200803664 (1) 九、發明說明 【發明所屬之技術領域】 本發明是關於可使用在電腦、手機、通訊機器、錄影 攝影機等的裝置內等所使用的印刷電路配線板的屏蔽薄膜 ，及使用此屏蔽薄膜的屏蔽印刷電路配線板者。 【先前技術】 傳統上，使用金屬薄膜的屏蔽薄膜是成爲公知，例如 有揭示於下述專利文獻1者。具體而言，揭示著在電性絕 緣性基材的一面形成金屬層，使用含有導電性塡料及難燃 性塡料的樹脂組成物於以具有導電性及難燃性的黏接層於 該金屬層上，作爲特徵的帶式電纜用屏蔽材。 但是，專利文獻1的屏蔽材是雖適用作爲所需要的帶式 電纜用的難燃性屏蔽薄膜，惟使用熱可塑性樹脂，在高溫下 施以流平安裝等之際，沒有耐熱性之故，因而無法使用作爲 印刷電路配線板的難燃性的屏蔽薄膜。 在此，本發明人等是具有耐燃性般地，在使用熱硬化 性樹脂的屏蔽薄膜（例如，記載於下述專利文獻2者）的該熱 硬化性樹脂調配難燃劑，證明是否具有耐熱性及難燃性的雙 方的屏蔽薄膜。 專利文獻1:日本特開2002 — 27983 1號公報 專利文獻2:日本特開2004 — 95566號公報 【發明內容】 -5- (2) (2)200803664 然而，進行上述證明的結果，若增加對於熱硬化性樹 脂的阻燃劑的調配量，雖可提昇難燃性，惟可知會產生對 於屏蔽薄膜的印刷電路等的密接性會降低的問題。 如此，本發明的目的是在於提供不會降低對於印刷電 路等的密接性，即使如進行流平安裝時地在未加熱時的環 境下，可使用難燃性的屏蔽薄膜，及使用此屏蔽薄膜的屏 蔽印刷電路配線板。 本發明的屏蔽薄膜是具有絕緣層與含有難燃性樹脂的 屏蔽層者。 藉由上述構成，本發明的屏蔽薄膜，是具有含有難燃 性樹脂的屏蔽層，藉由難燃性樹脂（尤其是，高耐熱性的 難燃性熱硬化性樹脂），可提供不會降低對印刷電路等的 密接性，在後續工程即使施以流平安裝等也無問題地可使 用的難燃性的屏蔽薄膜。 在本發明的屏蔽薄膜中，上述屏蔽層爲具有形成在一 述絕緣層的至少一面的一層以上的向同性導電性黏接劑層 較佳。依照上述構成，將本發明的屏蔽薄膜黏貼於印刷電 路之際，藉由接地電路的圖案的導電，向同性導電性黏接 劑層可發揮電磁波屏蔽性。 在本發明的屏蔽薄膜的上述屏蔽層中，具有：形成在 上述絕緣層的至少一面的一層以上的金屬層，及一層以上 向異性導電性黏接劑層較佳。依照上述構成，在印刷電路 黏貼本發明的屏蔽薄膜之際向異性導電性黏接劑層能導電 連接接地電路的圖案與本發明的屏蔽薄膜的金屬層之故， -6 - (3) (3)200803664 可發揮電磁波屏蔽性。 本發明的屏蔽薄膜中，上述導電性黏著劑層爲又含有 阻燃劑者，上述阻燃劑爲對於上述難燃性樹脂1 00重量部 調配10至180重量部較佳。依照上述構成，即使極薄至35μηι 以下的薄膜，也合格在UL 94的垂直燃燒性試驗（VTM規格） ’而且對於基材等的密接性較高，而確實地可提供在可撓性 及保存穩定性也優異的屏蔽薄膜。 在本發明的屏蔽薄膜中，上述難燃性樹脂爲含有磷含 有難燃性樹脂較佳。依照上述構成，確實地可提供高難燃性 的屏蔽薄膜。 本發明的屏蔽印刷電路配線板，是將上述任一的屏蔽 薄膜，具有於包括一層以上的印刷電路的基體的至少一面上 。依照上述構成，導電連接接地電路的圖案與本發明的屏 蔽薄膜的金屬膜之故，因而可提供電磁波屏蔽性優異的屏蔽 印刷電路配線板。又，可提供在UL 94的垂直燃燒性試驗（V 規格）上合格的屏蔽印刷電路配線板。 本發明的屏蔽印刷電路配線板，是上述基體爲撓性印 刷電路配線板較佳。依照上述構成，電磁波屏蔽性上優異， 而且基體爲具有可撓性的撓性印刷配線板，可提供在必須彎 曲的部位上可使用的屏蔽印刷電路配線板。 【實施方式】 以下，依據圖式，針對於本發明的實施形態加以說明 。第1圖是表示本發明的實施形態的屏蔽薄膜的斷面圖。 -7- (4) (4)200803664 表示於第1圖的屏蔽薄膜1，是在絕緣層2的一面依次 設置金屬層3，及黏接劑層4所成者。 絕緣層2是覆蓋薄膜或絕緣樹脂的塗膜層所構成。 覆蓋薄膜是由工程塑膠所構成。例如有聚丙烯、交聯 聚乙烯、聚酯、聚苯并咪唑、芳族聚醯胺、聚醯亞胺、聚 醯亞胺醯胺、聚醚醯亞胺、聚苯撐硫化物（PPS)、聚萘二 甲酸乙二醇酯（PEN)等。 未過度被要求耐熱性時，則低價格的聚酯薄膜較佳， 在被要求難燃性時，則以聚苯撐硫化物薄膜較佳，又，被 要求耐熱性時，則醯胺薄膜或醯亞胺薄膜較佳。 絕緣樹脂是具有絕緣性的樹脂就可以，例如有熱硬化 性樹脂或紫外線硬化性樹脂等。作爲熱硬化性樹脂，例如 有苯酚樹脂、丙烯酸樹脂、環氧樹脂、三聚氰胺甲醛樹脂 、矽氧樹脂、丙烯酸變性聚矽氧樹脂等。作爲紫外線硬化 性樹脂，例如有環氧丙烯酸酯樹脂、聚酯丙烯酸酯樹脂， 及此些的甲基丙烯酸酯變性品等。又，作爲硬化形態、熱 硬化、紫外線硬化、電子線硬化等都可以，而能加以硬化 者就可以。 又，絕緣層2的厚度是Ιμηι〜ΙΟμιη，較理想是3μιη〜7μπι 較佳。 作爲形成金屬層3的金屬材料，有銅、錦、銀、金等 。金屬材料是因應於所求得的屏蔽特性加以選擇就可以。 作爲金屬層3的形成方法，有真空蒸鍍、濺鍍、CVD法、 ΜΟ(金屬有機）、電鍍等，惟考慮量產性，以真空蒸鍍較 200803664 (5) 佳，以低價格又穩定地可得到金屬薄膜。又，金屬層3是 並不被限定於金屬薄膜，也可使用金屬箔。金屬層3的厚 度一般作成0.01〜ΙΟμιη較佳。若Ο.ΟΙμιη以下，則屏蔽效果 成爲不充分，相反地超過ΙΟμιη，則可撓性變差。尤其是 需要可撓性時，則2μπι以下較佳，又，尤其是需要屏蔽效 果時，則ΙΟμιη以下較佳。 作爲黏接劑層4，使用可耐於260 °C的基板安裝（流平） 的具耐性的耐熱性的熱硬化性樹脂，較理想爲使用難燃性 的熱硬化性樹脂，在此添加著阻燃劑或導電性塡料，具有 向同性導電性或向異性導電性。黏接劑層4的厚度是5 μπι 至3 0μιη較佳。若比5μιη更薄，則無法得到充分的密接性， 若超過30μπι，則會損及柔軟性。又，若黏接劑層4具有向 同性導電性時，則沒有金屬層3也可以。 作爲難燃性的熱硬化性樹脂，有磷含有熱硬化性樹脂 ，雙酚Α型、雙酚F型、酚醛清漆型等。 在此，作爲磷含有熱硬化性樹脂、有環氧樹脂、熱可 塑性樹脂、含有磷化合物者。 作爲此的環氧樹脂，以雙酚A、雙酣F或雙酣s作爲出 發原料而與環氧氯丙烷反應所得到。例如以雙酚A型環氧 樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、又，以酹、 〇 -甲氧基甲酣，或以萘二醇作爲出發原料，用甲醛進行 縮合者，與環氧氯丙烷進行反應所得到。例如有苯酣環氧 樹脂、0-甲酚酚醛清漆樹脂、萘酚醛清漆樹脂等，此些 是以單獨使用一種，或是混合使用兩種以上都可以。 200803664 (6) 又，作爲在此的熱可塑性樹脂，有聚醯胺系樹脂、苯 氧樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯撐氧撐樹脂、聚 氨基甲酸乙酯樹脂、聚甲醛樹脂、聚乙烯系樹脂、聚丙烯 系樹脂、聚乙烯基系樹脂等，此些是單獨使用一種，或是 混合使用兩種以上都可以。 在環氧樹脂調配熱可塑性樹脂，就可得到具柔軟性的 熱硬化性樹脂。 又，作爲在此的磷化合物，是與環氧樹脂等直接反應 的反應型，或不直接反應的非反應型的任一型都可以。與 環氧樹脂等直接反應的反應型，並未特別加以限定，惟具 有羥基、胺基、羧基、羥甲基、環氧基、異氰酸酯、矽烷 醇基、乙烯基等的官能基者，有耐熱性或黏接性等者。 磷含有熱硬化性樹脂的調配比率，對於（A)環氧樹脂 5〜60重量部，（B)熱可塑性樹脂100重量部，（C)(A)及（B)的 合計重量，爲10〜35質量％。藉由此，可提供耐於基板安裝（ 流平），且具有柔軟性的屏蔽薄膜。 作爲阻燃劑，從環境上的問題上，以無鹵素系阻燃劑 較佳，有蜜胺三聚氰酸酯等的金屬水和物，或磷酸酯、紅磷 等的磷系阻燃劑等，惟被要求耐熱性時，以蜜胺三聚氰酸酯 、氫氧化鎂較佳。阻燃劑的調配比率，是對於難燃性樹脂 1〇〇重量部作爲10〜80重量部較佳，更較佳爲作成50〜150重 量部較佳。若超過1 80重量部，則無法得到充分的密接，而 若爲1 〇重量部以下，則難燃性的性能成爲不充分。 作爲導電性塡料，使用著碳、銀、銅、鎳、焊錫、鋁 -10- 200803664 (7) 及在銅粉施加鍍銀的銀被覆銅塡料，又在樹脂球或玻璃珠等 施加鍍金屬的塡料或是此些塡料的混合體。銀是高價格、銅 是耐熱的信賴性上欠缺，鋁是耐濕的信賴性上欠缺，又焊錫 是無法得到充分的導電性之故，因而使用較低價格而具有導 電性。又，信賴性高的銀被覆銅塡料或鎳較佳。 導電性塡料的調配比率，也受到塡料的形狀等左右， 惟對難燃性樹脂100重量部作成10〜100重量部較佳，更理想 爲作成15〜50重量部較佳。