201136758 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種金屬薄膜轉印材料及其製造方法， 其係使容易腐蝕的島狀構造金屬薄膜之耐蝕性大幅提高， 由於具有絕緣性而抑制靜電破壞，能夠賦予電波穿透性， 具有優異的金屬光澤之設計性》 【先前技術】 $用島狀構造金屬之金屬薄膜轉印材料係用以將優異 的美感賦予電視、音響、錄影機等之家電製品；或行動電 言舌 '個人資訊終端機等之資訊通訊機器；汽車內的資訊通 訊機器等之框體，用於爲了將金屬光澤賦予表面。 爲了此目的，於專利文獻1及2中，有人提案將利用 真空蒸鍵法於轉印材料形成所獲得之金屬薄膜進行轉印至 必須具有美感的基材之方法，作成因此之金屬薄膜而防止 靜電破壞’基於穿透電波之目的下而使用錫或銦等之島狀 構造金屬薄膜。 於專利文獻3中揭示一種技術，其係規定蒸鎪錫之附 著量與光線穿透率之關係，具優越之外觀均勻性的金屬薄 膜轉印材料’亦即相對於錫之附著量而使被覆率上升’達 成更低的光線穿透率。 但是’島狀構造金屬薄膜係藉由氫氧化、氧化等，表 面之金屬光澤容易受損，雖然藉由此等之揭示技術而可以 獲得電波穿透性及絕緣性，但是耐蝕性不足。 201136758 於專利文獻4中，係已揭示一種具有優異 之絕緣性轉印薄膜，其係由剝離樹脂層、保護 緣性金屬薄膜層、由三聚氰胺樹脂而成之耐 層、接著層所構成；但是耐蝕性依然不足。 於專利文獻5中，揭示一種半色調金屬 膜，其係設置保護層而使耐蝕性提高。然而， 進一步耐熱性之提高，雖然專利文獻4揭示的 光澤轉印薄膜提高耐蝕性，但在已使用硫化鋅 有製品安全上的問題。 專利文獻1 :日本專利特公平3 -2 5 3 5 3號公報 專利文獻2:日本專利特開平10-324093號公_ 專利文獻3 :日本專利特開2008- 1 05 1 79號公幸 專利文獻4:日本專利特開2007-326300號公等 專利文獻5 :日本專利特開2008-207337號公专 【發明內容】 〔發明所欲解決之問題〕 本發明之目的係解決上述問題點，亦即在 具有優異的耐蝕性的金屬薄膜轉印材料。 〔解決問題之手段〕 爲了解決上述問題，本發明係由以下之結 亦即，本發明係一種金屬薄膜轉印材料， 明基材薄膜之至少單面上，依序積層有脫模棱 護樹脂層、絕緣性金屬薄膜層與接著劑層之途 印材料；絕緣性金屬薄膜層之厚度X爲5 nm 3 的耐腐蝕性 樹脂層 '糸色 腐蝕性樹脂 光澤轉印薄 近年來尋求 半色調金屬 之點上，具 於提供一種 構所構成。 其係在透 '脂層、保 :屬薄膜轉 ；10 0 nm » 201136758 於將全部光線透射率設爲 Tr ( % )時，符合BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal thin film transfer material and a method for producing the same, which are capable of greatly improving corrosion resistance of an island structure metal thin film which is easily corroded, and having insulation properties. It suppresses electrostatic breakdown, imparts radio wave penetration, and has excellent metallic luster design. [Prior Art] $Metal film transfer material made of island-like structure metal is used to impart excellent aesthetics to TVs, stereos, and video recorders. Such as home appliances; or mobile communication devices such as personal information terminals; information and communication devices in automobiles, etc., are used to impart metallic luster to the surface. For this purpose, in Patent Documents 1 and 2, it has been proposed to transfer a metal thin film obtained by forming a transfer material by a vacuum evaporation bonding method to a substrate which is required to have an aesthetic feeling, thereby preventing the metal thin film from being formed. The electrostatic breakdown 'is an island-shaped structural metal thin film such as tin or indium based on the purpose of penetrating the electric wave. Patent Document 3 discloses a technique for defining the relationship between the amount of deposited antimony tin and the light transmittance, and the metal film transfer material having superior appearance uniformity, that is, coating with respect to the amount of tin adhered. The rate rises to achieve a lower light penetration rate. However, the metal thin film of the island-shaped structure is easily damaged by hydrogenation, oxidation, or the like, and the radio wave permeability and the insulating property can be obtained by the above-described technique, but the corrosion resistance is insufficient. 201136758 Patent Document 4 discloses an excellent transfer printing film which is composed of a release resin layer, a protective edge metal film layer, a melamine resin-resistant layer, and an adhesive layer; Sex is still insufficient. Patent Document 5 discloses a halftone metal film which is provided with a protective layer to improve corrosion resistance. However, in the improvement of the heat resistance, although the gloss transfer film disclosed in Patent Document 4 improves the corrosion resistance, there is a problem in the safety of the use of the zinc sulfide. Patent Document 1: Japanese Patent Publication No. Hei 3 - 2 5 3 5 3 Patent Document 2: Japanese Patent Laid-Open No. Hei 10-324093--Patent Document 3: Japanese Patent Laid-Open No. 2008- 1 05 1 79 Japanese Patent Laid-Open No. 2007-326300 (Patent Patent Document 5: Japanese Patent Laid-Open No. Hei No. No. 2008-207337) [Summary of the Invention] The object of the present invention is to solve the above problems, that is, A metal film transfer material having excellent corrosion resistance. [Means for Solving the Problems] In order to solve the above problems, the present invention is a metal film transfer material in which at least one surface of a film of a base substrate is laminated with a release resin layer, Insulating metal film layer and adhesive layer printing material; insulating metal film layer thickness X is 5 nm 3 corrosion-resistant resin layer '糸色腐蚀性树脂光光转薄 In recent years, the point of seeking halftone metal In addition, it provides a structure. It is in the penetration of the 'lipid layer, the protective film is turned; 10 0 nm » 201136758 when the total light transmittance is set to Tr (%),
Tr 2 87.522 χΕχρ ( -0.0422 χΧ )之關係。 另外，本發明係一種金屬薄膜轉印材料，其係在透 明基材薄膜之至少單面上，依序積層有脫模樹脂層、保 護樹脂層、金屬薄膜層、絕緣性金屬薄膜層與接著劑層 之金屬薄膜轉印材料；金屬薄膜層之附著量爲15 ng/cm2 至7 00 ng/cm2、絕緣性金屬薄膜層之厚度X爲5 nm至 100 nm，於將全部光線透射率設爲 Tr ( % )時，符合 Tr2 87.522xExp(-0.0422xX)之關係。 另外，本發明係提案一種金屬薄膜轉印材料之製造 方法，其特徵爲在透明基材薄膜之至少單面上，積層有 脫模樹脂層、保護樹脂層之基材表面上，藉由減壓下之 電漿處理而進行表面處理，在其上形成絕緣性金屬薄膜 層，且在該絕緣性金屬薄膜層上積層接著性樹脂層。 〔發明之效果〕 本發明之金屬薄膜轉印材料係由於全部光線透射率爲 高的比例，且絕緣性金屬薄膜層的島狀構造中之每個島的 高度高，不會隨時間經過而使絕緣性金屬薄膜層容易腐 蝕，具有優異的耐蝕性。 尤其，在相較於行動電話或聲響製品之耐蝕性的評估 基準之耐飩性試驗（溫度60°C、濕度95% RH之條件下放 置96小時之試驗）爲嚴格的耐蝕性試驗（溫度85°C、濕 度85% RH之條件下放置48小時之試驗）下，因爲全部光 201136758 線透射率之變化率爲1至2.5倍，且不會因腐蝕而 性金屬薄膜層消失，以被強烈要求耐蝕性之行動電 響製品等爲首，而能夠使用於非常廣範圍之用途。 【實施方式】 以下，針對本發明之內容而詳加說明。 本發明之金屬薄膜轉印材料係由在透明基材薄 序設置脫模樹脂層、保護樹脂層，進一步依序形成 金屬薄膜層、接著劑層所構成。 於本發明中’透明基材薄膜能夠使用通常轉印 用之習知塑膠薄膜。就塑膠薄膜而言可舉例：聚酯 丙烯酸薄膜 '聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、_ 聚乙烯薄膜、聚丙烯薄膜等，其中，聚酯薄膜係在 與耐濕性上較佳。就聚酯薄膜而言可舉例：雙軸拉 苯二甲酸乙二酯薄膜、雙軸拉伸聚萘二甲酸乙二 等’其中雙軸拉伸聚對苯二甲酸乙二酯薄膜在耐熱 膜價格等上更佳。 上述透明基材薄膜之厚度較佳爲10 μιη至100 作成金屬薄膜轉印材料之情形的操作性之觀點，特 μπι至50 μπι之範圍。 另外’以設計性之提高爲目的，也可以在透明 膜之脫模樹脂層側實施毛紋（hairline)加工、壓紋力口 (mud)加工等之凹凸加工，藉由實施如此之加工， 之金屬薄膜轉印材料轉印至被轉印物之塑膠基材後 使絕緣 話或聲 膜上依 絕緣性 薄膜所 薄膜、 t薄膜、 耐熱性 伸聚對 酯薄膜 性與薄 μιη，從 佳爲1 2 基材薄 工、泥 本發明 所獲得 201136758 之成形物的轉印部分表面成爲凹凸形狀，能夠作成更具優 越設計性之完成的成形品。 於本發明之金屬薄膜轉印材料中，在透明基材薄膜之 單面設置脫模樹脂層。就脫模樹脂層而言，係爲磷脂質（卵 磷脂）、醋酸纖維素、蠟、脂肪酸、脂肪酸醯胺、脂肪酸 酯、松香、丙燦酸樹脂、矽氧烷、氟樹脂等。按照其剝離 容易性之程度’經適當選擇所使用。基底薄膜爲平滑之情 形係脫模樹脂層爲〇.