201108254 六、發明說明： 【發明所屬之技術領域】 本發明係有關適用於要求遮蔽電磁波及視認性之用途 的透明樹脂箔，及使用該透明樹脂箔之電磁波防護材料。 【先前技術】 電磁波防護材料之使用目的爲，遮蔽自家電用品、行 動電話、電腦、電視（電漿顯示器、液晶顯示器）等爲首 的電子機器發生之各式各樣電磁波用。電磁波恐藉由其能 量影響人體及誤導其他電子機器之動作。 自電磁波發生源去除影響力之方法大致可區分爲下述 2種。（1 )改良設計電子電路以抑制電磁波發生，（2 ) 以電磁波防護材料被覆電磁波發生源之方法。以（1)之 方法抑制電磁波時無需增加多餘的構件而爲佳，但電磁波 發生源係特定，且爲了進行電路改良設計之煩雜作業時， 常以使用（2)之方法較有效率。 現今市場上蓬勃發展的薄膜型顯示器之電漿顯示器中 係藉由（2 )插入電磁波防護材料（電磁遮蔽膜）以抑制 電磁波。電漿顯示器中’主要係以聚對苯二甲酸乙二醇酯 樹脂基板（以後記載爲PET膜）上貼合銅箔，或蒸鍍銅 後’藉由光阻法形成的具有銅網構造之導電性膜作爲電磁 波防護材料用。使用銅時導電性較高，一般可提高防護效 果。 又曾揭示取代上述銅網構造用，將銀等金屬微粒子分 -5- 201108254 散溶液塗佈於薄膜上的具有網目狀構造之導電性膜。比較 光阻法，本法無需特別裝置，且可減少蝕刻液或蝕刻時所 產生的銅等廢棄物，故爲有利於環境之方法（專利文獻1 、專利文獻2、專利文獻3 )。 前述電漿顯示器等製品爲了維持必要的電磁波防護性 及顯示機能，需求電磁波防護材料之光學透明性。 至於顯示用途以外的遮蔽信號電纜或電線電纜等不可 避免發生的電磁波之電磁波防護材料，及遮蔽電腦或筆電 等發生的電磁波或防止來自外部之電磁波誤導電腦或筆電 之動作的電磁波防護材料等已有各種市售品。 先前該類電磁波防護材料係使用組合鋁箔、金屬網、 纖維表面鍍金屬之導電布等，其可得充分的電磁波防護效 果。 近年來前述用途也要求能自外確認施行電磁波防護材 料之內容物般的視認性。 先前已知的形成透明導電性膜之方法如專利文獻1至 5之方法。 先前技術文獻 專利文獻 [專利文獻1]特表2005-530005號公報 [專利文獻2]特開2008 -07 844 1號公報 [專利文獻3]特開2006-3 1 3 89 1號公報 [專利文獻4 ]特開2 0 7 7 - 2 9 4 3 5 5號公報 201108254 [專利文獻5]特開2〇〇7-234299號公報 [非專利文獻1]日立化成技術報告No.42、2004-1、 3 5 - 3 8pp 【發明內容】 發明所欲解決之課題 推測今後接受來自家電用品、行動電話、電腦、電視 等爲首之電子機器'或連繫此等電子機器間之信號電纜或 電子機器連結電源用之電源電纜的電磁波，以及具有誤導 電子機器之動作般危險性的來自外部之電磁波會逐步增加 ，因此會逐步需求電磁波防護材料。 又，相對於電磁波遮蔽性，及顯示器、觸控面板以外 之用途中的光學透明性即遮蔽物之視認性的要求也很重要 ，另外隨著裝置之小型、輕量化也要求電磁波防護材料薄 膜化。 但，先前的電磁波防護材料中，例如信號電纜及電源 電纜所使用的電磁波防護材料爲金屬膜、金屬線網或導電 布等，其雖具有良好電磁波遮蔽性，但未曾考慮光學透明 性或視認性。 推斷上述電漿顯示器用途之電磁波防護材料爲，於 PET膜等基板表面上形成導電性部後，實施具有保護該導 電性部之功能的透明化樹脂層（非專利文獻1 )。 將前述之電磁波防護材料作爲顯示器用途以外例如電 源電纜之防護材料用等時，因不備有前述透明化膜等保護 201108254 膜，故作業時防護材料之間或電纜與防護材料恐產生磨擦 ，或防護材料彎曲時恐破壞導電性部。因此推斷需備有保 護層。 隨著今後逐步要求的電磁波防護材料薄膜化，前述電 磁波防護材料之課題爲’如何削減形成導電性部之基板的 厚度及保護層之厚度的2種厚度》 另外爲了提升電磁波遮蔽性一般係使用複數重合之電 磁波防護材料，因此前述2種厚度之課題爲，使該類層合 構造進一步薄膜化。 如上述般，先前的電磁波防護材料無法成爲備有電磁 波遮蔽性、及光學透明性或視認性，及導電性部之充分耐 久性，可薄層化之構造的電磁波防護材料。 本發明之課題爲，提供具有電磁波遮蔽性、光學透明 性或視認性、導電性部之耐久性，可薄層化的電磁波防護 材料及其製造方法。 解決課題之方法 即，本發明爲一種透明樹脂箔，其特徵爲，透明樹脂 層內包有自金屬微粒子所構成的網目狀構造物形成之導電 性層（本發明1 ) » 即，本發明爲本發明1所記載的透明樹脂箔，其中金 屬微粒子爲由 Au、Ag、Cu、Ni' Co、Fe、Cr、Zn、A1、 Sn、Pd、Ti、Ta、W、Mo、In、Pt、Ru 中所選出的金屬 微粒子或含有前述金屬二種以上之合金微粒子（本發明2 -8- 201108254 即’本發明爲本發明1或2所記載的透明樹脂箔，其 中透明樹脂箱之膜厚爲5至50ym(本發明3)。 即’本發明爲一種製造方法，其爲本發明1至3中任 何一項所記載的透明樹脂箔之製造方法中，係以下述1至 3之步驟製造， 1.將金屬微粒子分散溶液塗佈於基材上，乾燥後 於基材上形成網目狀構造之導電性層的導電性層形成步驟 » 2 ·將自透明性樹脂形成之塗液塗佈於前述導電性 層表面上’乾燥後層合透明樹脂層之透明樹脂層層合步驟 ，及 3.由基材剝離含有金屬微粒子所構成的網目狀構 造物之透明樹脂層的步驟（本發明4)。 即，本發明爲一種透明樹脂箔，其特徵爲，層合內包 有自金屬微粒子所構成的網目狀構造物形成之導電性層的 透明樹脂層（本發明5)。 即，本發明爲本發明5所記載的透明樹脂箔，其中金 屬微粒子爲由 Au、Ag、Cu、Ni、Co、Fe、Cr、Zn、A1、 Sn、Pd、Ti、Ta、W、Mo、In、Pt、Ru 中所選出的金屬 微粒子或含有前述金屬二種以上之合金微粒子（本發明6 )° 即’本發明爲本發明5或6所記載之透明樹脂箔，其 中透明樹脂箔之膜厚爲5至5 0 μ m (本發明7 )。 -9- 201108254 即，本發明爲一種製造方法，其爲本發明5至7中任 何一項所記載的透明樹脂箔之製造方法中，係以下述1至 3之步驟製造。 1.將金屬微粒子分散溶液塗佈於基材上，乾燥後 於基材上形成網目狀構造之導電性層的導電性層形成步驟 9 2 .將自透明性樹脂形成之塗液塗佈於前述導電性 層表面上，乾燥後層合透明樹脂層之透明樹脂層層合步驟 ，及 3-以塗佈該透明樹脂層之表面互相以面對面方式 重合前述形成含有金屬微粒子所構成的網目狀構造物之透 明樹脂層的基材，及以1至2之方法另外準備的形成含有 金屬微粒子所構成的網目狀構造物之透明樹脂層的基材後 ，使該透明樹脂層互相接著，再由含有金屬微粒子所構成 的網目狀構造物之透明樹脂層剝離2個基材之步驟（本發 明8 )。 即，本發明爲一種電磁波防護材料，其特徵爲，使用 本發明1至3及5至7中任何一項所記載的透明樹脂箔形 成（本發明9 )。 發明之效果 本發明之內包金屬微粒子所構成的網目狀構造物之透 明樹脂箔爲，藉由來自金屬微粒子之導電性部可具有電磁 波遮蔽性，及藉由網目狀構造物可具有優良光學透過性或 -10 - 201108254 確保視認性，又藉由透明樹脂可保護該導電性部故不爲先 前構造之基材，因此易達成薄膜化。 實施發明之最佳形態 本發明中透明樹脂層「內包」（Contain )有自金屬 微粒子所構成的網目狀構造物形成之導電性層係指，包括 網目狀構造物之至少部分形成表面的態樣及網目狀構造物 完全被埋沒之態樣。首先將說明本發明1至4之透明樹脂 箔及其製造方法。 首先如圖1之A所示，將金屬微粒子分散溶液塗佈 於基材上再乾燥。或將金屬微粒子分散油墨印刷於基板上 再乾燥。 所使用的金屬微粒子分散溶液可爲，塗佈於基材上乾 燥後，藉由金屬微粒子之自我組織化現象能形成網目狀構 造物，其後進行加熱處理及/或化學處理可於基材上形成 低電阻、高透過率之導電性層之物中任何一種金屬微粒子 分散溶液。 又所使用的金屬微粒子分散油墨可爲，藉由網印印刷 或照相凹版印刷等印刷法將網目狀構造印刷於基材上，再 進行加熱處理及/或化學處理可於基材上形成低電阻、高 透過率之導電性層之物中任何一種金屬微粒子分散油墨。 金屬微粒子分散溶液例如可參考專利文獻1、專利文 獻4或專利文獻5等調製而得。金屬微粒子分散油墨例如 可使用藤倉化成股份公司製XA-9053等市售品。 -11 - 201108254 金屬微粒子分散液所含的金屬微粒子爲，Au、Ag、 Cu ' Ni 、 Co 、 Fe 、 Cr 、 Zn ' Al 、 Sn 、 Pd 、 Ti 、 Ta 、 W 、[Technical Field] The present invention relates to a transparent resin foil which is suitable for use in applications requiring shielding of electromagnetic waves and visibility, and an electromagnetic wave protective material using the transparent resin foil. [Prior Art] The purpose of the electromagnetic wave protection material is to shield various electromagnetic waves generated by electronic equipment such as household appliances, mobile phones, computers, televisions (plasma displays, liquid crystal displays). Electromagnetic waves are caused by their energy affecting the human body and misleading other electronic machines. The method of removing the influence from the electromagnetic wave generation source can be roughly classified into the following two types. (1) A method of improving the design of an electronic circuit to suppress the occurrence of electromagnetic waves, and (2) a method of covering an electromagnetic wave generating source with an electromagnetic wave protective material. It is preferable to suppress electromagnetic waves by the method of (1), and it is preferable to add unnecessary members. However, the electromagnetic wave generation source is specific, and in order to perform complicated work for circuit improvement design, the method using (2) is often effective. In the plasma display of a film-type display which is booming in the market today, (2) an electromagnetic wave shielding material (electromagnetic shielding film) is inserted to suppress electromagnetic waves. In a plasma display, a copper foil is bonded to a polyethylene terephthalate resin substrate (hereinafter referred to as a PET film) or a copper mesh is formed by a photoresist method. The conductive film is used as an electromagnetic wave protective material. When copper is used, it has high conductivity and generally improves the protective effect. Further, a conductive film having a mesh structure in which a metal fine particle such as silver is applied to a film in place of the above-described copper mesh structure has been disclosed. In comparison with the photoresist method, this method is a method