若超過100重量部，則會降低對 於接地電路（銅箔）的黏接性，會使得屏蔽撓性印刷電路配線 板（以下，稱爲屏蔽FPC)等的可撓性變壞，而且會降低難燃 性能。又，低於1 〇重量部，則顯著降低導電性，而且會降 低難燃性能。金屬塡料的形狀是球狀、針狀、纖維狀、片 狀、樹脂狀的任一都可以。 依照上述實施形態，使用高耐熱性的熱硬化性樹脂之 故，因而在後續工程施以流平處理等也可提供無問題地也 可使用的難燃性的屏蔽薄膜。 又，即使在極薄到3 5 μηι以下的薄膜，確實地可提供 在UL 94的垂直燃燒性試驗（VTM規格）上也合格，而且對 基材等的密接性高之外，還在可撓性及保存穩定性上也優 異的屏蔽薄膜。 又，難燃性樹脂爲含有磷者之故，因而確實地可提供 高難燃性的屏蔽薄膜。 此外，在印刷電路黏貼本實施形態的屏蔽薄膜之際， 導電連接電路的圖案與本發明的屏蔽薄膜的金屬層之故， -11 - 200803664 (8) 因而此时可發揮電磁波屏蔽性。 又，本發明的屏蔽薄膜，是可利用在FPC、COF、RF ，多層撓性基板，剛性基板等，惟並不一定限制在此些。 又，作爲黏貼於FPC時的構造，例如成爲如第2圖所示的屛 蔽印刷電路配線板1 〇。在此，5是帶基薄膜，6是印刷電路， 7是絕緣薄膜，8是基體薄膜。 印刷電路6的表面是由訊號電路6a與接地電路6b所構成； 除了接地電路6b之至少一部分（非絕緣部）6c之外，藉由絕緣 薄膜施以被覆。絕緣薄膜7是在內部具有流進屏蔽薄膜1的黏 接劑層4的一部分的絕緣除去部7a。藉由此，接地電路6b與 金屬層3是電性地被連接。 在此，帶基薄膜5與印刷電路6之接合，是藉由黏接劑 施以黏接也可以，或是未使用黏接劑，而與所謂無黏接劑型 貼銅積層板同樣地接合也可以。又，絕緣薄膜7是使用黏接 劑進行黏貼可撓性絕緣薄膜在一起也可以，或是藉由感光性 絕緣樹脂的塗工、乾燥、曝光、顯像、熱處理事的一連串的 手法所形成也可以。還有，基體薄膜8是適當地採用僅在帶 基薄膜的一方的面具有印刷電路的單面型FPC，在帶基薄膜 的雙面具有印刷電路的雙面型FPC，積層複數層此種FPC的 多層型FPC，具有多層零件承載部與電纜部的扶累克斯佰特 (登錄商標），或將構成多層部的構件作爲硬質者的撓曲剛性 基板，或帶載封裝所用的TAB帶等而可實施。 又，帶基薄膜5，絕緣薄膜6都由工程塑膠所構成。例 如有聚丙烯、交聯聚乙烯、聚酯、聚苯并咪唑、聚醯亞胺 -12- 200803664 (9) 、聚醯亞胺醯胺、聚醚醯亞胺、聚苯撐硫化物（PPS)、等 的樹脂。未過度被要求耐熱性時，則低價格的聚酯薄膜較 佳，在被要求難燃性時，則以聚苯撐硫化物薄膜較佳，又 ，被要求耐熱性時，則醯亞胺薄膜較佳。 * 利用上述構成，導電連接接地電路6b的圖案與上述實 施形態的屏蔽薄膜1的金屬層3之故，因而可提供電磁波屏 蔽性優異的屏蔽印刷電路配線板1 0。又，即使極薄至 35μηα以下的薄膜，也可提供UL 94的垂直燃燒性試驗（V規 格）上合格的屏蔽印刷電路配線板。又，基體薄膜8爲FPC 之故，因而在電磁波屏蔽性上優異，而且具有可撓性，可 提供在必需彎曲的部位可使用的屏蔽印刷電路配線板1 〇。 實施例 製作與表示於第1圖的屏蔽薄膜1同樣構成的實施例 1〜4及比較例1〜4的屏蔽薄膜。以下，針對於此些的實施例 1〜4及比較例1〜4的屏蔽薄膜加以說明。又，針對於有關於 實施例1〜4及比較例1〜4的屏蔽薄膜，作爲絕緣層2使用厚 度5μιη的環氧樹脂所構成者，而作爲金屬層3使用厚度 Ο.ίμηι的銀蒸鍍層。黏接劑層4的厚度是17μηι，而在磷含 有環氧樹脂（難燃性樹脂）1 〇〇重量部，各添加所定量由蜜胺 聚三氰酸酯所構成的阻燃劑，又各添加20重量部由銀被覆鋼 粉所構成的導電性塡料（參照表1 )。 -13- 200803664 (10) [表1] 實方 _ 比較例 1 2 3 4 1 2 3 4 磷含有環氧樹脂 (重量部） 100 100 一 環氧樹脂(重量部） _ _ 100 阻燃劑(重量咅 10 50 150 180 0 5 200 150 特性 難燃性 VTM—0 〇 〇 〇 〇 X X 〇 X V-0 〇 〇 〇 〇 X 〇 〇 〇 流平性 〇 〇 〇 〇 〇 〇 〇 〇 密接性 〇 〇 〇 〇 〇 〇 X 〇 實施例1〜4及比較例1〜4的屏蔽薄膜的製作方法 首先，在絕緣層2的單面，設置金屬層3，及具有上述 表1的各實施例及各比較例的成分的黏接劑層4，作爲各實 施例及各比較例的屏蔽薄膜。又，在難燃性試驗及可撓性 試驗以外的試驗，爲了評價實施例1〜4及比較例1〜4的屏蔽 薄膜，使用將各實施例及各比較例的屏蔽薄膜在1 70 °C下 施以3分鐘的3MPa的沖壓，而黏貼於各試驗的基材之後， 在150°C下施以60分鐘的後硬化者。 耐流平試驗的方法 針對於實施例1〜4及比較例1〜4的屏蔽薄膜，進行以下 的耐流平試驗。在成爲基材的貼銅積層板（日嵌工業（股） -14- 200803664 (11) 所製F - 30VC1)的銅箔，黏接著黏接劑層般地黏貼各屏蔽 薄膜，而以屏蔽薄膜的絕緣層側作爲上面，通過IR流平爐 (峰値溫度：2 6 5 °C )。之後，藉由眼睛觀察有無屏蔽薄膜 的絕緣層表面的鼓出，剝落等的外觀異狀來進行。將未確 • 認鼓出及剝落等的外觀異狀者作爲〇，而確認有鼓出及剝 落等的外觀異狀者作爲X 5將結果表Tpc於表1。 難燃性試驗（VTM規格）的方法 針對於實施例1〜4及比較例1〜4的屏蔽薄膜，進行以下 的難燃性試驗。首先，使用上述製作方法，在各屏蔽薄膜 的黏著劑層表面形成轉印薄膜之後，將各屏蔽薄膜單體在 170°C下施以3分鐘的3MPa的沖壓。然後，剝離轉印薄膜 ，在1 5 0 °C下施以6 0分鐘的後硬化。將各屏蔽薄膜捲在心 軸成爲圓之後，拆下而針對於各屏蔽薄膜，依據UL - 94 的垂直難燃性試驗（VTM規格），進行難燃性的評價。將 VTM - 0上合格者作爲〇，而將不合格者作爲x，將結果表 示於表1。 難燃性試驗（V規格）的方法 針對於將實施例1〜4及比較例1〜4的屏蔽薄膜分別黏貼 於厚度25 μπι的聚醯亞胺薄膜（東麗•杜邦（股）所製，卡普 頓100Η)者，依據UL — 94的垂直難燃性試驗（V規格），進 行難燃性的評價。將V - 0上合格者作爲◦，而將不合格者 作爲X，將結果表示於表1。 -15- 200803664 (12) 密接性試驗的方法 針對於實施例1〜4及比較例1〜4的屏蔽薄膜，進行以下 的密接性試驗。首先，使用上述製作法，在成爲基材的厚 度爲25 μιη的聚醯亞胺薄膜（東麗•杜邦（股）所製，卡普頓 1 0 0Η)，黏接著黏接劑層般地黏貼各屏蔽薄膜。之後，剝 離聚醯亞胺薄膜1 80°，進行測定屏蔽薄膜的強度（密接性） 。將該強度4.0N/cm以上者作爲〇（合格），而將不足 4.0N/cm者作爲χ(不合格），將結果表示於表1。 由上述結果，可知可提供不會降低對於印刷電路等的 密接性，即使在後續工程進行流平安裝等，也無問題地可 使用的難燃性的屏蔽薄膜，及使用此的屏蔽印刷電路配線 板。 又，本發明是在未超越申請專利範圍可設計變更者， 並不被限定在上述實施形態者。 【圖式簡單說明】 第1圖是表示本發明的實施形態的屏蔽薄膜的局部橫 斷面圖。 第2圖是表示黏貼第1圖的屏蔽薄膜的FPC的局部橫斷面 圖。 【主要元件對照表】 1 :屏蔽薄膜 -16- 200803664 (13) 2 :絕緣層 3 :金屬層 4 :黏接劑層 5 :帶基薄膜 6 :印刷電路 ' 6a :訊號電路 6 b :接地電路 6 c :非絕緣部 7 :絕緣薄膜 7a :絕緣除去部 8 :基體薄膜 1 〇 :屏蔽印刷電路配線板 -17-200803664 (1) The present invention relates to a shielding film for a printed circuit board that can be used in a device such as a computer, a mobile phone, a communication device, a video camera, etc., and uses the same. Shielded film shielded printed circuit board. [Prior Art] Conventionally, a shielding film using a metal thin film has been known, and is disclosed, for example, in Patent Document 1 below. Specifically, it is disclosed that a metal layer is formed on one surface of an electrically insulating