V and a plasma treatment was performed for 6 seconds. Substrate. The initial peel strength of the obtained two-layer flexible substrate was 612 N/m, the number of pinholes of the dry plating was 7,428 / m 2 ', and none of the pinholes having a diameter exceeding 30 / an, the amount of the oligomer was 50%, and the concave defect The number is 889/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 5) 100108894 29 201139730 Two layers of Example 5 were produced in the same manner as in Example 1 except that the argon gas pressure was 1.6 Pa, and a DC of 2,200 V was applied to the plasma electrode and plasma treatment was performed for 6 seconds. Flexible substrate. The initial peel strength of the obtained two-layer flexible substrate was 627 N/m, the number of pinholes of the dry bell was 5142/m2, and none of the needles having a diameter exceeding 30/rni, and the amount of the oligomer was 70%. Further, the measurement of the concave defects of the two-layer flexible substrate of Example 5 was not carried out. (Example 6) The two-layer flexibility of Example 6 was produced in the same manner as in Example 1 except that the argon gas pressure was 3.6 Pa, and the plasma electrode was applied with a direct current of 1600 V and a plasma treatment was performed for 6 seconds. Substrate. The initial peel strength of the obtained two-layer flexible substrate was 626 N/m, the number of pinholes for dry plating was 6428/m2, and there were no pinholes having a diameter exceeding 30 μm, and the amount of the oligomer was 70%. Further, the measurement of the concave defects of the two-layer flexible substrate of Example 6 was not carried out. (Comparative Example 4) Although an argon gas pressure of 0.7 Pa was applied and a direct current of 500 V was applied to the plasma electrode for 6 seconds, the discharge was unstable and processing was impossible. (Comparative Example 5) Although argon gas pressure of 4.7 Pa was applied and a direct current of 3,500 V was applied to the plasma electrode for 6 seconds of plasma treatment, wrinkles appeared on the surface, and subsequent evaluation of characteristics was impossible. 100108894 30 201139730 (Example 7) Except that the mixing gas pressure of 75 vol% argon-25 vol% nitrogen~ is 1.6 Pa, and the plasma electrode is applied with 1800 V DC for 6 seconds, the rest is implemented. Example 1 A two-layer flexible substrate of Example 7 was produced in the same manner. The initial peel strength of the obtained two-layer flexible substrate was 608 N/m, the number of pinholes for dry plating was 8571/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomers was 70%, and the number of concave defects was 1855 pieces/m2, and all have no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 8) The same procedure as in Example 1 except that the mixing gas pressure of 75 vol% argon-25 vol% nitrogen was 1.6 Pa, and the plasma electrode was subjected to a direct current 2300 V and a plasma treatment was performed for 6 seconds. A two-layer flexible substrate of Example 8 was produced. The initial peel strength of the obtained two-layer flexible substrate was 599 N/m, the number of pinholes for dry plating was 7143/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomers was 50%, and the number of concave defects was 1554 pieces/m2, and all have no concave defects with a diameter or a maximum defect length exceeding 20/xm. (Example 9) The same procedure as in Example 1 except that the mixing gas pressure of 75 vol% argon to 25 vol% nitrogen was 3.6 Pa, and 1500 V DC was applied to the plasma electrode and plasma treatment was performed for 6 seconds. A two-layer flexible substrate of Example 9 was produced. The initial peel strength of the obtained two-layer flexible substrate was 593 N/m, the number of pinholes of the dry plating was 24,000/m2, and none of the needles having a diameter exceeding 3 μm was 100108894 31 201139730, and the amount of the oligomer was 60%. The number of concave defects is 1762 pieces/m2, and there are no concave defects of straight pinching or maximum defect length exceeding 20 μm. (Comparative Example 6) Although a mixing pressure of 75% by volume of argon to 25% by volume of nitrogen was 〇7 Pa, and a DC of 500 V was applied to the plasma electrode for 6 seconds, the discharge was unstable and could not be processed. (Comparative Example 7) Although a mixed gas pressure of 7.5 vol of argon--25 vol% nitrogen was set to 4.7 Pa, and