which is advantageous for the environment (Patent Document 1, Patent Document 2, and Patent Document 3), since it does not require a special device and can reduce waste such as copper generated during etching or etching. The above-mentioned products such as plasma displays require optical transparency of electromagnetic wave protection materials in order to maintain necessary electromagnetic wave protection and display functions. Electromagnetic wave protection materials for electromagnetic waves that are inevitable, such as shielding signal cables or wires and cables, and electromagnetic waves that block electromagnetic waves generated by computers or laptops, or electromagnetic wave protection materials that prevent external electromagnetic waves from misleading computers or laptops. There are various commercial products available. Previously, such electromagnetic wave protection materials used a combination of aluminum foil, a metal mesh, a conductive cloth coated with metal on the surface of the fiber, etc., which provided sufficient electromagnetic wave protection effect. In recent years, the above-mentioned use is also required to be able to confirm the visibility of the contents of the electromagnetic wave shielding material from the outside. The previously known method of forming a transparent conductive film is as in the methods of Patent Documents 1 to 5. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-530005 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2008-07 844 No. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. 3 5 - 3 8 pp. [Invention] The problem to be solved by the invention is to accept a signal cable or an electronic device that is connected to electronic devices such as home appliances, mobile phones, computers, and televisions. The electromagnetic wave of the power cable for connecting the power source and the electromagnetic wave from the outside with the danger of the operation of the misconducting sub-machine will gradually increase, so the electromagnetic wave protection material will be gradually required. In addition, it is important to ensure the optical transparency of the display and the use of the touch panel, that is, the visibility of the shield, and the electromagnetic wave protective material is required to be thinner as the device is smaller and lighter. . However, in the prior electromagnetic wave protection materials, for example, the electromagnetic wave protection material used for the signal cable and the power cable is a metal film, a metal wire mesh or a conductive cloth, and although it has good electromagnetic wave shielding properties, optical transparency or visibility has not been considered. . In the electromagnetic wave protective material for the plasma display, the transparent resin layer having the function of protecting the conductive portion is formed after the conductive portion is formed on the surface of the substrate such as a PET film (Non-Patent Document 1). When the above-mentioned electromagnetic wave shielding material is used as a protective material for a power cable other than the display, for example, since the film 102108254 is protected by the transparent film or the like, friction between the protective materials or the cable and the protective material may occur during operation, or protection. When the material is bent, the conductive portion is damaged. Therefore, it is inferred that a protective layer is required. With the thinning of the electromagnetic wave protective material that is required to be gradually required in the future, the electromagnetic wave protective material has a problem of "how to reduce the thickness of the substrate on which the conductive portion is formed and the thickness of the protective layer". In addition, in order to improve the shielding property of the electromagnetic wave, the plural is generally used. Since the electromagnetic wave shielding material is superposed, the problem of the above two kinds of thicknesses is to further thinify such a laminated structure. As described above, the conventional electromagnetic wave shielding material cannot be an electromagnetic wave shielding material having a structure in which the electromagnetic shielding property, the optical transparency or the visibility, and the conductivity portion are sufficiently durable and can be thinned. An object of the present invention is to provide an electromagnetic wave protective material which has electromagnetic wave shielding properties, optical transparency, visibility, and durability of a conductive portion, and which can be thinned, and a method for producing the same. The present invention is a transparent resin foil characterized in that a transparent resin layer is provided with a conductive layer formed of a mesh-like structure composed of metal fine particles (Invention 1). The transparent resin foil according to the first aspect of the invention, wherein the metal fine particles are made of Au, Ag, Cu, Ni' Co, Fe, Cr, Zn, Al, Sn, Pd, Ti, Ta, W, Mo, In, Pt, Ru The metal fine particles selected in the above or the alloy fine particles containing the two or more kinds of the above-mentioned metal (2-8-201108254, the present invention is the transparent resin foil according to the invention 1 or 2, wherein the transparent resin case has a film thickness of 5 The present invention is a method for producing a transparent resin foil according to any one of the first to third aspects of the present invention, which is produced by the following steps 1 to 3, 1 a conductive layer forming step of forming a conductive layer of a mesh structure on a substrate after drying the metal fine particle dispersion solution, and forming a coating liquid formed