substrate, and a resin composition containing a conductive material and a flame retardant coating is used for the metal layer having conductivity and flame retardancy. A shield for a tape cable as a feature on the layer. However, the shielding material of the patent document 1 is suitable as a flame-retardant shielding film for a tape type cable which is required, and it is a heat-resistant resin, and it is not heat-resistant, and it is a heat-resistant- Therefore, it is impossible to use a flame-retardant shielding film as a printed circuit board. Here, the inventors of the present invention have a heat-resistant resin which is a flame-retardant film (for example, described in Patent Document 2 below), and is formulated with a flame retardant to prove whether or not it has heat resistance. Shielding film for both sex and flame retardant. Patent Document 1: Japanese Laid-Open Patent Publication No. 2002- 27983 No. 1 Patent Publication No. JP-A-2004-95566A SUMMARY OF THE INVENTION -5- (2) (2) 200803664 However, if the result of the above proof is performed, if The blending amount of the flame retardant of the thermosetting resin can improve the flame retardancy, but it is known that the adhesion to the printed circuit of the shield film is lowered. In view of the above, it is an object of the present invention to provide a flame-retardant shielding film and a shielding film which can be used in an environment where it is not heated, such as when performing leveling, without providing adhesion to a printed circuit or the like. Shielded printed circuit board. The shielding film of the present invention is a barrier layer having an insulating layer and a flame retardant resin. According to the above configuration, the shielding film of the present invention has a barrier layer containing a flame retardant resin, and can be provided without being lowered by a flame retardant resin (especially a flame retardant thermosetting resin having high heat resistance). A flame-retardant shielding film that can be used without problems even in a subsequent process, such as a leveling property in a printed circuit. In the shielding film of the present invention, the shielding layer is preferably one or more isotropic conductive adhesive layers having at least one surface formed on one of the insulating layers. According to the above configuration, when the shielding film of the present invention is adhered to the printing circuit, the electromagnetic shielding property can be exhibited to the isotropic conductive adhesive layer by the conduction of the pattern of the grounding circuit. In the shield layer of the shielding film of the present invention, it is preferable that one or more metal layers formed on at least one surface of the insulating layer and one or more layers of an isotropic conductive adhesive layer are provided. According to the above configuration, when the printed circuit is adhered to the shielding film of the present invention, the pattern of the grounding circuit and the metal layer of the shielding film of the present invention can be electrically connected to the opposite-conductive conductive adhesive layer, -6 - (3) (3) ) 200803664 can play electromagnetic shielding. In the shielding film of the present invention, the conductive adhesive layer further contains a flame retardant, and the flame retardant is preferably 10 to 180 parts by weight to 100 parts by weight of the flame retardant resin. According to the above configuration, even if the film is extremely thin to 35 μm or less, it is qualified in the vertical burning property test (VTM specification) of UL 94', and the adhesion to the substrate or the like is high, and it is surely provided