a direct current of 3500 V was applied to the plasma electrode for 6 seconds of plasma treatment, wrinkles appeared on the surface, resulting in subsequent Feature evaluation is not possible. (Example 10) The same procedure as in Example 1 except that the mixed gas pressure of 50 vol% argon-50 vol% nitrogen was 1.6 Pa, and a direct current 3000 V was applied to the plasma electrode and a plasma treatment was performed for 50 seconds. A two-layer flexible substrate of Example 1 was produced. The initial peel strength of the obtained two-layer flexible substrate was 681Ν/Π1, the number of pinholes of dry plating was 18276/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomers was 70%, and the number of concave defects was 2076 pieces/m2, and all have no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 11) The same procedure as in Example 1 except that the mixing gas pressure of 50 vol% argon _50 vol% nitrogen was 1.6 Pa, and the plasma electrode was applied with a direct current of 1800 V and a plasma treatment for 6 seconds. A two-layer flexible substrate of Example 11 was produced. 100108894 32 201139730 The initial separation strength of the obtained two-layer flexible substrate is 572 N/m, the number of pinholes for dry ore is 15286/m2, and there are no pinholes with a diameter exceeding qingm, and the amount of oligomers is 30%. 'The number of concave defects is 1,861/claw 2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 12) A argon-50 volume was set to 50% by volume. /. A two-layer flexible substrate of Example 12 was produced in the same manner as in Example 1 except that the nitrogen gas was mixed at a pressure of 3 6 Pa and a DC voltage of 2000 V was applied to the plasma electrode for 6 seconds. The initial peel strength of the obtained two-layer flexible substrate was 583 N/m, the number of pinholes of the dry plating was 21,286 / m 2 , and none of the pinholes having a diameter exceeding 3 〇 / im, the amount of the oligomer was 40%, concave The number of defects is 1889/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20/mi. (Comparative Example 8) Although a mixed gas pressure of 7 vol of 50 vol% argon-50 vol% nitrogen was used, and a direct current of 500 V was applied to the plasma electrode for 6 seconds, the discharge was unstable and could not be processed. : (Comparative Example 9): Although a mixing pressure of 4.7 Pa of 50% by volume of argon-50% by volume of nitrogen was applied, and a DC of 3500 V was applied to the plasma electrode for 6 seconds, the surface was wrinkled, resulting in wrinkles on the surface. Subsequent feature evaluations cannot be performed. (Example 13) Except that the mixing gas pressure of 25% by volume of argon-75 vol% nitrogen was 1.6 Pa, and DC voltage of 1600 V was applied to the 100108894 33 201139730 plasma electrode, and plasma treatment was performed for 6 seconds, A two-layer flexible substrate of Example 13 was produced in the same manner. The initial peel strength of the obtained two-layer flexible substrate was 586 N/m, the number of pinholes for dry plating was 8,857/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomers was 55%, and the number of concave defects was There are 1428 pieces/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 14) The same procedure as in Example 1 except that the mixing gas pressure of 25% by volume of argon-75 vol% nitrogen was 1.6 Pa, and the plasma electrode was applied with a direct current of 1800 V and a plasma treatment for 6 seconds. A two-layer flexible substrate of Example 14 was produced. The initial peel strength of the obtained two-layer flexible substrate was 567 N/m, the number of pinholes for dry plating was 11,569/m2, and none of the pinholes having a diameter exceeding 30/rni, the amount of the oligomer was 50%, and the concave defect The number is 1276/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 15) The same procedure as in Example 1 except that the mixing gas pressure of 5% by volume of argon-75 vol% nitrogen was 3.6 Pa, and the plasma electrode was applied with a direct current of 2000 V for 6 seconds. A two-layer flexible substrate of Example 15 was produced. The initial peel strength of the obtained two-layer flexible substrate was 584 N/m, the number of pinholes of the dry plating was 22,429 / m 2 , and none of the pinholes having a diameter exceeding 30/rni, the amount of the oligomer was 70%, and the concave defect The number is 