〇1 μιη至2 μιη之厚度，更佳爲使用 0.1 μιη至1 μιη之厚度。 脫模樹脂層能夠利用凹版塗布法、反向（reverse)塗布 法、模具（die)塗布法等之習知方法而形成。 於本發明之金屬薄膜轉印材料中，爲了保護轉印後之 絕緣性金屬薄膜層而具有保護樹脂層。如此之保護樹脂層 的樹脂係使用與脫模樹脂層及絕緣性金屬薄膜層中任一層 接著性佳的熱硬化性樹脂、熱可塑性樹脂或是藉由紫外線 等所導致的光硬化性樹脂。具體而言，保護樹脂層係能夠 根據蒸鍍金屬之種類、依照用途所導致的必要各種性能（機 械特性 '耐熱性、耐溶劑性、光學特性、耐候性等）而適 當選擇，例如能夠使用由丙烯酸樹脂、三聚氰胺樹脂、胺 甲酸酯樹脂、環氧樹脂、醇酸樹脂、纖維素系、聚氯乙烯 系等所選出的一種或二種以上。一般而言，其厚度爲0.2 μπι 至5 μιη左右，更佳爲1 μιη至3 μιη。此等之樹脂係使用透 明性佳者，也能夠加入染料、顏料或消光劑而著色。另外， 201136758 藉由在保護樹脂層之表面實施全像（hologram)加工，也 能夠賦予虹彩色或全像效果。 保護樹脂層能夠利用凹版塗布法、反向塗布法、模具 塗布法等之習知方法而形成。 形成本發明之脫模樹脂層及保護樹脂層的樹脂也可以 爲根據丙烯酸系樹脂等所獲得之同種樹脂。此情形下，金 屬薄膜轉印材料係使接著劑介於中間而接著於被黏著物 後’於剝離透明基材薄膜之際，引起因脫模樹脂層中之凝 聚破壞所造成的剝離，也包含轉印保護樹脂層及脫模樹脂 一部分而作爲保護樹脂層之機能的層設計。 必要時，基於使與絕緣性金屬薄膜層的接著性提高之 目的，本發明也可以進一步在該保護樹脂層上積層易接著 層。 本發明之金屬薄膜轉印材料係將絕緣性金屬薄膜層設 置於上述保護樹脂層上。所謂本發明中之絕緣性金屬薄膜 係指兼具金屬光澤與絕緣性之金屬薄膜，且島狀構造之不 連續的金屬薄膜。 於本發明中，絕緣性金屬薄膜層之厚度X必須爲5 nm 至lOOnm，較佳爲20nm至80nm，更佳爲50nm至80nm。 若厚度低於5 nm，光線穿透率大，無法獲得修飾所期待的 金屬光澤感。另外，厚度超過100 nm之情形，由於無法確 保本發明視爲必要的蒸鍍膜之絕緣性，則抑制不住靜電破 壞，無法確保更充分之電波穿透性。 201136758 於本發明中，較佳爲將絕緣性金屬薄膜層之全部光線 透射率Tr ( % )設爲5%至50%之範圍，其與絕緣性金屬 薄膜層之厚度X(nm)的關係必須符合式1，更佳爲符合 式2。 式 1 Tr 2 87·522 χΕχρ ( -0·0422 χΧ ) 式 2 Tr ^ 1 20.52 χΕχρ ( -0.0418χΧ) 此等之式係意指如下所示。亦即，右邊係絕緣性金屬 薄膜層之厚度X的函數，顯示若X增大時，則指數函數値 將變小，顯示全部光線透射率Tr爲此X函數値以上。換言 之，顯示此等之.式設爲等式之情形的絕緣性金屬薄膜係具 有相對於某透射率Tr的厚度X以上之厚度。 若根據習知技術，一旦增厚絕緣性金屬薄膜層之厚度 時，由於島之間隔將變窄，所以爲了確保絕緣性而不得不 減少金屬量，則其容易受到因氧化、氫氧化所造成的腐蝕 之影響。本發明爲即使增厚絕緣性金屬薄膜層之厚度也能 夠某種程度地保持島之間隔，故能夠一邊將Tr保持於一定 値以上且一邊確保絕緣性。因此，並無減少金屬量之必要， 所以難以受到因氧化等所導致的腐蝕之影響。若符合式2， 則附著許多的絕緣性金屬，同時也能.夠達成高的光線穿透 率，故能夠確保更高的耐蝕性。 於本發明中，絕緣性金屬薄膜層之島的尺寸或間隔係 根據所使用的金屬之種類、設計性、絕緣性之程度等而異， 從設計性之觀點，島之尺寸較佳爲1 nm至2 μπι;從絕緣 -10- 201136758 性之觀點，島之間隔較佳爲2 n m至5 0 Ο n m。 於本發明中，絕緣性金屬薄膜層之全部光線 佳爲5%至50%。藉由將絕緣性金屬薄膜層之厚 範圍，則耐蝕性、設計性將提高。從此等效果之 預先將全部光線透射率設爲8%至3 0%的話，則 本發明之金屬薄膜轉印材料係將轉印至透明 曝露於溫度85°C、濕度85%RH之環境下48小時 光線透射率，其較佳爲相對於曝露該環境下之前 線透射率之1至2.5倍。若爲2.5倍以下時，金屬 時間經過所造成的外觀變化小，故成爲具有更優 性。 絕緣性金屬薄膜層之厚度係根據所使用的金 設計性等，最好於上述範圍內而適當決定。 針對將絕緣性金屬薄膜層作成島狀構造， 錫、銦、鋅、鉍、鈷、鍺或此等之合金所構成之 選出者作爲所使用的金屬。絕緣性金屬薄膜層更 由錫、銦、鋅所構成之族群中所選出的一種或二 金屬薄膜’從絕緣性之觀點，進一步較佳爲錫、 使用錫之情形的絕緣性金屬層的厚度較佳爲 8 Ο ητη 0 絕緣性金屬薄膜層能夠藉由真空蒸鍍法、 法、EB蒸鍍法等而形成上述金屬。就符合式1或 制絕緣性金屬薄膜層之厚度X與全部光線透射率 透射率較 度設爲此 觀點，若 更佳。 基體之物 後的全部 的全部光 光澤之隨 異的實用 屬種類或 較佳爲由 族群中所 佳爲至少 種以上之 銦。 2 0 n m 至 濺鍍蒸鍍 式2來控 Tr的方法 -11- 201136758 而言，例如能夠以蒸鍍法.中之感應加熱方式之蒸發量、薄 膜速度來控制；於濺鍍法中，能夠以放電氣壓與放電電力 及薄膜速度來控制。 於本發明中發現：符合式1或式2來控制絕緣性金屬 薄膜層之厚度X與全部光線透射率Tr的方法，係藉由在透 明基材薄膜之至少單面上，積層脫模樹脂層與保護樹脂 層：在此保護樹脂層之表面，依照減壓下之電漿處理而進 行表面處理，在其上形成絕緣性金屬薄膜層而能夠達成。 另外也發現：依照濺鍍而使微量金屬附著於基材表面，即 使依照利用所謂的核附著法（seeding method)所進行的表 面處理，也使上述絕緣性金屬薄膜層之厚度X與全部光線 透射率Tr符合式1或式2之關係。於此情形之核附著處理 中，由於保護樹脂層曝露於電漿中，所以能夠定義爲一種 電漿處理。 於上述電漿處理之際，藉由放電電極（陰極）材料與 放電氣體之組合，也有放電電極材料實質上未被濺鍍之情 形，另外依照濺鍍現象而濺鍍放電電極材料，放電電極材 料之金屬也將附著於保護樹脂層上。本發明申請案係無關 於因此等電漿處理所導致的放電電極材料有無附著，提供 符合於式1之關係。 利用減壓下電漿處理中附著放電電極材料的金屬之情 形，係附著量成爲電漿處理之處理強度的指標。亦即，此 情形之本發明係在透明基材薄膜之至少單面，依序積層有 -12- 201136758 脫模樹脂層、保護樹脂層、金屬薄膜層 層及接著層的金屬薄膜轉印材料；金屬 15 ng/cm2至7 00 ng/cm2，絕緣性金屬薄 nm至100 nm，於將全部光線透射率設 合 Tr287.522xExp( -0.0422χΧ)之關係 料。 金屬薄膜層係使15 ng/cm2至700 5〇1^/<：1112至50〇1^/(：1112之金屬附著。使 量成爲15 ng/cm2至700 ng/cm2之範圍 的絕緣性金屬薄膜層之厚度X成爲5 15 ng/cm2之情形，則耐蝕性爲不足；超 形，則電波穿透性或絕緣性將惡化。設 法係如上所述，依照與減壓下之電漿處 所進行的方法，或是也可以爲積極的濺 之放電電極材料或是利用濺鍍法所使用 用由鋁、銀、金、錫、銦、鉛、鋅、鉍' 鎳、矽、鍺或此等之合金所構成之族群 波穿透性之觀點，較佳爲使用銦、錫。 如上所述，絕緣性金屬層較佳爲含 構成之族群中所選出的一種或二種以上 穿透性之觀點，金屬薄膜層較佳爲與絕 同種；使用異種金屬之情形，與原本所 的金屬光澤成爲不同的色調；從此觀點 、絕緣性金屬薄膜 薄膜層之附著量爲 膜層之厚度X爲5 爲Tr ( % )時，符 的金屬薄膜轉印材 ng/cm2，較佳爲使 金屬薄膜層之附著 內，使其後所’形成 m至100 nm。低於 過700 ng/cm2之情 置金屬薄膜層之方 理同時發生的濺鏟 鍍法。電漿處理中 的靶金屬種能夠使 •鈦、絡、鐵、銘、 中所選出者。從電 有由錫、銦、鋅所 之金屬者，從電波 緣性金屬層之金屬 期待的絕緣性金屬 ，較佳爲使用同種 201136758 金屬。 本發明之金屬薄膜轉印材料中之接著劑層係在絕緣性 金屬薄膜層上所形成，於轉印後，接著塑膠基材與轉印層 (脫模樹脂層、保護層、絕緣性金屬薄膜層及接著劑層） 者。 使用於接著劑層之樹脂能夠使用丙烯酸系樹脂、聚酯 系樹脂、三聚氰胺系樹脂、環氧系樹脂、氯乙烯系樹脂、 醋酸乙烯系樹脂、氯乙烯-醋酸乙烯共聚物樹脂等。 接著劑層能夠利用凹版塗布法、反向塗布法、模具塗 布法等之習知方法而形成。 能夠使用本發明之金屬薄膜轉印材料而獲得半色調金 屬光澤薄膜’進一步能夠藉由熱輥轉印或模內成型而獲得 半色調金屬光澤成形物，藉由模內成型而獲得半色調金屬 光澤成形物之情形，以提高透明基材薄膜與脫模樹脂層之 脫模性、且防止轉印時發生塑膠薄膜之剝離不良或破裂之 目的下，在透明基材薄膜與脫模樹脂層之間，較佳形成下 塗層，而藉由該下塗層之形成，以便能夠穩定獲得複雜形 狀之成形物。使用於下塗層之樹脂，能夠使用三聚氰胺系 樹脂、胺基醇酸系樹脂、環氧系樹脂、丙烯酸系樹脂、砂 氧烷系樹脂等之熱化性樹脂或蠟等，特佳爲三聚氰胺系樹 脂或丙烯腈-三聚氰胺系樹脂。 本發明之金屬薄膜轉印材料係利用針對如上所述之行 動電話或音響製品之耐腐蝕性的評估基準之高溫高濕試驗 -14- 201136758 (溫度85°C、濕度85% RH之條件下放置48小時之試驗）， 藉由使試驗後之全部光線透射率成爲相對於試驗前的全部 光線透射率之1至2 · 5倍，因爲不會藉腐蝕而使絕緣性金 屬薄膜層消失’以被強烈要求耐蝕性之行動電話或聲響製 品爲首，而使可用於非常廣範圍的用途。 〔實施例〕 以下，根實施例而具體說明本發明之形態，但本發明 並不受此等實施例所限定。再者，本發明中之評估法係如 下所述： (1)金屬薄膜層之金屬附著量 將5 cm xl cm之試料薄膜置入以1:4之比混合鹽酸與 硝酸的溶液中，放置24小時以上。 使用島津製作所製原子吸光分光光度計AA-6300，以 測定波長：2 8 6.3 nm、燈電流·· 1 〇 m A '狹縫寬度：0 · 7 nm、 點燈模式：BGC-2、1 %吸光光度：5.0 ppm而測定此溶液。 (2 )全部光線透射率（％ ) 於用乙醇擦拭厚度1111111><寬度10(；111><長度20(：111之西 烯酸板之表面上，使用輥壓杵（太平工業（股）製 RT-3 00X )，以輥溫度220°C、速度5 cm/秒轉印後，剝離 薄膜，製得將保護層作爲表面之測試珠。使用日本電色工 業（股）製混濁度計NDH-2000，依照JIS-K7136 ( 2000年 制定）而測定所製得之測試珠的全部光線透射率Tr ( % )。 (3 )絕緣性金屬薄膜層之厚度X ( nm ) -15- 201136758 將設置根據蒸鍍加工所獲得之絕緣性金屬層之薄膜作 爲試料，使用日立會聚離子束加工觀察裝置FB2000A，作 成試料剖面後，利用日立穿透型電子顯微鏡（TEM)HF-2100 而以加速電壓30 kV、觀測倍率421，000倍觀察絕緣性金屬 薄膜層之剖面，從其照片之單位視野內所觀察到的島之數 目與島之厚度（從島之保護樹脂層側邊界面起之高度）， 採取數量平均而算出絕緣性金屬薄膜層之厚度X(nm)。 此情形下，島間之間隔並未考量，計算島之最高的部分之 厚度的數量平均値。例如，於第1圖中，計算係（48.9 + 56.6 + 42.6 + 56.7 ) /4 = 51.2 nm。 (4 )耐蝕性試驗 準備厚度1 mm之透明丙烯酸板（透明基體），用乙 醇等擦拭表面，使用輥壓杵（太平工業（股）製RT-300X)， 以輥溫度220°C、速度5 cm/秒轉印作爲絕緣性金屬薄膜轉 印材料之薄膜，剝離薄膜而製得將保護樹脂層作爲表面之 測試珠。使用日本電色工業（股）製混濁度計NDH-2 000 (依照HS-K7 1 3 6 ( 2 000年制定））而測定所製得之測試 珠的全部光線透射率，用夾子吊在Tab ai E spec (股）製恆 溫恆濕烘箱（PL-1SP )之試樣設置網上，於溫度85t、濕 度85%RH之環境下放置48小時。48小時經過物也與上述 同樣地測定全部光線透射率，與環境負荷前之試樣作一比 較。將負荷前（試驗前）穿透率設爲A(%)、負荷後（試 驗後）穿透率設爲B(%)，將B/A之倍率作爲穿透率變 -16 - 201136758 化而算出。 (5)電波穿透性試驗 將切割成15 cmx 15 cm之金屬薄膜轉E Microwave Factory(股）製 KEC法屏蔽效果 MAM101 內，使用 Agilent Technologies \ Analyzer Agilent E5062A，測定 800 MHz 之電 (dB)。電波穿透性係由於金屬薄膜爲不連續 而發現，同時也確保絕緣性。値越小則具有越 穿透性，較佳爲1 dB以下，更佳爲0.5 dB以] (實施例1至3 ) 作爲透明基材薄膜，係使用東洋紡製雙軸 二甲酸乙二酯E5001型25 μηι;在該薄膜之單 脫模樹脂層，係利用照相凹版型塗布機，使乾 爲0.5 g/m2來塗布形成醋酸纖維素樹脂；進一 樹脂層上，使用該塗布機而進行含有甲基丙烯 烯酸-2-羥乙酯、甲基丙烯酸正丁酯、三聚氰胺 溶液的塗布、乾燥、樹脂硬化，而得厚度1 μιη 層；接著，藉由濺鑛法而在該保護樹脂層面 ng/cm2作爲金屬薄膜層。濺鍍條件係使用氬氣 體’將錫電極作爲陰極使用。在該金屬薄膜層 爲絕緣性金屬層，調節Tr而作成5 %、1 5 %及 自之値設爲實施例1、2、3。該絕緣性金屬層 加熱方式真空蒸鍍機（曰本真空製EB52〇7)， 0.04 Pa，藉由蒸鑛加工所設置。使用照相凹版 ;P膜設置於 :測定裝置 製 N e t w 〇 rk 波的衰減率 之島狀構造 優異的電波 c 〇 拉伸聚對苯 面上，作爲 燥後厚度成 步於該脫模 酸、甲基丙 樹脂之甲苯 之保護樹脂 設置錫 50 作爲放電氣 面，將錫作 46%，將各 係使用感應 以操作壓力 塗布機，在 -17- 201136758 該蒸鍍面塗布飽和聚酯樹脂，乾燥後形成厚度1 g/m2之接 著劑層。將評估此處所獲得之金屬薄膜轉印薄膜之性能的 結果顯示於表1。於實施例1、2、3中，任一種皆顯示良 好之電波穿透性，同時在耐蝕性試驗中，試驗前後之變化 (B/A)爲2.5倍以下’故爲良好。