in flexibility and preservation. A shielding film that is also excellent in stability. In the shielding film of the present invention, the flame retardant resin is preferably a phosphorus-containing resin containing a flame retardant resin. According to the above configuration, a highly flame-retardant shielding film can be surely provided. In the shield printed circuit board of the present invention, any of the above-mentioned shielding films is provided on at least one surface of a substrate including one or more printed circuits. According to the above configuration, the pattern of the conductive connection grounding circuit and the metal film of the shielding film of the present invention can provide a shield printed wiring board excellent in electromagnetic wave shielding properties. Further, a shield printed wiring board that is qualified in the vertical flammability test (V specification) of UL 94 can be provided. In the shield printed circuit board of the present invention, it is preferable that the base is a flexible printed circuit board. According to the above configuration, the electromagnetic wave shielding property is excellent, and the base body is a flexible flexible printed wiring board, and a shield printed wiring board which can be used in a portion where bending is required can be provided. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a cross-sectional view showing a shielding film according to an embodiment of the present invention. -7- (4) (4) 200803664 The shielding film 1 shown in Fig. 1 is formed by sequentially providing a metal layer 3 and an adhesive layer 4 on one surface of the insulating layer 2. The insulating layer 2 is composed of a coating layer covering a film or an insulating resin. The cover film is made of engineering plastics. For example, there are polypropylene, crosslinked polyethylene, polyester, polybenzimidazole, aromatic polyamine, polyimine, polyamidamine, polyetherimide, polyphenylene sulfide (PPS) , polyethylene naphthalate (PEN) and the like. When the heat resistance is not excessively required, a polyester film of a low price is preferable, and when a flame retardancy is required, a film of a polyphenylene sulfide is preferable, and when a heat resistance is required, a film of a guanamine film or The quinone imine film is preferred. The insulating resin may be an insulating resin, and examples thereof include a thermosetting resin or an ultraviolet curable resin. Examples of the thermosetting resin include a phenol resin, an acrylic resin, an epoxy resin, a melamine formaldehyde resin, a silicone resin, and an acrylic denatured polyoxyn resin. Examples of the ultraviolet curable resin include epoxy acrylate resin, polyester acrylate resin, and methacrylate modified products. Further, it may be cured, cured, cured by ultraviolet rays, hardened by electron beam, or the like, and may be cured. Further, the thickness of the insulating layer 2 is Ιμηι to ΙΟμιη, and more preferably 3 μm to 7 μm. As the metal material forming the metal layer 3, there are copper, brocade, silver, gold, and the like. The metal material can be selected in accordance with the obtained shielding characteristics. As a method of forming the metal layer 3, there are vacuum deposition, sputtering, CVD, ruthenium (metal organic), electroplating, etc., but considering mass productivity, vacuum evaporation is better than 200803664 (5), and is stable at a low price. A metal film is obtained. Further, the metal layer 3 is not limited to the metal thin film, and a metal foil may be used. The thickness of the metal layer 3 is generally preferably 0.01 to ΙΟμηη. If Ο.