of the transparent resin on the conductive material On the surface of the layer, 'dry and transparent after drying a step of laminating a transparent resin layer of a resin layer, and a step of peeling off a transparent resin layer containing a mesh-like structure composed of metal fine particles from a substrate (Invention 4). That is, the present invention is a transparent resin foil. A transparent resin layer in which a conductive layer formed of a mesh-like structure composed of metal fine particles is laminated (Invention 5). The present invention is a transparent resin foil according to Invention 5, wherein the metal The microparticles are metal microparticles selected from Au, Ag, Cu, Ni, Co, Fe, Cr, Zn, Al, Sn, Pd, Ti, Ta, W, Mo, In, Pt, Ru or contain the aforementioned two metals. The present invention is a transparent resin foil according to the invention of claim 5 or 6, wherein the transparent resin foil has a film thickness of 5 to 50 μm (Invention 7). The present invention is a method for producing a transparent resin foil according to any one of the fifth to seventh aspects of the present invention, which is produced by the following steps 1 to 3. 1. Coating a metal fine particle dispersion solution Deployed on a substrate, dried to form a mesh on the substrate Step 9 of forming a conductive layer of a conductive layer having a structure, applying a coating liquid formed of a transparent resin onto the surface of the conductive layer, drying a transparent resin layer laminating step of laminating the transparent resin layer, and (3) a substrate on which the surface of the transparent resin layer is applied to face each other to form a transparent resin layer which forms a mesh-like structure composed of metal fine particles, and a metal-containing fine particle which is separately prepared by the method of 1 to 2. After the base material of the transparent resin layer of the mesh-like structure, the transparent resin layer is adhered to each other, and the two base materials are peeled off from the transparent resin layer of the mesh-like structure including the metal fine particles (the present invention) 8 ). In other words, the present invention is an electromagnetic wave shielding material which is characterized by using the transparent resin foil according to any one of Inventions 1 to 3 and 5 to 7 (Invention 9). Advantageous Effects of Invention The transparent resin foil of the mesh-like structure comprising the metal fine particles of the present invention has electromagnetic wave shielding properties by the conductive portion from the metal fine particles, and excellent optical transmission through the mesh-like structure. Sex or -10 - 201108254 It is easy to achieve film formation by ensuring visibility and protecting the conductive portion by a transparent resin. BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the transparent resin layer "contains" a conductive layer formed of a mesh-like structure composed of metal fine particles, and includes a state in which at least a portion of the mesh-like structure forms a surface. The sample and the mesh-like structure are completely buried. First, the transparent resin foils of the inventions 1 to 4 and a method for producing the same will be explained. First, as shown in A of Fig. 1, the metal fine particle dispersion solution is applied onto a substrate and then dried. Alternatively, the metal fine particle dispersed ink is printed on the substrate and dried. The metal microparticle dispersion solution used may be a mesh-like structure formed by self-organization of metal microparticles after being dried on a substrate, and then subjected to heat treatment and/or chemical treatment on the substrate. Forming any one of the metal fine particle dispersion solutions of the low-resistance, high-transmittance conductive layer. The metal fine particle-dispersed ink used may be a screen-like structure printed on a substrate by a printing method such as screen printing or gravure printing, and then subjected to heat treatment and/or chemical treatment to form a low resistance on the substrate. Any one of the metal microparticles in the high transmittance conductive layer disperses the ink. The metal fine particle dispersion solution can be prepared, for example, by referring to Patent Document 1, Patent Document 4, or Patent Document 5. For the metal fine particle-dispersed ink, for example, a commercially available product such as XA-9053 manufactured by Fujikura Kasei Co., Ltd. can be used. -11 - 201108254 The metal fine particles contained in the metal fine particle dispersion are Au, Ag, Cu 'Ni , Co , Fe , Cr , Zn ' Al , Sn , Pd , Ti , Ta , W ,
Mo、In、Pt、Ru等金屬微粒子或金屬合金微粒子。較佳 爲使用含有Au'Ag'Cu中1種以上之金屬微粒子分散溶 液或金屬微粒子先驅物溶液。 基材較佳爲使用具有優良耐熱性、耐藥性之材料。 本發明係將金屬微粒子分散溶液塗佈、乾燥於基材上 ，或將金屬微粒子分散油墨印刷、乾燥於基材上，再進行 加熱處理及/或化學處理，以形成具有充分低電阻性、高 透過率性之電磁波防護材料，因此基材需爲耐此等操作、 處理之物。基材的選擇不適當，而無法充分進行加熱處理 及/或化學處理時，將無法得到具有充分低電阻性、高透 過率性之電磁波防護材料。例如金屬微粒子分散液或金屬 分散油墨含有機溶劑時，基材需具有耐溶劑性。 將金屬微粒子分散液塗佈於基材上乾燥後，或將金屬 微粒子分散油墨塗佈、乾燥於基材後，需浸潰於鹽酸水溶 液類時，需選擇具有耐酸性之基材，其後進行加熱處理時 ，需選擇同時具有耐酸性及耐熱性之基材。 本發明所使用的基材除了玻璃基材，較佳爲使用工業 上較低廉之樹脂基材。具體上可使用玻璃、聚對苯二甲酸 乙二醇酯、聚萘二甲酸乙二醇酯、聚醯胺、聚醯亞胺、聚 伸苯基硫化物等。基材又以具有柔軟性爲佳。基材可重覆 使用。 又，塗佈金屬微粒子分散溶液或印刷金屬微粒子分散 -12- 201108254 油墨之基材的表面，爲了以良好再現性自金屬微粒子形成 網目狀構造，或可良好印刷，較佳爲預先進行底漆處理、 電暈處理或以酸、鹼處理進行洗淨等。上述方法無特別限 定，較佳爲進行適用於各金屬微粒子分散溶液之處理。 將金屬微粒子分散溶液塗佈於基材上之方法可使用旋 塗機、棒塗機、模塗機、噴塗機等一般於基材上進行塗佈 處理時所使用的塗佈方法。 將金屬微粒子分散油墨印刷於基材上之方法可爲，網 印印刷、照相凹版印刷、噴墨印刷，以分配器印刷等一般 印刷於基材上的方法。 將金屬微粒子分散溶液塗佈、乾燥於基材上或將金屬 微粒子分散油墨印刷、乾燥於基材上，形成金屬微粒子所 構成的網目狀構造物後，進行加熱處理時之溫度會因基材 種類而異，但爲了形成充分低電阻之導電性層較佳爲100 至300°c，更佳爲100至200°c。 將金屬微粒子分散溶液塗佈、乾燥於基材上或將金屬 微粒子分散油墨印刷、乾燥於基材上，形成金屬微粒子所 構成的網目狀構造物後，浸漬於具有可去除金屬微粒子中 所含的分散劑或樹脂等之作用及促進金屬微粒子間燒結之 作用的有機溶劑及無機酸或有機酸中，由此可得層合具有 低電阻性、高透過率性、耐紋路性之導電性層的基材。 