還有，針對實施例2所 獲得之絕緣樹脂材料的島狀金屬層之構造，將在TEM之剖 面照片顯示於第1圖。 (實施例4至6 ) 實施例4係將金屬薄膜層之厚度成爲15 ng/cm2、實施 例5則成爲200 ng/cm2、實施例6則成爲500 ng/cm2。接 著，各自的絕緣性金屬薄膜係使光線穿透率Tr成爲1 5 % 的方式來形成錫。其他條件係進行相同於實施例1、2、3 的方式，將作成金屬薄膜轉印材料而評估特性的結果顯示 於表1。實施例4、5、6皆具有良好之電波穿透性、絕緣 性，同時在耐蝕性試驗中之Tr變化爲2.5倍以下。 (實施例7 ) 利用濺鍍法而在保護樹脂層面設置作爲金屬薄膜層之 銅50 ng/cm2。濺鍍條件係將氬氣作爲放電使用，陰極係使 用銅電極。絕緣性金屬係使Tr成爲15%的方式來蒸鍍銦。 (實施例8 ) 進行相同於實施例1的方式而將積層直到所準備的保 護樹脂層爲止的基材薄膜輥設置於感應加熱方式真空蒸鑪 機（日本真空製EB 5207)內，捲起薄膜後，藉由於真空中 使用錫電極之整平方式的電漿處理裝置，一邊流通氮氣且 -18 - 201136758 一邊進行電漿處理’接著蒸鍍作爲絕緣性金屬之錫而使Tr 成爲25%者。再者，藉由僅進行電漿處理且不進行蒸鍍之 事先探討’確3忍錫之附著量爲45 ng/cm2，但利用一連串之 蒸鍍而將錫作爲絕緣性金屬所形成者係推定爲同樣的附著 量。 (實施例9 ) 進行相同於實施例8的方式而藉由於真空中使用銅電 極之整平方式的電漿處理裝置，一邊流通氮氣且一邊進行 電漿處理’接著蒸鍍作爲絕緣性金屬之錫而使Tr成爲23 %者。再者’藉由僅進行電漿處理且不進行蒸鍍之事先探 討’確認銅之附著量爲55 ng/cm2，但利用一連串之蒸鑛而 將錫作爲絕緣性金屬所形成者係推定爲同樣的附著量。 (實施例1 0 ) 進行相同於實施例6的方式而使附著700 ng/cm2之錫 者作成實施例10。雖然電波穿透性被斷定變大至0.6 8 dB 之傾向，但爲實用範圍內，可以獲得良好之物。 (實施例1 1 ) 進行大致相同於實施例7的方式而利用濺鍍法來在保 護樹脂層面上設置3 00 ng/cm2之銅作爲金屬薄膜層之外， 成爲Tr 1 8 %的方式來蒸鍍錫作爲絕緣性金屬。雖然於耐蝕 性試驗中爲良好之結果，但由於核附著之銅金屬的影響， 基材薄膜剝離後之金屬光澤稍微帶有紅色，也成爲電波穿 透性也成爲超過1 dB者。 (實施例1 2 ) -19- 201136758 進行相同於實施例7的方式而將絕緣性金屬層作成 95.8 nm。由於電波穿透性惡化至1 .23 dB，雖然成爲難以 使用於將電波穿透性視爲必要之用途的性能，但能夠適合 使用於僅通常之金屬光澤視爲必要之用途者。 (實施例1 3 ) 進行相同於實施例4的方式而將金屬薄膜之附著量作 成15 ng/cm2，全部光線透射率作成22%，穿透率之變化 成爲2.6倍，耐蝕性成爲稍微不足。 (實施例1 4 ) 進行相同於實施例8、9的方式而同樣地在真空蒸鏟機 中進行電漿處理，連續進行錫之蒸鍍，將電漿處理之電漿 作爲玻璃被覆之電極，電源係使用1 1 〇 kHz之高頻者而以 50W·分鐘/m2之強度進行電漿處理。放電氣體係氧，實質 上，放電電極材料之濺鎪未發生，但符合式1之結果’成 爲具優越之電波穿透性、耐蝕性。 (比較例1、2 ) 未設置金屬薄膜層而設置Tr=6%、17%之錫蒸鍍膜’ 其他條件係進行相同於實施例1之方式，分別將各自作爲 比較例1、比較例2而評估其特性。將評估結果顯示於表1。 於比較例1中，電波穿透性低、絕緣性也不佳。另外比較 例1、2皆爲耐餽性低的結果。還有，將比較例2之TEM 剖面照片顯示於第2圖。 (比較例3 ) 利用相同於實施例1之濺鏟法’以1 0 ng/cm2之附著量 -20- 201136758 而形成金屬薄膜層，使光線穿透率Tr%成爲14%的方式來 形成錫。其他條件係進行相同於實施例1之方式而作爲比 較例3，評估性能而將其結果顯示於表1。於耐蝕性試驗 中，耐蝕試驗前後之Tr的變化率超過2.5倍，故不佳。 (比較例4 ) 利用相同實施例1之濺鍍法，以800 ng/cm2之附著量 而形成金屬薄膜層，使光線穿透率Tr成爲I5%的方式來 形成錫。其他條件係進行相同於實施例1之方式而作爲比 較例4，評估性能而將其結果顯示於表1。電波穿透性將惡 化成1.56dB，絕緣性也成爲不足。金屬之附著量變多，推 定電波穿透性已惡化。 (比較例5 ' 6 ) 進行相同於實施例1之方式而分別將絕緣性金屬層之 厚度作成4.5 11111與108 nm、分別將全部光線透射率作成 7 4 %、2.6 %，分別作爲比較例5、6。於比較例5中，全部 光線透射率高，金屬光澤成爲不足。於比較例6中’無法 確保絕緣性’電波穿透性已惡化。 (比較例7 ) 與實施例13同樣地’於真空蒸鍍機中’使用玻璃被覆 電極而進行電漿處理’將處理強度設爲6 W’分鐘/m2’不 符合式1，耐蝕性變得不足。 -21- 201136758 一撇 耐蝕性試驗 穿透率變化 Β/Α 〇〇 IT) ψ-^ 〇 <N 00 rr rn ΓΟ (N οο ίΝ CN rn (Ν 1.4氺 rn rn 光線透射率(％) Β試驗後Tr(%) σ\ rn CN Ο 〇〇 (Ν fN CN m CN m (N (N rs (N rn 00 CN (N 00 m rn 試驗珠之全部 A:試驗前Tr(%) »〇 ir> •Τ) U-i yr) (Ν (N 卜 00 F-H (N CN (N VO \〇 卜 丨·Η 2 in O (N v〇 ***^ 式2 之右邊 o 14.2 49.1 16.3 12.5 15.2 12.8 , 23.8 20.4 1_14,8_I 14.7 (N (N 30.0 13.5 15.8 39.6 24.1 26.8 - 99.9 27.8 式1 之右邊 ΓΛ 10.1 35.3 11.6 〇\ 〇6 10.8 〇\ 17.0 1__I | 10.5 1 10.4 21.5 αί 11.3 28.5 17.2 19.2 72.4 〇 19.9 電波 穿透性 (dB) 0.117 0.065 0.030 0.050 0.055 0.060 0.045 0.035 0.040 0.680 1.150 1.230 0.045 0.065 6.230 0.065 0.041 1.560 0.010 2.980 0.890 絕緣性金屬 層厚度X i 76.2 51.2 21.5 47.8 . 54.3 49.6 53.6 38.8 42.5 50.2 50.4 95.8 33.3 52.3 48.6 26.6 38.5 36.0 »n — 108.0 F-H ΓΟ 金屬薄膜層 金屬附著量 fS ε 200 i 500 (45) (55) 700 300 *〇 1 ο ο ο 800 1 放電電 極材料 eg eg eg U <5 c3 eg 5 eg 玻璃 1 1 eg eg eg 玻璃 測試珠 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 比較例1 比較例2 1比較例3 1 比較例4 比較例5 比較例6 比較例7 201136758 【圖式簡單說明】 第1圖係在實施例2之絕緣性金屬薄膜層之剖面照片 (穿透式電子顯微鏡照片42 1,000倍）。 第2圖係在比較例2之絕緣性金屬薄膜層之剖面照片 (穿透式電子顯微鏡照片42 1,000倍）。 【主要元件符號說明】 1 保護樹脂層 2 絕緣性金屬薄膜層 -23-The relationship between Tr 2 87.522 χΕχρ ( -0.0422 χΧ ). In addition, the present invention is a metal film transfer material which is laminated on at least one side of a transparent substrate film, and sequentially has a release resin layer, a protective resin layer, a metal film layer, an insulating metal film layer and an adhesive. a metal film transfer material of the layer; the adhesion amount of the metal film layer is 15 ng/cm 2 to 700 ng/cm 2 , and the thickness X of the insulating metal film layer is 5 nm to 100 nm, and the total light transmittance is set to Tr (%), in accordance with the relationship of Tr2 87.522xExp (-0.0422xX). Further, the present invention proposes a method for producing a metal thin film transfer material, which is characterized in that at least one surface of a transparent base film is laminated on a surface of a substrate on which a release resin layer and a protective resin layer are laminated, by decompression The surface treatment is performed by the plasma treatment, and an insulating metal thin film layer is formed thereon, and an adhesive resin layer is laminated on the insulating metal thin film layer. [Effects of the Invention] The metal thin film transfer material of the present invention has a high light transmittance, and the height of each island in the island structure of the insulating metal thin film layer is high, and does not cause over time. The insulating metal thin film layer is easily corroded and has excellent corrosion resistance. In particular, it is a strict corrosion resistance test (temperature 85) in the durability test (the test is carried out for 96 hours under the conditions of temperature 60 ° C and humidity 95% RH) compared with the evaluation criteria of the corrosion resistance of a mobile phone or an acoustic product. Under the condition of °C and humidity 85% under the condition of RH for 48 hours), since the rate of change of the line transmittance of all light 201136758 is 1 to 2.5 times, and the metal film layer does not disappear due to corrosion, it is strongly required. Corrosion-resistant mobile electro-acoustic products, etc., can be used for a wide range of applications. [Embodiment] Hereinafter, the contents of the present invention will be described in detail. The metal thin film transfer material of the present invention comprises a release resin layer and a protective resin layer in a transparent substrate sequence, and further forms a metal thin film layer and an adhesive layer in this order. In the present invention, the conventional transparent plastic film can be used for the transparent substrate film. For the plastic film, for example, a polyester acrylic film, a polyimide film, a polyimide film, a polyethylene film, a polypropylene film, etc., wherein the polyester film