ΟΙμη or less, the shielding effect is insufficient, and conversely, when ΙΟμιη is exceeded, the flexibility is deteriorated. In particular, when flexibility is required, it is preferably 2 μm or less, and particularly, when a shielding effect is required, it is preferably ΙΟμη or less. As the adhesive layer 4, a thermosetting resin which is resistant to heat resistance at a substrate (leveling) of 260 ° C is used, and a thermosetting resin which is difficult to burn is preferably used. A flame retardant or conductive coating having isotropic conductivity or anisotropic conductivity. The thickness of the adhesive layer 4 is preferably from 5 μm to 30 μm. If it is thinner than 5 μm, sufficient adhesion cannot be obtained, and if it exceeds 30 μm, the flexibility is impaired. Further, when the adhesive layer 4 has an isotropic conductivity, the metal layer 3 may not be used. As the flame retardant thermosetting resin, phosphorus contains a thermosetting resin, a bisphenol oxime type, a bisphenol F type, a novolak type, and the like. Here, the phosphorus contains a thermosetting resin, an epoxy resin, a thermoplastic resin, and a phosphorus-containing compound. As such an epoxy resin, bisphenol A, biguanide F or biguanide is used as a starting material to be reacted with epichlorohydrin. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and further, using hydrazine, fluorenyl-methoxymethyl hydrazine, or naphthalene diol as a starting material, using formaldehyde The condensate is obtained by reacting with epichlorohydrin. For example, there are benzoquinone epoxy resin, 0-cresol novolak resin, naphthol novolak resin, etc., and these may be used alone or in combination of two or more. 200803664 (6) Further, as the thermoplastic resin herein, there are a polyamido resin, a phenoxy resin, a polyester resin, a polycarbonate resin, a polyphenylene oxide resin, a polyurethane resin, and a polyoxymethylene. A resin, a polyethylene resin, a polypropylene resin, a polyvinyl resin, etc. may be used alone or in combination of two or more. A thermosetting resin having flexibility can be obtained by blending a thermoplastic resin with an epoxy resin. Further, the phosphorus compound herein may be a reaction type which is directly reacted with an epoxy resin or the like, or a non-reactive type which does not directly react. The reaction type which is directly reacted with an epoxy resin or the like is not particularly limited, but has a functional group of a hydroxyl group, an amine group, a carboxyl group, a methylol group, an epoxy group, an isocyanate group, a stanol group, a vinyl group or the like, and has heat resistance. Sex or adhesiveness, etc. The blending ratio of phosphorus containing thermosetting resin is 10 to 60 parts by weight of (A) epoxy resin, (B) 100 parts by weight of thermoplastic resin, and the total weight of (C) (A) and (B) is 10~ 35 mass%. Thereby, it is possible to provide a shielding film which is resistant to substrate mounting (leveling) and has flexibility. As a flame retardant, a halogen-free flame retardant is preferred from the viewpoint of environmental problems, such as metal water and a substance such as melamine cyanurate, or a phosphorus-based flame retardant such as a phosphate or a red phosphorus. When it is required to have heat resistance, it is preferred to use melamine cyanurate or magnesium hydroxide. The blending ratio of the flame retardant is preferably from 10 to 80 parts by weight to the weight portion of the flame retardant resin, and more preferably from 50 to 150 parts by weight. If it exceeds 180 parts by weight, sufficient adhesion cannot be obtained, and if it is 1 part by weight or less, the performance of flame retardancy is insufficient. As the conductive