有機溶劑較佳爲甲醇、乙醇、異丙醇等醇類、丙酮、 甲基乙基酮等酮類等。無機酸較佳爲鹽酸、硝酸等，有機 酸較佳爲甲酸、乙酸等。 -13- 201108254 加熱處理及化學處理可使用任何一種或組合。爲了防 止耐候性、耐藥性及來自氧化還原電位的惡化，可電鍍導 電性層之表面。 層合層合於基材上的上述方法製得之含有金屬微粒子 所構成的網目狀構造物之導電性層的基材7(圖1(A) )之電氣特性中，表面電阻爲1〇〇 Ω/□以下。光學上透過 率較佳爲透過率60%以上。更佳爲表面電阻30 Ω /□以下 ，透過率70%以上。表面電阻大於100 Ω/□時電磁波防 護特性將不足，透過率未達60%時，^減少本發明之課 題的光學明性之優越性而不宜。 其次如圖1 (B)所示，於層合前述導電性層之基材7 的導電性層上，形成被覆導電性層般的透明樹脂層3。 透明樹脂層3所使用的樹脂如，聚氯乙烯、聚碳酸酯 、聚苯乙烯、聚甲基甲基丙烯酸酯、聚丁基甲基丙烯酸酯 、聚酯、聚颯、聚乙烯基丁縮醛、聚乙烯基乙縮醛、聚伸 苯基氧化物、聚丁二烯、聚（N-乙烯基咔唑）、聚乙烯基 吡咯烷酮、碳化氫樹脂、酮樹脂、苯氧樹脂、聚醯胺、氯 化聚丙烯、脲、纖維素 '乙酸乙烯、ABS樹脂、聚胺基甲 酸乙酯、苯酚樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、醇 酸樹脂、環氧樹脂、聚矽氧烷樹脂及此等之共聚物所成群 中至少1種’及此等之任何混合物等。又目的爲使最終所 得的電磁波防護材料得到高耐性時，可添加異氰酸酯系、 三聚氰胺系、環氧系等先前已知的硬化劑。 又’必要時透明樹脂層3可適當使用添加劑用之紫外 14- 201108254 線吸收劑 '著色顏料、防靜電劑、防氧化劑、矽烷偶合劑 等。 形成透明樹脂層3之方法可使用，將上述透明樹脂材 料溶解於有機溶劑或水中，或分散於水中調整黏度製作塗 佈劑後，藉由照相凹版塗佈、旋塗等先前已知的塗佈法塗 佈乾燥之方法。透明樹脂層3之厚度較佳爲5至50//m。 透明樹脂層3之厚度未達5 # m時會使最終所得的電磁波 防護材料用之耐久性變差而不宜》又透明樹脂層3之厚度 超過50//m時透明性會變差而不宜。 又，爲了確保作爲電磁波防護材料用時之耐久性，透 明樹脂層3之厚度較佳爲比金屬微粒子所構成的網目狀構 造物之高度更厚，但無特別限定。 其次自基材2剝離含有金屬微粒子所構成的網目狀構 造物之透明樹脂層3，可製作內包金屬微粒子所構成的網 目狀構造物之透明樹脂箔4(圖1之（C))。藉由各種 被貼物貼合該透明樹脂箔，可使被貼物得到電磁波防護材 料用之性能。 本發明之透明樹脂箔的電磁波遮蔽特性爲，1MHz至 1 GHz下的電磁波衰退率爲20dB以上，較佳爲25 dB以上 ，更佳爲30dB以上。小於20dB時將無法得到充分的遮 蔽性用效果。 本發明之透明樹脂箔的光學性透過率爲60%以上。 光學性透過率未達60 %時將難得到充分透明性且視認性 差。 -15- 201108254 評估導電性層之耐久性可藉由耐擦過性試驗進行° — 般進行膠帶試驗也可評估導電性層之強度，但實際使用於 電磁波防護材料時，無法稱爲適當之試驗法。其因爲’實 際使用於電磁波防護材料時，電磁波防護材料之間會有磨 擦，且電纜先端等產生搔刮之頻率高，而磨擦及搔刮會破 壞導電性層之構造，’因此會使導電性變差而使電磁波遮蔽 特性變差。 前述之耐擦過性試驗較佳爲，即使加重19.6Pa下棉 布往返擦過100次也不會損傷導電性層般之耐久性。耐擦 過性低於上述時易因電磁波防護材料之間的磨擦及電纜先 端的搔刮而破壞導電性層故不宜》 接著將說明本發明5至8之透明樹脂箔及其製造方法 〇 首先如圖2之（A )所示，將金屬微粒子分散溶液塗 佈於基材上再乾燥。或將金屬微粒子分散油墨印刷於基材 上再乾燥。層合圖2之（A)所示導電性層的基材實質上 係與說明本發明1至4所使用的圖1之（A)所示導電性 層相同，所使用的材料、方法、性狀等可全部採用說明本 發明1至4所使用之物。 其次如圖2(B)所示，於層合前述導電性層之基材7 的導電性層上’形成被覆導電性層般的透明樹脂層3。圖 2(B)之6的形成含有金屬微粒子所構成的網目狀構造物 之透明樹脂層的基材，實質上係與說明本發明1至4所使 用的層合圖1(B)所示導電性層之基材7的導電性層上 -16- 201108254 ’形成被覆導電性層般的透明樹脂層3之物相同’所使用 的材料、方法、性狀等可全部採用說明本發明1至4所使 用之物。 其次形成含有前述金屬微粒子所構成的網目狀構造物 之透明樹脂層的基材，及自相同方法另外準備的形成含有 金屬微粒子所構成的網目狀構造物之透明樹脂層的基材， 以塗佈該透明樹脂層之表面互相以面對面的方式重合，使 該透明樹脂層互相接著後（圖2之（C))，自含有金屬 微粒子所構成的網目狀構造物之透明樹脂層剝離2個基材 ，可得內包雙層金屬微粒子所構成的網目狀構造物之透明 樹脂箔4’（圖2之（D))。 使透明樹脂層互相接著之方法可使用先前己知的塗佈 黏著劑及接著劑接著之方法。又透明樹脂係使用具有熱接 著性之熱可塑性樹脂時可僅以熱壓合接著透明樹脂層相互 之層，此時無需接著劑或黏著劑。前述方法製作之透明樹 脂箔係由2枚金屬微粒子所構成的網目狀構造物層合構成 ，因此具有特別優良之電磁波防護性能。將該透明樹脂箔 貼合於各種被貼物時，被貼物可得電磁波防護材料用之性 能。 又，將內包雙層金屬微粒子所構成的網目狀構造物之 透明樹脂箔4’，重合於另外準備的形成含有金屬微粒子 所構成的網目狀構造物之透明樹脂層的基材之透明樹脂層 表面上，接著透明樹脂箔4’及透明樹脂層後剝離基材， 可得內包3層金屬微粒子所構成的網目狀構造物之透明樹 -17- 201108254 脂箔5 (圖3)。以該透明樹脂箔5作爲電磁波防護材料 用時可得極優良的電磁波防護性能。 將本發明的內包雙層金屬微粒子所構成的網目狀構造 物之透明樹脂箔4’或內包三層金屬微粒子所構成的網目 狀構造物之透明樹脂箔5層合於各種被貼物後使用時’該 透明樹脂箔之至少一方表面可塗佈接著劑或黏著劑再使用 〇 接著劑材料如，聚氯乙烯、聚碳酸酯、聚苯乙烯、聚 甲基甲基丙烯酸酯、聚丁基甲基丙烯酸酯、聚酯、聚颯、 聚乙烯基丁縮醛、聚乙烯基乙縮醛、聚伸苯基氧化物、聚 丁二烯、聚（N-乙烯基咔唑）、聚乙烯基吡咯烷酮、碳化 氫樹脂、酮樹脂、苯氧樹脂、聚醯胺、氯化聚丙烯、脲、 纖維素、乙酸乙烯、ABS樹脂、聚胺基甲酸乙酯、苯酚樹 脂、三聚氰胺樹脂、不飽和聚酯樹脂、醇酸樹脂、環氧樹 脂、聚砂氧院樹脂及此等之共聚物所成群的至少一種，及 此等之任何混合物。 黏著劑可使用以丙烯酸基系黏著劑爲首的各種黏著劑 ’其可自以異氰酸酯系、三聚氰胺系、環氧系等已知之交 聯劑’使單體主要爲丙烯酸丁酯、丙烯酸乙酯、2-乙基己 基丙烯酸酯等的低Tg單體與丙烯酸、甲基丙烯酸、羥基 乙基甲基丙烯酸酯、羥基乙基丙烯酸酯、丙烯醯胺、丙烯 腈等官能基單體共聚合而得的丙烯酸基共聚物交聯而得。 【實施方式】 -18- 201108254 實施例 下面將舉實施例更詳細說明本發明，但下述實施例單 純爲例示，本發明非限定於下述實施例。下述實施例1-1 至1-3及比較例1-1至1-2係有關本發明1至4之透明樹 脂箔及其製造方法之實施例，實施例2-1至2-4及比較例 2-1至2-2係有關本發明5至8之透明樹脂箔及其製造方 法。下面將說明實施例及比較例所使用的評估方法。 測定製作於基材上之導電性層及內包金屬微粒子所構 成的網目狀構造物之透明樹脂箔的電阻時，係依據 JIS-K-7 194使用洛雷斯GP (戴安斯股份公司製，型號： MCP-T610)中直列的4支探針（ASP)以4端子4探針法 實施。 光學性透過率係以全光線透過率評估。使用霧化計器 (型號：NDH-2000，日本電飾工業股份公司製）依 JIS K-7 105測定前述導電性層及內包金屬微粒子所構成的 網目狀構造物之透明樹脂箔。 使用微計器測定基材厚度、內包金屬微粒子所構成的 網目狀構造物之透明樹脂箔厚度。 所使用的電磁波防護特性之測定法爲KEC法，以 1 MHz至1 GHz之周波數測定電場成份之衰退率。 耐久性試驗爲，加重1 9.6 P a下以棉布進行往返1 〇 0 次之耐擦過性試驗（試驗機：八.八.1\(：.(：.鐘表式計器模 型CM-1，艾德拉電氣裝置公司製），評估導電性層之損 傷度。 · -19- 201108254 <銀微粒子1之調製法> 以銀微粒子之液相還原調製法爲金屬微粒子例進行說 明，但無限定金屬微粒子之種類及製造法。 加入硝酸銀40g、丁基胺37.9g及甲醇200mL後攪拌 1小時調製A液。另取異抗壞血酸62.2g，加入水400mL 後攪拌溶解，再加入甲醇2 0 0mL調製B液。攪拌B液的 同時以1小時2 0分鐘將A液滴入B液中。結束滴液後持 續攪拌3小時30分鐘。攪拌後靜置30分鐘使固體物沈澱 。藉由傾析去除上層澄清液後，重新加入水500mL，攪拌 、靜置再藉由傾析去除上層澄清液。重覆3次該精製操作 後，於40 °C之乾燥機中乾燥沈澱的固體物以去除水分。 又，將所得的銀微粒子20g及DISPERBYK-106(日本巨 化公司製）〇.2g混入甲醇lOOmL及純水5mL之混合溶液 中，混合1小時後加入純水100mL再過濾膠體，40°C之 乾燥機中乾燥後得銀微粒子1。使用電子顯微鏡觀察銀微 粒子，結果一次粒子之平均粒徑爲60nm。 <調製銀微粒子分散溶液2 > 調製銀微粒子分散溶液係參考專利文獻1進行（參考 特表2005-530005號公報調製）。 即，混合前述銀微粒子1 4g、甲苯30g、BYK-410( 曰本巨化公司製）〇.2g後，以輸出力180W之超音波分散 機進行1 . 5分鐘的分散化處理，加水純水1 5 g後以輸出力 -20- 201108254 1 80W之超音波分散機將所得的乳濁液分散處理30秒 製銀微粒子分散溶液2。 <導電性層之形成法> 使用棒塗機將前述銀微粒子分散液2塗佈於厚度 从m之聚對苯二甲酸乙二醇酯基材上。其次於大氣中 乾燥，藉由自己組織化現象使銀微粒子形成網目狀構 。其次，以150°C加熱2分鐘後，各自浸漬於丙酮;5 鹽酸中，再以1 50°C加熱乾燥5分鐘，形成含有銀微 之網目狀構造物。於基材上形成自含有銀微粒子之網 構造物形成的導電性層後之全光線透過率爲8 5 %， 電阻値爲4.5 Ω /匚1。 實施例1-1 : 將下述透明樹脂層塗佈液1 -1以乾燥後厚度爲1 之方式塗佈於層合上述方法所製作的含有銀微粒子之 狀構造物的聚對苯二甲酸乙二醇酯基材上，以100°c 5分鐘後形成透明樹脂層。其次自聚對苯二甲酸乙二 基材2剝離內包含有銀微粒子之網目狀構造物的透明 層，得內包含有銀微粒子之網目狀構造物的透明樹脂 <透明樹脂層塗佈液1 -1 > 將聚乙烯基丁縮醛樹脂（積水化學製，耶斯雷 )15g溶解於正丁醇85g中，得透明樹脂層塗佈液1- ，調 100 自然 造物 ：1N 粒子 目狀 表面 5 /z m 網目 乾燥 醇酯 樹脂 箔。 BX-1 -21 - 201108254 實施例1-2 : 除了所使用的透明樹脂層塗佈液爲透明樹脂層塗佈液 1-2，塗佈乾燥後之透明樹脂層厚爲2〇βιη外，同實施例 1-1製作內包含有銀微粒子之網目狀構造物的透明樹脂箔 <透明樹脂層塗佈液1-2 > 將纖維素乙酸酸丁酸酯樹脂（戶斯特公司製， CAB381-1) 15g溶解於甲基乙基酮85g中，得透明樹脂層 塗佈液1 - 2。 實施例1-3 : 除了所使用的透明樹脂層塗佈液爲透明樹脂層塗佈液 1-3，塗佈乾燥後之透明樹脂層厚爲20/zm外，同實施例 1-1製作內包含有銀微粒子之網目狀構造物的透明樹脂箔 <透明樹脂層塗佈液1-3 > 將氯乙烯-乙酸乙烯共聚合樹脂（日信化學製，索魯 拜CN) 20g溶解於甲基乙基酮80g中，得透明樹脂層塗 佈液1-3 。 比較例1 -1 : 22- 201108254 所使用的電磁波防護材料爲鋁箔，測定電磁波防護特 性。