is in comparison with moisture resistance. good. For the polyester film, for example, a biaxial phthalate film, a biaxially stretched polyethylene naphthalate, etc., wherein the biaxially stretched polyethylene terephthalate film is in the price of the heat resistant film. Better to wait. The thickness of the transparent base film is preferably from 10 μm to 100 in terms of operability in the case of forming a metal film transfer material, and is in the range of μπι to 50 μπι. In addition, for the purpose of improving the design, the concave and convex processing such as hairline processing and embossing force processing may be performed on the release resin layer side of the transparent film, and by performing such processing, After the metal film transfer material is transferred to the plastic substrate of the transferred material, the insulating film or the sound film is formed by the film of the insulating film, the film of t, and the heat resistance are stretched to the film properties of the film and the thin film, from 1 to 1 2 Substrate thin work and mud The surface of the transfer portion of the molded article obtained in the invention of 201136758 has an uneven shape, and can be formed into a molded article which is more excellent in design. In the metal thin film transfer material of the present invention, a release resin layer is provided on one side of the transparent base film. The release resin layer is a phospholipid (lecithin), cellulose acetate, a wax, a fatty acid, a fatty acid decylamine, a fatty acid ester, a rosin, a propanol resin, a decyl alkane, a fluororesin or the like. It is used as appropriate according to the degree of easiness of peeling. The base film is smooth, and the release resin layer has a thickness of from 0.1 μm to 2 μm, more preferably from 0.1 μm to 1 μm. The release resin layer can be formed by a conventional method such as a gravure coating method, a reverse coating method, or a die coating method. In the metal thin film transfer material of the present invention, a protective resin layer is provided in order to protect the insulating metal thin film layer after transfer. The resin for protecting the resin layer is a thermosetting resin which is excellent in adhesion to any of the release resin layer and the insulating metal thin film layer, a thermoplastic resin, or a photocurable resin which is caused by ultraviolet rays or the like. Specifically, the protective resin layer can be appropriately selected depending on the type of the vapor-deposited metal and various properties (mechanical properties 'heat resistance, solvent resistance, optical properties, weather resistance, and the like) depending on the application, and for example, can be used. One or more selected from the group consisting of acrylic resin, melamine resin, urethane resin, epoxy resin, alkyd resin, cellulose resin, and polyvinyl chloride. In general, the thickness is from about 0.2 μm to about 5 μm, more preferably from 1 μm to 3 μm. These resins are excellent in transparency, and can be colored by adding a dye, a pigment or a matting agent. In addition, 201136758 can also impart iridescent or holographic effects by performing hologram processing on the surface of the protective resin layer. The protective resin layer can be formed by a conventional method such as a gravure coating method, a reverse coating method, or a die coating method. The resin forming the release resin layer and the protective resin layer of the present invention may be the same resin obtained by an acrylic resin or the like. In this case, the metal thin film transfer material is such that the adhesive is interposed and then adheres to the transparent base film after the adherend, causing peeling due to agglomeration damage in the release resin layer, and also includes A portion of the protective resin layer and the release resin is transferred as a layer for protecting the function of the resin layer. If necessary, the present invention may further laminate an easy-adhesion layer on the protective resin layer for the purpose of improving the adhesion to the insulating metal thin film layer. The metal thin film transfer material of the present invention is provided with an insulating metal thin film layer on the protective resin layer. The insulating metal thin film according to the present invention is a metal thin film which has both a metallic luster and an insulating metal film and has a discontinuous island structure. In the present invention, the thickness X of the insulating metal thin film layer must be 5 nm to 100 nm, preferably 20 nm to 80 nm, more preferably 50 nm to 80 nm. If the thickness is less than 5 nm, the light transmittance is large, and the metallic luster which is expected to be modified cannot be obtained. Further, in the case where the thickness exceeds 100 nm, since the insulation of the vapor deposited film which is considered to be necessary in the present invention cannot be ensured, the static electricity can not be suppressed, and the sufficient radio wave penetration cannot be ensured. In the present invention, it is preferable that the total light transmittance Tr (%) of the insulating metal thin film layer is in the range of 5% to 50%, and the relationship with the thickness X (nm) of the insulating metal thin film layer is necessary. It conforms to Equation 1, and more preferably conforms to Equation 2. Equation 1 Tr 2 87·522 χΕχρ ( -0·0422 χΧ ) Equation 2 Tr ^ 1 20.52 χΕχρ ( -0.0418χΧ) These equations are as follows. That is, the function of the thickness X of the insulating metal thin film layer on the right side shows that if X is increased, the exponential function 値 becomes smaller, and the total light transmittance Tr is shown to be X or more. In other words, the insulating metal thin film in the case where the equation is set to the equation has a thickness X or more with respect to a certain transmittance Tr. According to the conventional technique, when the thickness