material, carbon, silver, copper, nickel, solder, aluminum-10-200803664 (7), and a silver-coated copper-coated copper material coated with copper powder are applied, and plating is applied to a resin ball or a glass bead. A metal crucible or a mixture of such dips. Silver is a high price, copper is a lack of heat resistance, aluminum is lack of moisture resistance, and solder is not sufficiently conductive, so it is electrically conductive at a lower price. Further, a silver-coated copper crucible or nickel having high reliability is preferable. The blending ratio of the conductive material is also about to be about 10 to 100 parts by weight, more preferably 10 to 100 parts by weight, and more preferably 15 to 50 parts by weight. When the weight exceeds 100 parts by weight, the adhesion to the ground circuit (copper foil) is lowered, and the flexibility of the shielded flexible printed circuit board (hereinafter referred to as a shielded FPC) is deteriorated, and the difficulty is lowered. Combustion performance. Moreover, below 1 〇 of the weight portion, the conductivity is remarkably lowered, and the flame retardancy is lowered. The shape of the metal crucible may be any of a spherical shape, a needle shape, a fiber shape, a sheet shape, and a resin shape. According to the above embodiment, since a thermosetting resin having high heat resistance is used, it is possible to provide a flame-retardant barrier film which can be used without problems even if it is subjected to a leveling treatment or the like in a subsequent process. Moreover, even in the case of a film which is extremely thin to 3 5 μηι or less, it is surely provided in the vertical flammability test (VTM specification) of UL 94, and it is also highly flexible in adhesion to a substrate or the like. A shielding film excellent in properties and storage stability. Further, since the flame retardant resin is phosphorus-containing, it is possible to provide a highly flame-retardant barrier film. Further, when the shield film of the present embodiment is adhered to the printed circuit, the pattern of the conductive connection circuit and the metal layer of the shield film of the present invention are -11 - 200803664 (8), and thus electromagnetic wave shielding properties can be exhibited. Further, the shielding film of the present invention can be used in FPC, COF, RF, multilayer flexible substrate, rigid substrate, etc., but is not necessarily limited thereto. Further, as a structure to be adhered to the FPC, for example, the printed circuit board 1 is shielded as shown in Fig. 2 . Here, 5 is a base film, 6 is a printed circuit, 7 is an insulating film, and 8 is a base film. The surface of the printed circuit 6 is composed of a signal circuit 6a and a ground circuit 6b; and is covered with an insulating film in addition to at least a part (non-insulating portion) 6c of the ground circuit 6b. The insulating film 7 is an insulating removal portion 7a having a part of the adhesive layer 4 flowing into the shielding film 1 inside. Thereby, the ground circuit 6b and the metal layer 3 are electrically connected. Here, the bonding of the tape-based film 5 to the printed circuit 6 may be performed by bonding with an adhesive or without using an adhesive, and may be joined in the same manner as the so-called non-adhesive type copper-clad laminate. can. Further, the insulating film 7 may be formed by bonding a flexible insulating film together with an adhesive, or by a series of methods of coating, drying, exposing, developing, and heat-treating the photosensitive insulating resin. can. Further, the base film 8 is a double-sided FPC having a printed circuit only on one surface of the base film, a double-sided FPC having a printed