Metal fine particles such as Mo, In, Pt, or Ru or metal alloy fine particles. It is preferable to use a metal fine particle dispersion solution or a metal fine particle precursor solution containing one or more of Au'Ag'Cu. The substrate is preferably a material having excellent heat resistance and chemical resistance. In the present invention, the metal microparticle dispersion solution is coated and dried on a substrate, or the metal microparticle dispersion ink is printed and dried on a substrate, and then subjected to heat treatment and/or chemical treatment to form a sufficiently low resistance and high. Transmissive electromagnetic wave protection materials, so the substrate needs to be resistant to such operations and treatments. When the selection of the substrate is not appropriate and the heat treatment and/or chemical treatment cannot be sufficiently performed, an electromagnetic wave protective material having sufficiently low electrical resistance and high permeability cannot be obtained. For example, when the metal fine particle dispersion or the metal dispersion ink contains an organic solvent, the substrate needs to have solvent resistance. After the metal fine particle dispersion is applied to a substrate and dried, or after the metal fine particle-dispersed ink is applied and dried on a substrate, it is required to be impregnated with an aqueous hydrochloric acid solution, and then a substrate having an acid resistance is selected, followed by When heat treatment, it is necessary to select a substrate having both acid resistance and heat resistance. In addition to the glass substrate, the substrate used in the present invention is preferably an industrially inexpensive resin substrate. Specifically, glass, polyethylene terephthalate, polyethylene naphthalate, polyamine, polyimide, polyphenylene sulfide, or the like can be used. The substrate is preferably soft. The substrate can be reused. Further, the surface of the substrate coated with the metal fine particle dispersion solution or the printed metal fine particle dispersed -12-201108254 ink is preferably subjected to primer treatment in order to form a mesh structure from the metal fine particles with good reproducibility or to be printed well. , corona treatment or washing with acid or alkali treatment, etc. The above method is not particularly limited, and it is preferred to carry out a treatment suitable for each metal fine particle dispersion solution. The method of applying the metal fine particle dispersion solution to the substrate can be carried out by a coating method generally used for coating treatment on a substrate, such as a spin coater, a bar coater, a die coater, or a spray coater. The method of printing the metal fine particle-dispersed ink on the substrate may be a method of generally printing on a substrate such as screen printing, gravure printing, ink jet printing, and dispenser printing. The metal fine particle dispersion solution is applied to a substrate, or the metal fine particle dispersed ink is printed and dried on a substrate to form a mesh structure composed of metal fine particles, and the temperature at the time of heat treatment is determined by the type of the substrate. However, the conductive layer for forming a sufficiently low resistance is preferably 100 to 300 ° C, more preferably 100 to 200 ° C. The metal fine particle dispersion solution is applied onto a substrate, or the metal fine particle dispersed ink is printed and dried on a substrate to form a mesh structure composed of metal fine particles, and then immersed in the metal fine particles contained therein. An organic solvent and an inorganic acid or an organic acid which act as a dispersing agent or a resin and promote the sintering between the fine metal particles, thereby obtaining a conductive layer having low electrical resistance, high transmittance, and grain resistance. Substrate. The organic solvent is preferably an alcohol such as methanol, ethanol or isopropyl alcohol, or a ketone such as acetone or methyl ethyl ketone. The inorganic acid is preferably hydrochloric acid, nitric acid or the like, and the organic acid is preferably formic acid, acetic acid or the like. -13- 201108254 Heat treatment and chemical treatment can be used in any combination or combination. The surface of the conductive layer can be plated in order to prevent weather resistance, chemical resistance, and deterioration from the oxidation-reduction potential. In the electrical characteristics of the substrate 7 (Fig. 1 (A)) of the conductive layer containing the mesh-like structure composed of the metal fine particles obtained by laminating the above-mentioned method, the surface resistance is 1 〇〇. Below Ω/□. The optical transmittance is preferably 60% or more. More preferably, the surface resistance is 30 Ω / □ or less, and the transmittance is 70% or more. When the surface resistance is more than 100 Ω/□, the electromagnetic wave protection characteristics will be insufficient, and when the transmittance is less than 60%, it is not preferable to reduce the superiority of the optical clarity of the subject of the present invention. Next, as shown in Fig. 1(B), a transparent resin layer 3 coated with a conductive layer is formed on the conductive layer of the substrate 7 on which the conductive layer is laminated. The resin used for the transparent resin layer 3 is, for example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polyfluorene, polyvinyl butyral, poly Vinyl acetal, polyphenylene oxide, polybutadiene, poly(N-vinylcarbazole), polyvinylpyrrolidone, hydrocarbon resin, ketone resin, phenoxy resin, polyamine, chlorination Polypropylene, urea, cellulose 'vinyl acetate, ABS resin, polyurethane, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, polyoxyalkylene resin and the like At least one of the groups of the copolymers and any mixtures thereof. Further, in order to obtain high resistance to the finally obtained electromagnetic wave shielding material, a previously known curing agent such as an isocyanate type, a melamine type or an epoxy type may be added. Further, when necessary, the transparent resin layer 3 may be suitably used as an ultraviolet ray for the use of an additive, a coloring pigment, an antistatic agent, an antioxidant, a decane coupling agent, or the like. The method of forming the transparent resin layer 3 can be carried out by dissolving the above transparent resin material in an organic solvent or water, or