of the insulating metal thin film layer is increased, since the interval between the islands is narrowed, it is necessary to reduce the amount of metal in order to secure the insulating property, which is easily caused by oxidation and oxidation. The effect of corrosion. According to the present invention, even if the thickness of the insulating metal thin film layer is increased, the interval between the islands can be maintained to some extent. Therefore, the insulating property can be ensured while maintaining Tr at a constant level or more. Therefore, there is no need to reduce the amount of metal, so it is difficult to be affected by corrosion caused by oxidation or the like. If the formula 2 is adhered to, a large amount of insulating metal is adhered, and at the same time, a high light transmittance can be achieved, so that higher corrosion resistance can be ensured. In the present invention, the size or interval of the island of the insulating metal thin film layer varies depending on the type of metal used, the design property, the degree of insulation, and the like. From the viewpoint of design, the size of the island is preferably 1 nm. To 2 μπι; from the viewpoint of insulation-10-201136758, the island spacing is preferably from 2 nm to 50 Ο nm. In the present invention, the total light of the insulating metal thin film layer is preferably from 5% to 50%. When the thickness of the insulating metal thin film layer is thick, the corrosion resistance and the design property are improved. When the total light transmittance is set to 8% to 30% in advance from these effects, the metal film transfer material of the present invention is transferred to a transparent exposure temperature of 85 ° C and a humidity of 85% RH. The hourly light transmittance, which is preferably from 1 to 2.5 times the line transmittance before exposure to the environment. When it is 2.5 times or less, the appearance change caused by the metal time is small, so that it is more preferable. The thickness of the insulating metal thin film layer is preferably determined within the above range, depending on the gold design property to be used and the like. For the insulating metal thin film layer to have an island structure, a tin, indium, zinc, antimony, cobalt, antimony or the like is selected as the metal to be used. The insulating metal thin film layer is one or two metal thin films selected from the group consisting of tin, indium, and zinc. From the viewpoint of insulation, it is more preferable that the thickness of the insulating metal layer in the case of using tin or tin is higher. Preferably, the insulating metal thin film layer can be formed by a vacuum deposition method, a method, an EB vapor deposition method or the like. It is preferable to set the thickness X of the formula 1 or the insulating metal thin film layer and the transmittance of the total light transmittance. It is preferable that all of the light gloss of the substrate is a practical type or a low indium of at least one kind selected from the group. For example, in the case of the sputtering method, it is possible to control the evaporation amount of the induction heating method in the vapor deposition method and the film speed, and the sputtering method can control the evaporation amount and the film speed in the vapor deposition method. Controlled by discharge air pressure and discharge power and film speed. In the present invention, it has been found that the method of controlling the thickness X of the insulating metal thin film layer and the total light transmittance Tr according to Formula 1 or Formula 2 is to laminate the release resin layer on at least one side of the transparent base film. The protective resin layer can be obtained by subjecting the surface of the protective resin layer to surface treatment in accordance with plasma treatment under reduced pressure, and forming an insulating metal thin film layer thereon. Further, it has been found that a trace amount of metal adheres to the surface of the substrate in accordance with sputtering, and the thickness X of the insulating metal thin film layer and all the light are transmitted even in accordance with surface treatment by a so-called seeding method. The rate Tr conforms to the relationship of Equation 1 or Equation 2. In the nuclear adhesion treatment in this case, since the protective resin layer is exposed to the plasma, it can be defined as a plasma treatment. In the above plasma treatment, by the combination of the discharge electrode (cathode) material and the discharge gas, there is also a case where the discharge electrode material is not substantially sputtered, and the discharge electrode material is sputtered according to the sputtering phenomenon, and the discharge electrode material is used. The metal will also adhere to the protective resin layer. The present invention is related to the relationship of Equation 1 irrespective of the presence or absence of adhesion of the discharge electrode material caused by the plasma treatment. The amount of adhesion of the metal to which the discharge electrode material is attached during the plasma treatment under reduced pressure is an indicator of the treatment strength of the plasma treatment. That is, the present invention in this case is a metal film transfer material having a release film layer of -12-201136758, a protective resin layer, a metal film layer, and an adhesive layer on at least one side of the transparent substrate film; The metal is 15 ng/cm2 to 700 ng/cm2, and the insulating metal is thin from nm to 100 nm, and the total light transmittance is set to Tr287.522xExp (-0.0422 χΧ). The metal thin film layer is attached to a metal of 15 ng/cm 2 to 700 5 〇 1 ^ / <: 1112 to 50 〇 1 ^ / (: 1112. The insulating property is in the range of 15 ng/cm 2 to 700 ng/cm 2 . When the thickness X of the metal thin film layer is 5 15 ng/cm 2 , the corrosion resistance is insufficient; in the case of super shape, the radio wave