circuit on both sides of the base film, and a plurality of layers of such a FPC. Multi-layer FPC, which has a multi-layer part bearing portion and a cable portion of the Phillips (registered trademark), or a member that constitutes a multi-layered part as a rigid flexible substrate, or a TAB tape for a package. It can be implemented. Further, the base film 5 and the insulating film 6 are all made of engineering plastics. For example, there are polypropylene, cross-linked polyethylene, polyester, polybenzimidazole, polyimine-12-200803664 (9), polyamidamine, polyetherimine, polyphenylene sulfide (PPS) ), etc. Resin. When the heat resistance is not excessively required, a polyester film having a low price is preferable, and when a flame retardancy is required, a polyphenylene sulfide film is preferable, and when heat resistance is required, a bismuth imide film is required. Preferably. According to the above configuration, the pattern of the conductive connection grounding circuit 6b and the metal layer 3 of the shielding film 1 of the above-described embodiment can provide the shield printed wiring board 10 having excellent electromagnetic wave shielding properties. Further, even if the film is extremely thin to 35 μηα or less, a shielded printed wiring board which is acceptable in the vertical burning property test (V specification) of UL 94 can be provided. Further, since the base film 8 is FPC, it is excellent in electromagnetic wave shielding properties and flexible, and can provide a shield printed wiring board 1 which can be used in a portion where bending is required. [Examples] Shield films of Examples 1 to 4 and Comparative Examples 1 to 4 which were formed in the same manner as the mask film 1 shown in Fig. 1 were produced. Hereinafter, the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4 of the above will be described. Further, for the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4, an epoxy resin having a thickness of 5 μm was used as the insulating layer 2, and a silver vapor-deposited layer having a thickness of Ο.ίμηι was used as the metal layer 3. . The thickness of the adhesive layer 4 is 17 μm, and the phosphorus-containing epoxy resin (flammable resin) has a weight of 1 〇〇, and each of the flame retardants composed of melamine polytricylate is added. A conductive material composed of silver-coated steel powder of 20 parts by weight was added (refer to Table 1). -13- 200803664 (10) [Table 1] Real _ Comparative Example 1 2 3 4 1 2 3 4 Phosphorus Containing Epoxy Resin (Weight) 100 100 Epoxy Resin (Weight) _ _ 100 Flame Retardant ( Weight 咅 10 50 150 180 0 5 200 150 Characteristic flame retardant VTM—0 〇〇〇〇 XX 〇X V-0 〇〇〇〇X 〇〇〇 Leveling 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇 〇〇 〇〇〇〇X 制作 Preparation methods of the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4 First, the metal layer 3 is provided on one surface of the insulating layer 2, and each of the examples and comparisons of the above Table 1 are provided. The adhesive layer 4 of the component of the example was used as a shielding film of each of the examples and the comparative examples. Further, in tests other than the flame retardancy test and the flexibility test, in order to evaluate Examples 1 to 4 and Comparative Example 1 The shielding film of 4 was subjected to a stamping of 3 MPa in which the shielding films of the respective examples and the comparative examples were applied at 1 70 ° C for 3 minutes, and after adhering to the substrate of each test, 60 at 150 ° C was applied. After the minute hardening. The method of the leveling resistance test is directed to the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4. The following leveling