dispersing in water to adjust the viscosity to prepare a coating agent, and then previously known coating by gravure coating, spin coating or the like. Method of coating and drying. The thickness of the transparent resin layer 3 is preferably 5 to 50 / / m. When the thickness of the transparent resin layer 3 is less than 5 #m, the durability of the finally obtained electromagnetic wave protective material is deteriorated. When the thickness of the transparent resin layer 3 exceeds 50/m, the transparency may be deteriorated. Further, in order to secure the durability as the electromagnetic wave protective material, the thickness of the transparent resin layer 3 is preferably thicker than the height of the mesh-like structure composed of the metal fine particles, but is not particularly limited. Then, the transparent resin layer 3 containing the mesh-like structure composed of the metal fine particles is peeled off from the substrate 2, and the transparent resin foil 4 containing the mesh-like structure composed of the metal fine particles can be produced (Fig. 1 (C)). By adhering the transparent resin foil to various stickers, the article can be obtained with an electromagnetic wave shielding material. The electromagnetic wave shielding property of the transparent resin foil of the present invention is such that the electromagnetic wave decay rate at 1 MHz to 1 GHz is 20 dB or more, preferably 25 dB or more, more preferably 30 dB or more. When it is less than 20 dB, sufficient shielding effect cannot be obtained. The transparent resin foil of the present invention has an optical transmittance of 60% or more. When the optical transmittance is less than 60%, it is difficult to obtain sufficient transparency and visibility is poor. -15- 201108254 Evaluating the durability of the conductive layer can be evaluated by the scratch resistance test. The strength of the conductive layer can also be evaluated. However, when it is actually used in electromagnetic wave protective materials, it cannot be called a suitable test method. . Because 'the actual use of electromagnetic wave protection materials, there will be friction between the electromagnetic wave protection materials, and the frequency of the squeegee of the cable tip is high, and the friction and scratching will destroy the structure of the conductive layer, 'so the conductivity will be The deterioration causes the electromagnetic wave shielding characteristics to deteriorate. The above-mentioned scratch resistance test is preferably such that the durability of the conductive layer is not impaired even if the cotton is rubbed back and forth 100 times at a weight of 19.6 Pa. When the scratch resistance is lower than the above, it is easy to damage the conductive layer due to the friction between the electromagnetic wave protective material and the scratch at the tip of the cable. Next, the transparent resin foil of the present invention 5 to 8 and the manufacturing method thereof will be described first. As shown in (A) of 2, the metal fine particle dispersion solution is applied onto a substrate and then dried. Alternatively, the metal fine particle dispersed ink is printed on a substrate and dried. The base material of the conductive layer shown in (A) of FIG. 2 is substantially the same as the conductive layer shown in (A) of FIG. 1 used in the description of the first to fourth embodiments of the present invention, and the materials, methods, and properties used. The materials used in the inventions 1 to 4 can be used as a whole. Next, as shown in Fig. 2(B), a transparent resin layer 3 coated with a conductive layer is formed on the conductive layer of the substrate 7 on which the conductive layer is laminated. The substrate of the transparent resin layer containing the mesh-like structure composed of the metal fine particles of FIG. 2(B) is substantially the same as the laminate shown in FIG. 1(B) for explaining the first to fourth embodiments of the present invention. The materials, methods, properties, and the like used in the conductive layer of the substrate 7 of the layer 7 - 201108254 'the same thing as the transparent resin layer 3 coated with the conductive layer' may be used to describe the inventions 1 to 4 Use of things. Next, a base material which forms a transparent resin layer containing the mesh-like structure composed of the metal fine particles, and a base material which is prepared separately from the same method and which forms a transparent resin layer containing a mesh-like structure composed of metal fine particles is coated. The surfaces of the transparent resin layer are superposed on each other in a face-to-face manner, and after the transparent resin layers are adhered to each other (Fig. 2(C)), two substrates are peeled off from the transparent resin layer of the mesh-like structure composed of metal fine particles. A transparent resin foil 4' of a mesh-like structure composed of double-layered metal fine particles is obtained ((D) of Fig. 2). The method of adhering the transparent resin layers to each other can be carried out by using a previously known coating adhesive and an adhesive. Further, when a transparent resin is used as the thermoplastic resin having heat bonding property, only the layers of the transparent resin layer can be bonded together by thermocompression bonding, and in this case, an adhesive or an adhesive is not required. Since the transparent resin foil produced by the above method is formed by laminating a mesh structure composed of two metal fine particles, it has particularly excellent electromagnetic wave protection performance. When the transparent resin foil is bonded to various objects to be attached, the object to be coated can obtain the