penetration or the insulation property is deteriorated. The above is determined according to the plasma space under the reduced pressure. The method performed may also be used for active sputtering of the electrode material or by sputtering, using aluminum, silver, gold, tin, indium, lead, zinc, bismuth, nickel, bismuth, antimony or the like. From the viewpoint of the group wave penetration of the alloy, it is preferable to use indium or tin. As described above, the insulating metal layer is preferably one or more penetrating viewpoints selected from the constituent groups. The metal thin film layer is preferably of the same kind; when the dissimilar metal is used, the metallic luster is different from the original metallic luster; from this point of view, the adhesion amount of the insulating metal thin film layer is the thickness X of the film layer is 5 Tr (%), the metal film transfer material of ng/cm2 is preferably made thin The adhesion of the layer is such that it forms 'm to 100 nm. It is lower than the shovel plating method of the metal film layer over 700 ng/cm2. The target metal species in the plasma treatment can make • Titanium, complex, iron, Ming, and selected. From the metal of tin, indium, and zinc, the insulating metal expected from the metal of the electric wave metal layer, it is preferable to use the same type of 201136758 metal. The adhesive layer in the metal film transfer material of the present invention is formed on the insulating metal film layer, and after transfer, the plastic substrate and the transfer layer (release resin layer, protective layer, insulating metal film) Layer and adhesive layer. Acrylic resin, polyester resin, melamine resin, epoxy resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate can be used as the resin for the adhesive layer. The copolymer layer can be formed by a conventional method such as a gravure coating method, a reverse coating method, or a die coating method. The metal film transfer material of the present invention can be used to obtain a halftone gold. The glossy film 'further can be obtained by hot roll transfer or in-mold forming to obtain a halftone metallic luster molded article, and a halftone metallic luster molded article is obtained by in-mold molding to improve the transparent base film and the release resin. The undercoat layer is preferably formed between the transparent substrate film and the release resin layer for the purpose of releasing the layer and preventing the peeling or cracking of the plastic film during transfer, and the undercoat layer is formed by the undercoat layer. It is formed so that a molded product having a complicated shape can be stably obtained. For the resin used for the undercoat layer, a melamine resin, an amino alkyd resin, an epoxy resin, an acrylic resin, a sand oxide resin, or the like can be used. A melamine-based resin or an acrylonitrile-melamine-based resin is particularly preferred as the heating resin or the wax. The metal film transfer material of the present invention is placed under the conditions of a high temperature and high humidity test-14-201136758 (temperature 85 ° C, humidity 85% RH) for evaluation of corrosion resistance of a mobile phone or an audio product as described above. 48 hours test), by making the total light transmittance after the test 1 to 2.5 times relative to the total light transmittance before the test, because the insulating metal film layer does not disappear by corrosion Mobile phones or sound products that are strongly resistant to corrosion are the first to be used for a very wide range of applications. [Examples] Hereinafter, the form of the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. Furthermore, the evaluation method in the present invention is as follows: (1) Metal adhesion amount of the metal thin film layer A sample film of 5 cm x l cm is placed in a solution of hydrochloric acid and nitric acid in a ratio of 1:4, and placed in 24 More than an hour. Atomic absorption spectrophotometer AA-6300 manufactured by Shimadzu Corporation was used to measure the wavelength: 2 8 6.3 nm, lamp current ·· 1 〇m A 'slit width: 0 · 7 nm, lighting mode: BGC-2, 1 % The solution was measured by absorbance: 5.0 ppm. (2) The total light transmittance (%) was wiped with ethanol to a thickness of 1111111 > width 10 (; 111 >< length 20 (: 111 on the surface of the urethane plate, using a roller compactor (Taiping Industrial Co., Ltd.) RT-3 00X), after transfer at a roll temperature of 220 ° C and a speed of 5 cm / sec, the film was peeled off to obtain a test bead having a protective layer as a surface. A turbidity meter manufactured by Nippon Denshoku Industries Co., Ltd. was used. NDH-2000, the total light transmittance Tr (%) of the test beads produced is measured in accordance with JIS-K7136 (established in 2000). (3) Thickness of the insulating metal film layer X (nm) -15- 201136758 A thin film of an insulating metal layer obtained by vapor deposition was used as a sample, and a Hitachi concentrated ion beam processing observation apparatus FB2000A was used to prepare a sample cross section, and then an acceleration voltage of 30 was obtained by using a Hitachi transmission electron microscope (TEM) HF-2100. kV, observation magnification 421,000 times. The cross section of the insulating metal thin film layer was observed, and the number of islands observed from the unit field of view of the photograph and the thickness of the island (the height from the side boundary surface of the protective resin layer of the island), Calculate insulation by taking the average number The thickness of the metal film layer is X (nm). In this case, the interval between the islands is not considered, and the number average thickness of the highest portion of the island is calculated. For example, in Fig. 1, the calculation system (48.9 + 56.6 + 42.6) + 56.7 ) /4 = 51.2 nm (4) Corrosion resistance test Prepare a transparent acrylic plate (transparent substrate) with a