1987/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20/ζη. 100108894 34 201139730 (Comparative Example 10) Although the mixing pressure of 25% by volume of argon-75 vol% nitrogen was 〇7 Pa, and the direct current of 500 V was applied to the plasma electrode for 6 seconds, the discharge was unstable and could not be performed. deal with. (Comparative Example 11) Although a mixed gas pressure of 7.5 vol of argon-75 vol% nitrogen was set to 4.7 Pa, and a direct current of 3500 V was applied to the plasma electrode for 6 seconds of plasma treatment, wrinkles appeared on the surface, resulting in subsequent Feature evaluation is not possible. (Example 16) The same procedure as in Example 1 except that the mixing gas pressure of 25% by volume of argon-75 vol% nitrogen was 1.6 Pa, and a high frequency of 600 V was applied to the plasma electrode and plasma treatment was performed for 12 seconds. A two-layer flexible substrate of Example 16 was produced. The initial peel strength of the obtained two-layer flexible substrate was 598 N/m 'the number of pinholes of the dry plating was 9847/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of the oligomer was 65%, and the number of concave defects was 1564 pieces/m2, and all have no concave defects with a diameter or a maximum defect length exceeding 20/mi. (Example Π) The same as Example 1 except that the mixing gas pressure of 25% by volume of argon-75 vol% nitrogen was 1.6 Pa, and a high frequency of 1000 V was applied to the plasma electrode and a Π second plasma treatment was performed. A two-layer flexible substrate of Example 17 was produced. The initial peel strength of the obtained two-layer exchangeable substrate was 608 N/m, the number of pinholes for dry plating was 15098/m2′, and none of the needles having a diameter exceeding 30 μm 100108894 35 201139730, the amount of oligomers was 63%, concave The number of defects is 2〇17/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Example 18) A volume of 25% by volume of argon-75 was used. /. A two-layer flexible substrate of Example 18 was produced in the same manner as in Example 1 except that the mixed gas pressure of nitrogen was 2.4 Pa, and a high-frequency 600 V was applied to the electropolymer electrode to carry out a plasma treatment for 12 seconds. The initial peel strength of the obtained two-layer flexible substrate was 6i4 N/m, the number of pinholes for dry plating was 19,713/m2', and the pinhole 'oligomer amount system having a diameter exceeding 3 〇μη was 70%, concave defect The number is 1798/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20 μm. (Comparative Example 12) The mixing gas pressure of 25% by volume of argon-75 vol% nitrogen was 0 3 Pa, and the high frequency of 600 V was applied to the plasma electrode for 12 seconds, but the discharge was unstable and could not be processed. (Comparative Example 13) Although the mixing gas pressure of 5% by volume of argon-75 vol% was 4.7 Pa, and the high frequency of 600 V was applied to the electrode of the electric field, and the electric wave was applied for 12 seconds: treatment, but the surface appeared to be enemies' This will prevent subsequent feature evaluations from proceeding. (Example 19) Example 19 was produced in the same manner as in Example 1 except that the argon gas pressure was 1.6 Pa' and the high frequency 6 〇〇v was applied to the plasma electrode and the plasma treatment was performed for 12 seconds. Layer flexible substrate. 100108894 36 201139730 The initial peel strength of the obtained two-layer flexible substrate is 598 N/m, the number of pinholes for dry plating is 25673/m2, and there are no pinholes with a diameter exceeding 30 μm, and the amount of oligomer is 56%. The number of defects is 1897/m2, and there are no concave defects with a diameter or a maximum defect length exceeding 20/im. (Example 20) The same procedure as in Example 1 except that the mixing gas pressure of 75 vol% argon-25 vol% nitrogen was 1.6 Pa, and the plasma electrode was subjected to a high frequency of 600 V and a plasma treatment was performed for 12 seconds. A two-layer flexible substrate of Example 20 was produced. The initial peel strength of the obtained two-layer flexible substrate was 587 N/m, the number of pinholes for dry plating was 19,476/m2, and none of the pinholes having a diameter exceeding 30 μm, the amount of the polymer was 66%, and the number of concave defects was 1674 pieces/m2, and