performance for an electromagnetic wave protective material. In addition, the transparent resin foil 4' of the mesh-like structure composed of the double-layered metal fine particles is superposed on the transparent resin layer of the base material of the transparent resin layer which forms the mesh-like structure which consists of metal microparticles separately. On the surface, after the transparent resin foil 4' and the transparent resin layer are followed by peeling off the substrate, a transparent tree -17-201108254 fat foil 5 (Fig. 3) having a mesh structure composed of three layers of metal fine particles can be obtained. When the transparent resin foil 5 is used as an electromagnetic wave protective material, excellent electromagnetic wave protection performance can be obtained. The transparent resin foil 4' of the mesh-like structure composed of the double-layered metal fine particles of the present invention or the transparent resin foil 5 of the mesh-like structure composed of the three-layered metal fine particles is laminated on various decorative objects. When used, at least one surface of the transparent resin foil may be coated with an adhesive or an adhesive, and then an adhesive material such as polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutylmethyl. Acrylate, polyester, polyfluorene, polyvinyl butyral, polyvinyl acetal, polyphenylene oxide, polybutadiene, poly(N-vinylcarbazole), polyvinylpyrrolidone, Hydrocarbon resin, ketone resin, phenoxy resin, polyamine, chlorinated polypropylene, urea, cellulose, vinyl acetate, ABS resin, polyurethane, phenol resin, melamine resin, unsaturated polyester resin, At least one of an alkyd resin, an epoxy resin, a polyoxagen resin, and a copolymer of such a copolymer, and any mixture thereof. As the adhesive, various adhesives including acrylic-based adhesives can be used, which can be made of butyl acrylate or ethyl acrylate by a known crosslinking agent such as isocyanate, melamine or epoxy. A low Tg monomer such as 2-ethylhexyl acrylate is copolymerized with a functional monomer such as acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylamide or acrylonitrile. The acrylic-based copolymer is obtained by crosslinking. [Embodiment] -18-201108254 EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the following examples are purely exemplified, and the invention is not limited to the following examples. The following Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2 are examples of the transparent resin foils of the inventions 1 to 4 and the method for producing the same, Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 are transparent resin foils according to Inventions 5 to 8 and a method for producing the same. The evaluation methods used in the examples and comparative examples will be described below. When measuring the electric resistance of the transparent resin foil of the mesh-like structure which consists of a conductive layer and the metal microparticles which are formed on the base material, it is based on JIS-K-7 194. Lores GP (Dai Ansi Co., Ltd. , Model: MCP-T610) The four probes (ASP) in the in-line are implemented in a 4-terminal 4-probe method. Optical transmittance is evaluated as total light transmission. The transparent resin foil of the mesh-like structure composed of the conductive layer and the metal fine particles contained therein was measured in accordance with JIS K-7 105 using a nebulizer (Model: NDH-2000, manufactured by Nippon Denshi Kogyo Co., Ltd.). The thickness of the base material and the thickness of the transparent resin foil of the mesh-like structure composed of the metal fine particles were measured using a micrometer. The electromagnetic wave protection characteristic used is determined by the KEC method, and the decay rate of the electric field component is measured by the number of cycles from 1 MHz to 1 GHz. The durability test is to increase the rubbing resistance of 1 〇 0 times with cotton cloth under the weight of 1 9.6 P a (test machine: VIII.1. (:. (:. chronograph model CM-1, Aide) Lat Electric Equipment Co., Ltd., to evaluate the degree of damage of the conductive layer. · -19- 201108254 <Modulation method of silver microparticles 1> The liquid phase reduction preparation method of silver microparticles is described as an example of metal microparticles, but no metal is defined. Types of microparticles and production method: 40 g of silver nitrate, 37.9 g of butylamine and 200 mL of methanol were added, and the mixture was stirred for 1 hour to prepare solution A. Another 62.2 g of isoascorbic acid was added, 400 mL of water was added, and the mixture was stirred and dissolved, and then methanol was added to prepare 250 ml of liquid B. While stirring the B solution, A was dropped into the solution B at 1 hour and 20 minutes. After the completion of the dropwise addition, stirring was continued for 3 hours and 30 minutes. After stirring, the mixture was allowed to stand for 30 minutes to precipitate the solid matter. The upper layer was clarified by decantation. After the solution, 500 mL of water was added again, stirred, and allowed to stand, and the supernatant liquid was removed by decantation. After the refining operation was repeated three times, the precipitated solid was dried in a dryer at 40 ° C to remove moisture. The obtained silver microparticles 20g and DISPERBYK-10 6 (manufactured by Japan Juhua Co., Ltd.) 2 2g was mixed with a mixed solution of methanol 100 mL and pure water 5 mL, and after mixing for 1 hour, 100 mL of pure water was added, and the colloid was filtered, and dried in a dryer at 40 ° C to obtain silver fine particles 1. When the silver microparticles were observed by an electron microscope, the average particle diameter of the primary particles was 60 nm. <The silver fine particle dispersion solution 2 was prepared. The silver fine particle dispersion solution was prepared by referring to Patent Document 1 (refer to JP-A-2005-530005). After mixing the above-mentioned silver fine particles of 14 g, toluene 30 g, and BYK-410 (manufactured by Sakamoto Juju Co., Ltd.) 2. 