thickness of 1 mm, wipe the surface with ethanol, etc., using a roll press (RT-300X manufactured by Taiping Industrial Co., Ltd.). A film as an insulating metal film transfer material was transferred at a roll temperature of 220 ° C and a speed of 5 cm / sec, and the film was peeled off to obtain a test bead having a protective resin layer as a surface. The turbidity was made using Nippon Denshoku Industries Co., Ltd. NDH-2 000 (according to HS-K7 1 3 6 (2000)), the total light transmittance of the test beads prepared was measured, and the constant temperature and humidity were measured by Tab ai E spec. The sample of the oven (PL-1SP) was placed on the net and placed in an environment of temperature 85t and humidity 85% RH for 48 hours. The 48 hours of the same material was measured for the same light transmittance as before, and the sample before the environmental load. Make a comparison. Set the pre-load (pre-test) penetration rate to A ( %), after the load (after the test), the penetration rate is set to B (%), and the B/A magnification is calculated as the penetration rate -16 - 201136758. (5) The radio wave penetration test will be cut into 15 The metal film of cmx 15 cm was transferred to the MAM101 shielding effect of the E Microwave Factory (manufactured by E Microwave Factory) using an Agilent Technologies \ Analyzer Agilent E5062A to measure the electric power (dB) at 800 MHz. The radio wave penetration is found because the metal thin film is discontinuous, and insulation is also ensured. The smaller the ruthenium, the more penetrating, preferably less than 1 dB, more preferably 0.5 dB. (Examples 1 to 3) As a transparent substrate film, a biaxially modified ethylene dicarboxylate E5001 type is used. 25 μηι; a single release resin layer of the film, coated with a gravure coater to a dry weight of 0.5 g/m 2 to form a cellulose acetate resin; on a resin layer, using the coater to carry a methyl group Coating of 2-hydroxyethyl acrylate, n-butyl methacrylate, melamine solution, drying, and resin hardening to obtain a layer having a thickness of 1 μm; and then, at the protective resin layer ng/cm 2 by sputtering method As a metal thin film layer. The sputtering conditions were performed using a argon gas as a cathode using argon gas. In the case where the metal thin film layer is an insulating metal layer, Tr is adjusted to be 5% and 15%, and 値 is used as Examples 1, 2, and 3. The insulating metal layer was heated by a vacuum vapor deposition machine (EB52〇7), 0.04 Pa, which was set by a steam processing. The gravure plate is used; the P film is disposed on the surface of the N w 〇 波 波 波 波 波 波 波 波 波 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异The protective resin of toluene of the base-acrylic resin is provided with tin 50 as the discharge gas surface, and tin is used as 46%. Each system is inductively used to operate the pressure coater, and the saturated polyester resin is coated on the vapor-deposited surface at -17-201136758, and dried. An adhesive layer having a thickness of 1 g/m 2 was formed. The results of evaluating the properties of the metal film transfer film obtained herein are shown in Table 1. In any of Examples 1, 2, and 3, good radio wave penetration was exhibited, and in the corrosion resistance test, the change (B/A) before and after the test was 2.5 times or less, which was good. Further, the structure of the island-shaped metal layer of the insulating resin material obtained in Example 2 is shown in Fig. 1 in a cross-sectional photograph of the TEM. (Examples 4 to 6) In Example 4, the thickness of the metal thin film layer was 15 ng/cm2, and in Example 5, it was 200 ng/cm2, and in Example 6, it was 500 ng/cm2. Then, each of the insulating metal thin films formed tin in such a manner that the light transmittance Tr was 15%. The other conditions were the same as in the examples 1, 2, and 3, and the results of evaluating the characteristics of the metal film transfer material were shown in Table 1. Each of Examples 4, 5, and 6 has good radio wave penetration and insulation properties, and the Tr change in the corrosion resistance test was 2.5 times or less. (Example 7) 50 ng/cm 2 of copper as a metal thin film layer was provided on the protective resin layer by a sputtering method. The sputtering conditions were performed using argon gas as a discharge and a cathode using a copper electrode. The insulating metal was vapor-deposited in such a manner that Tr was 15%. (Example 8) The substrate film roll which was laminated until the prepared protective resin layer was placed in the induction heating type vacuum steaming machine (EB 5207, manufactured by Nippon Vacuum Co., Ltd.) in the same manner as in Example 1, and the film was rolled up. Then, the plasma treatment apparatus was used to perform the plasma treatment while flowing nitrogen gas and -18 - 201136758 by the plasma processing apparatus using the flattening method of the tin electrode in vacuum. Then, the tin was made into the insulating metal and the Tr was 25%. Furthermore, it is preliminarily investigated by the fact that only the plasma treatment is carried out and the vapor deposition is not performed, and it is determined that the adhesion amount of the tin-bearing tin is 45 ng/cm2, but it is estimated that the tin is formed as an insulating metal by a series of vapor deposition. For the same amount of adhesion. (Example 9) In the same manner as in Example 8, a plasma processing apparatus using a flattening method using a copper electrode in a vacuum was used to carry out plasma treatment while flowing nitrogen gas, followed by vapor deposition as a tin of an insulating metal. And make Tr become 23%. In addition, 'the amount of adhesion of copper was 55 ng/cm2 by the prior investigation of only performing the plasma treatment and not performing the vapor deposition, but the formation of tin as an insulating metal by a series of steamed ores was estimated to be the same. The amount of adhesion. (Example 10) The