resistance test was carried out. The copper foil of the copper-clad laminate which was used as the substrate (F- 30VC1 made by Nikkei Industrial Co., Ltd. -14-200803664 (11)) was adhered to the adhesive layer. Each of the shielding films is formed on the insulating layer side of the shielding film as an upper surface, and passed through an IR leveling furnace (peak temperature: 2 6 5 ° C). Thereafter, the surface of the insulating layer having the shielding film is observed by the eyes, peeling off, etc. The appearance of the appearance is abnormal. If the appearance is abnormal, such as bulging and peeling, it is confirmed that there is an abnormal appearance such as bulging or peeling, and the result table Tpc is shown in Table 1. Method of flammability test (VTM specification) The following flame retardancy test was performed on the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4. First, the surface of the adhesive layer of each shielding film was used by the above-described production method. After the transfer film was formed, each of the shielding film monomers was subjected to a 3 MPa press at 170 ° C for 3 minutes, and then the transfer film was peeled off and subjected to post-curing at 60 ° C for 60 minutes. Each of the shielding film rolls is removed after the mandrel becomes a circle, and is targeted for each The film was evaluated for flame retardancy according to the vertical flame retardancy test (VTM specification) of UL-94. Those who passed the VTM-0 were regarded as 〇, and those who failed were regarded as x, and the results are shown in Table 1. The method of the flame retardancy test (V-size) was carried out by adhering the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4 to a polyimide film (Toray Dupont Co., Ltd.) having a thickness of 25 μm. The Kapton 100 Η) was evaluated for flame retardancy according to the UL-94 vertical flame retardancy test (V specification). The qualified person on V-0 is taken as ◦, and the unqualified person is taken as X, and the result is shown in Table 1. -15- 200803664 (12) Method of adhesion test The following adhesion test was carried out for the shielding films of Examples 1 to 4 and Comparative Examples 1 to 4. First, using the above-mentioned production method, a polyimide film having a thickness of 25 μm as a substrate (manufactured by Toray Dupont Co., Ltd., Kapton 100 Η) was adhered to the adhesive layer. Each shielding film. Thereafter, the polyimide film was peeled off at 180 °, and the strength (adhesiveness) of the mask film was measured. The strength of 4.0 N/cm or more was defined as 〇 (pass), and the amount of less than 4.0 N/cm was taken as χ (failed), and the results are shown in Table 1. According to the above-mentioned results, it is possible to provide a flame-retardant shielding film that can be used without any problem in adhesion to a printed circuit or the like, and which can be used without any problem in a subsequent process, and a shield printed circuit wiring using the same. board. Further, the present invention is not limited to the above embodiments, and may be modified without departing from the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing a shielding film according to an embodiment of the present invention. Fig. 2 is a partial cross-sectional view showing the FPC to which the shielding film of Fig. 1 is attached. [Main component comparison table] 1 : Shielding film-16- 200803664 (13) 2 : Insulation layer 3 : Metal layer 4 : Adhesive layer 5 : Base film 6 : Printed circuit ' 6a : Signal circuit 6 b : Ground circuit 6 c : non-insulating portion 7 : insulating film 7 a : insulating removing portion 8 : base film 1 〇 : shield printed circuit board -17-