none have concave defects with a diameter or a maximum defect length exceeding 20/mi. (Example 21) The same procedure as in Example 1 except that the mixed gas pressure of 50% by volume of argon-50% by volume of nitrogen was 1.6 Pa, and a high frequency of 600 V was applied to the plasma electrode and plasma treatment was performed for 12 seconds. A two-layer flexible substrate of Example 21 was produced. The initial peel strength of the obtained two-layer flexible substrate was 569 N/m, the number of pinholes for dry plating was 24,384 / m 2 ', and none of the pinholes having a diameter exceeding 30 μm, the amount of oligomers was 62%, and the number of concave defects was 1720 / m2, and no concave defects with a diameter or maximum defect length exceeding 20 / mi. (Example 22) Example 22 was produced in the same manner as in Example 1 except that a nitrogen gas pressure of 1.6 Pa was applied, and a high frequency of 600 V was applied to the plasma electrode, and 100108894 37 201139730 for 12 seconds of plasma treatment was applied. 2 layers of flexible substrate. The initial peel strength of the obtained two-layer flexible substrate was 601 N/m, the number of pinholes of the dry plating was 27,846/m2, and none of the pinholes having a diameter exceeding 30/rni, the amount of the oligomer was 59%, and the concave defect The number is 2008/m2, and there are no concave defects with a diameter or a maximum defect length exceeding. The results of the above examples and comparative examples are shown in Table 1. 100108894 38 20 ο 3 97 3 Bucket 1<〕 3 fli S Γ〇§ 1 K- 柘€ wt.l 铋W 0 00 5 κ 佥vi ml B? m 00 fH V*) S 卜r*H κ- Μ vi fw.l Bv w l_ o § a 00 % H- Sweatshirt t V? (bJ R) 0 00 CM 2 rs oo ow ff dhI pBr € s? 鲧rpBT El S 1 t> oo σ\ r- 1 1 w: mill £^tD W\ j 1 1 1 1 1 ! 1 1 1 1 1 1 1 Break ί! vi mt 8? 00 v〇R 00 1 w < shouting iDHg3j 11^ (4giJ Ο ο Ο Ο 8 tn g 8 8 o , 0 1 0 1 oo 0 1 0 1 〇»r! <Τ) 0 1 oojo in v〇〇o CO VO ooo: Ol 1 1 o V〇OS 1 o 〇\ dry Single-sided needle of woven substrate?_μ数[/m2] 3; ν〇2 Π \T) ώ 00 00 § s 00 ~1 O 8 o cs 00 g ?! os rs 00 00 O\ v〇— 〇\ < ;N CN 卜ON 00 g ro σ\ Ρ·Η . ~~1 1 Pi s〇' «1 1 VO »—1. A os f5 After the first touch CT 〇P !〇?! o 0\ CO CN (N i〇S in w-) !n ~iu^l 1 *〇00 »r> PCT [N/m] CN s δ IT) 00 cs !2 cs 00 (S ~·1 § CN s ΓΛ om ~1 U ^) 〇\ (N sm cn —1 (N ro u·) cn 卜 CN cn 00 On CN s CO s Paste II Os 00 00 « ο s cs cs g § ΓΛ rn rn m S rs 00 σ\ 00 00 cn 〇to v〇ml〇00 ro s〇? S gm initial [N/m] _ 5 Ό 2 CN s rs oo 'O s 00 sa <n $ rj E S3 vo 00 δ s oo On <n 00 s inch w 0 00 〇\ ^T) ss iTi $ \ns The more ti i ΐ ? ί 1 II μ: 〇〇__ 00 00 __ 00 oo 00 00 u. 00 L 00 oo 00 00 00 00 00 00 00 00 00 L 00 00 L_ 00 1 L IOO 00 1 L Dry key bond, copper film layer [nm] ο Ο — or·^ o rH ooo B o O ogoo ο oor·^ I—ooo !〇iH 0 j 1 _ 1 'O 1 underlying metal layer S ο S 〇S ogd (N § CNJ P oososo 1 gd — (NP osdsos 〇sdodsdgdsosd 1 iS 1° [_ gd 11 (4) li 1 沄1 Ό 1 Ο Ό Ό 1 Γ <〇沄卜r° o 1 VD SO 1 v〇CN cs r4 i cs cs is 1 1 (N 8 8 8 S 8 00 pi o CN 8 ο 8 CO 8 22 8 SI ο ΚΓϊ 8 8 s 22 g ο vTi 8 in m IBHIHIIII I just mi 1 1 UP a 卜 UQ 8 δ SS a H δ δ δ δ S -1 gas pressure [Pa] 1 vq 〇 co co 'O CO inch · VO NO CO 卜ο Bu O so rn Bu Ο Bu· ^«4 sD r〇卜d卜寸· v〇NO s 卜寸· \q ρ·Η \D vq mixing ratio 1 1 〇O 8 o ^H 〇° o ° ο ° ~~ ~ in jn JO JQ JO LO 卜 jO r ° o L 1 Ο ooo 〇oo a o »»H ο f—^ s Γ |〇*n LO jn O t: s CS o Gas type _ truJ Bv ml Βν ΓΗ.Ι Ε» 1 _. 1 ΙΛ I l % 1 i〇 1 1 0 1 1 ί 1 S? 〇% g 1 if , Ar-75%N2 i , 1 JO i 1 m L_ 1 I SIS 1 1 1 1 III lil s£55 1 BESSIE] 1 ill I5S5 ι^ί § - $0 .. 6ε [%οΛ]υί : Γ sil 201139730 It is known from Table 1 that the amount of oligomer of the insulator film can be made by subjecting the insulator film to the surface treatment of the plasma treatment according to the conditions specified in the present invention. 70% or less of the amount of the oligomer before the surface treatment, and the number of pinholes of the dry plating can be suppressed to 45,000 pieces/m2 or less, and the number of concave defects of the copper wet plating layer can be suppressed to 2,200 pieces/m2 or less. . Further, when the environmental pressure of the surface-treated plasma treatment was less than 0.8 Pa, it was confirmed that the discharge was unstable, and the surface treatment of the insulator film could not be performed. Further, it has been found that if the applied voltage of the plasma electrode is too high, wrinkles of the insulator film occur, and it is impossible to manufacture a two-layer flexible substrate. 100108894 40