same procedure as in Example 6 was carried out to prepare a tin of 700 ng/cm2. Although the radio wave penetration is judged to be as large as 0.6 8 dB, a good thing can be obtained in a practical range. (Example 1 1) In a manner similar to that of Example 7, a 300 ng/cm 2 of copper was provided as a metal thin film layer on the protective resin layer by a sputtering method, and Tr 18% was steamed. Tin plating is used as an insulating metal. Although it was a good result in the corrosion resistance test, the metallic luster after the peeling of the base film was slightly reddish due to the influence of the copper metal adhered to the core, and the radio wave permeability was also more than 1 dB. (Example 1 2) -19-201136758 The same manner as in Example 7 was carried out to make the insulating metal layer 95.8 nm. Since the radio wave penetration is deteriorated to 1.23 dB, it is difficult to use it for the purpose of using radio wave penetration as a necessary use, but it can be suitably used for applications where only ordinary metallic luster is necessary. (Example 1 3) In the same manner as in Example 4, the adhesion amount of the metal thin film was 15 ng/cm2, the total light transmittance was 22%, and the change in transmittance was 2.6 times, and the corrosion resistance was slightly insufficient. (Example 1 4) The same procedure as in Examples 8 and 9 was carried out, and plasma treatment was carried out in a vacuum shovel, and vapor deposition of tin was continuously performed, and the plasma-treated plasma was used as a glass-coated electrode. The power source was plasma treated at a high frequency of 1 〇 kHz and at an intensity of 50 W·min/m 2 . In the electrical system oxygen, in essence, the sputtering of the discharge electrode material did not occur, but the result of the formula 1 was superior in radio wave penetration and corrosion resistance. (Comparative Examples 1 and 2) A tin-deposited film of Tr = 6% and 17% was provided without providing a metal thin film layer. Other conditions were the same as in the first embodiment, and each was used as Comparative Example 1 and Comparative Example 2, respectively. Evaluate its characteristics. The evaluation results are shown in Table 1. In Comparative Example 1, the radio wave penetration was low and the insulation was not good. Further, in Comparative Examples 1 and 2, the results of low feed resistance were low. Further, a TEM cross-sectional photograph of Comparative Example 2 is shown in Fig. 2 . (Comparative Example 3) A metal thin film layer was formed in the same manner as in the sputtering method of Example 1 at a bonding amount of 10 ng/cm 2 -20 to 201136758, and the light transmittance Tr% was 14% to form tin. . The other conditions were the same as in Example 1 and Comparative Example 3, and the results were evaluated and the results are shown in Table 1. In the corrosion resistance test, the rate of change of Tr before and after the corrosion resistance test was more than 2.5 times, which was not preferable. (Comparative Example 4) Using the sputtering method of the same Example 1, a metal thin film layer was formed at an adhesion amount of 800 ng/cm 2 to form tin so that the light transmittance Tr was 15%. The other conditions were the same as in Example 1 and Comparative Example 4, and the results were evaluated and the results are shown in Table 1. The radio wave penetration will deteriorate to 1.56 dB, and the insulation is also insufficient. The amount of metal adhesion increases, and it is estimated that the radio wave penetration has deteriorated. (Comparative Example 5 '6) In the same manner as in Example 1, the thickness of the insulating metal layer was changed to 4.5 11111 and 108 nm, respectively, and the total light transmittance was 7 4 % and 2.6%, respectively, as Comparative Example 5, respectively. 6, 6. In Comparative Example 5, all of the light transmittance was high, and the metallic luster was insufficient. In Comparative Example 6, 'the inability to ensure insulation' radio wave penetration has deteriorated. (Comparative Example 7) In the same manner as in Example 13, 'in a vacuum vapor deposition machine', a glass-coated electrode was used for plasma treatment. The treatment intensity was set to 6 W'min/m2', which did not conform to Formula 1, and the corrosion resistance became insufficient. -21- 201136758 撇Corrosion resistance test penetration change Β/Α 〇〇IT) ψ-^ 〇<N 00 rr rn ΓΟ (N οο ίΝ CN rn (Ν 1.4氺rn rn light transmittance (%) Β After test Tr(%) σ\ rn CN Ο 〇〇(Ν fN CN m CN m (N (N rs (N rn 00 CN (N 00 m rn test beads all A: pre-test Tr(%) »〇ir> ;Τ) Ui yr) (Ν (N 00 00 FH (N VO 〇 丨 Η in in in in in in in in in in in o 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 14. 20.4 1_14,8_I 14.7 (N (N 30.0 13.5 15.8 39.6 24.1 26.8 - 99.9 27.8 The right side of Equation 1 ΓΛ 10.1 35.3 11.6 〇\ 〇6 10.8 〇\ 17.0 1__I | 10.5 1 10.4 21.5 αί 11.3 28.5 17.2 19.2 72.4 〇19.9 Radio wave wear Permeability (dB) 0.117 0.065 0.030 0.050 0.055 0.060 0.045 0.035 0.040 0.680 1.150 1.230 0.045 0.065 6.230 0.065 0.041 1.560 0.010 2.980 0.890 Insulating metal layer thickness X i 76.2 51.2 21.5 47.8 . 54.3 49.6 53.6 38.8 42.5 50.2 50.4 95.8 33.3 52.3 48.6 26.6 38.5 36.0 »n — 108.0 FH ΓΟ Metal film layer metal adhesion fS ε 200 i 500 (45) (55) 700 300 *〇1 ο ο ο 800 1 Discharge electrode material eg eg eg U <5 c3 eg 5 eg Glass 1 1 eg eg eg Glass test bead Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 1 Comparative Example 3 1 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 201136758 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional photograph (transmission electron micrograph 42 1,000 times) of the insulating metal thin film layer of Example 2. Fig. 2 is a photograph of a cross section of the insulating metal thin film layer of Comparative Example 2 (transmission electron microscope photograph 42 1,000 times). [Main component symbol description] 1 Protective resin layer 2 Insulating metal film layer -23-