2 g, the dispersion was treated for 1.5 minutes by an ultrasonic disperser having an output of 180 W, and water was added thereto. After 5 g, the obtained emulsion was subjected to dispersion treatment for 30 seconds to prepare a silver fine particle dispersion solution 2 by an ultrasonic disperser having an output force of -20-201108254 1 80 W. <Formation of Conductive Layer> The silver fine particle dispersion 2 is applied to a polyethylene terephthalate substrate having a thickness of m. Secondly, it is dried in the atmosphere, and the silver fine particles are formed into a mesh structure by self-organization phenomenon. Secondly, at 150°. C heating 2 points Thereafter, each was immersed in acetone; 5 hydrochloric acid, and dried by heating at 150 ° C for 5 minutes to form a mesh-like structure containing silver microparticles. A conductive layer formed from a mesh structure containing silver fine particles was formed on the substrate. The total light transmittance was 85 % and the resistance 値 was 4.5 Ω / 匚 1. Example 1-1: The following transparent resin layer coating liquid 1 - 1 was applied to the layer after drying to a thickness of 1 The transparent resin layer was formed on the polyethylene terephthalate substrate containing the silver fine particle structure produced by the above method at 100 ° C for 5 minutes. Next, the transparent layer containing the mesh-like structure of the silver fine particles is peeled off from the polyethylene terephthalate base material 2, and the transparent resin containing the mesh-like structure of the silver fine particles is included. The transparent resin layer coating liquid 1 -1 > 15 g of a polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 85 g of n-butanol to obtain a transparent resin layer coating liquid 1-, adjusted to 100 natural creations: 1N particle-like surface 5 /zm mesh dried alcohol ester resin foil. BX-1 -21 - 201108254 Example 1-2: The transparent resin layer coating liquid used is a transparent resin layer coating liquid 1-2, and the thickness of the transparent resin layer after coating drying is 2 〇 βιη, the same Example 1-1 Production of a transparent resin foil containing a mesh-like structure containing silver fine particles <Transparent resin layer coating liquid 1-2 > Cellulose acetate butyrate resin (manufactured by Hoffst, CAB381) -1) 15 g was dissolved in 85 g of methyl ethyl ketone to obtain a transparent resin layer coating liquid 1-2. Example 1-3: The transparent resin layer coating liquid used was a transparent resin layer coating liquid 1-3, and the thickness of the transparent resin layer after coating and drying was 20/zm, which was produced in the same manner as in Example 1-1. Transparent resin foil containing a mesh-like structure of silver fine particles <Transparent resin layer coating liquid 1-3 > 20 g of a vinyl chloride-vinyl acetate copolymer resin (manufactured by Nissin Chemical Co., Ltd., Solube CN) was dissolved in A In 80 g of ethyl ethyl ketone, a transparent resin layer coating liquid 1-3 was obtained. Comparative Example 1 -1 : 22-201108254 The electromagnetic wave protective material used was an aluminum foil, and the electromagnetic wave protection characteristics were measured.
防護特性的1MHz至1GHz下之衰退率爲充分的40dB 以上，但全光線透過率爲0%完全無視認性。 比較例1 - 2 : 依實施例1-1於PET膜（厚100 y m )上形成含有銀 微粒子之網目狀構造物作爲電磁波防護材料用，測定電磁 波防護材料特性，結果防護特性1MHz至1 GHz下之衰退 率爲充分的30dB以上。又全光線透過率爲85%，視認性 也優良。 但進行耐擦過性試驗後會看見導電性層遭破壞，耐久 性較低。 實施例1 -1至1 -3及比較例1 -1至1 -2所得的樣品之 評估結果如表1所示。 [表1] 全光線透過率 (%) 電磁波衰退率 _ 耐擦過性試驗 表面電阻値 (Ω /□) 實施例1-1 85 30dB以上 無損傷 4.5 實施例1-2 86 30dB以上 無損傷 4.6 實施例1-3 85 30dB以上 無損傷 4.5 比較例1-1 0 40dB以上 無損傷 0.01 比較例1-2 85 30dB以上 導電性層破壞 4.5 實施例2 -1 : -23- 201108254 將下述透明樹脂層塗佈液2-1以乾燥後厚度爲1 之方式塗佈於層合上述方法所製作的含有銀微粒子之 狀構造物的聚對苯二甲酸乙二醇酯基材上，以loot 5分鐘後，得形成含有銀微粒子所構成的網目狀構造 透明樹脂層的基材A。其次以同上述方法另外製作形 有銀微粒子所構成的網目狀構造物之透明樹脂層的基 。以前述基材A及基材B之形成透明樹脂層的表面 面對面方式重合後，使用熱層合機（大成層合製，大 速層合機VAII-700)以170°C壓合，再剝離2個聚對 甲酸乙二醇酯基材，得內包雙層銀微粒子所構成的網 構造物之透明樹脂箔。所得透明樹脂箔之全光線透過 71%，表面電阻値爲4.5Ω/1Ι]。 <透明樹脂層塗佈液2-1 > 將聚乙烯基丁縮醛樹脂（積水化學製，耶斯雷 )15g溶解於正丁醇85g中，得透明樹脂層塗佈液2- 實施例2-2 : 除了所使用的透明樹脂層塗佈液爲透明樹脂層塗 2-2，塗佈乾燥後之透明樹脂層厚爲20 /z m外，同實 2-1製作內包雙層含有銀微粒子之網目狀構造物的透 脂箔。 <透明樹脂層塗佈液2 - 2 > 5 β m 網目 乾燥 物之 成含 材B 同士 成快 苯二 目狀 率爲 BX-1 1 ° 佈液 施例 明樹 -24- 201108254 將氯乙烯-乙酸乙烯共聚合樹脂（日信化學製，索魯 拜CN ) 2 0g溶解於甲基乙基酮8〇g中，得透明樹脂層塗 佈液2-2 。 實施例2 - 3 : 製作與實施例2-1相同之形成含有銀微粒子所構成的 網目狀構造物之透明樹脂層的基材A，及以相同方法另外 準備的形成含有銀微粒子所構成的網目狀構造物之透明樹 脂層的基材B。其次將下述黏著層塗佈液1以乾燥膜厚爲 15/zm之方式塗佈於基材A之透明樹脂層表面上，以1〇〇 °C的溫度下乾燥5分鐘，使黏著層層合於基材A之透明 樹脂層表面，接著以該黏著層面面對基材B之透明樹脂層 面的方式重合，使用層合機（大成層合機製，大成快速層 合體VAII-700 )以常溫壓合後，剝離2個聚對苯二甲酸 乙二醇酯基材，得內包雙層銀微粒子所構成的網目狀構造 物之透明樹脂箔。 <黏著層塗佈液1> 將丁基丙烯酸酯與羥基丁基丙烯酸酯之共聚物3〇g及 伸苄基二異氰酸酯之三聚異氰酸酯物lg溶解於乙酸乙酯 69g中，得黏著層塗佈液1。 ^ 實施例2-4 : 藉由同實施例2-1之方法製作內包雙層含有銀微粒子 -25- 201108254 之網目狀構造物的透明樹脂箔》其次藉由同實施例2-1之 方法另外製作形成含有銀微粒子所構成的網目狀構造物之 透明樹脂層的基材C。重合內包雙層含有前述銀微粒子之 網目狀構造物的透明樹脂箔與基材C之形成該透明樹脂層 的表面，使用熱層合機（大成層合機製，大成快速層合體 VAII-7〇0)以170°C壓合後，剝離基材C之聚對苯二甲酸 乙二醇酯基材’製作內包三層銀微粒子所構成的網目狀構 造物之透明樹脂箔。 比較例2-1 : 所使用的電磁波防護材料爲蒸鍍厚0.15jizm之銅的 PET膜（厚度1 2 a m )，測定電磁波防護特性。 防護特性的1MHz至1GHz下之衰退率爲充分的50dB 以上’但全光線透過率爲0 %完全無視認性。 比較例2 - 2 : 依實施例2-1於PET膜（厚度1〇〇 μπ〇上形成含有 銀微粒子之網目狀構造物作爲電磁波防護材料用，測定電 磁波防護特性’結果防護特性1 Μ Η ζ至1 G Η Ζ下之衰退率 爲充分的3 OdB以上。全光線透過率爲8 5 %，視認性也優 良。 但耐擦過試驗的結果導電性層遭破壞，耐久性較低。 實施例2-1至2-4及比較例2-1至2-2所製作的樣品 之評估結果如表1所示。 -26- 201108254 [表2] 全光線透過率 (%) 電磁波衰退率 (dB) 耐擦過性試驗 表面電阻値 (Ω /□) 實施例2-1 71 40dB以上 無損傷 4.5 實施例2-2 70 40dB以上 無損傷 4.7 實施例2-3 69 40dB以上 無損傷 4.6 實施例2-4 62 45dB以上 無損傷 4.6 比較例2-1 0 50dB以上 無損傷 〇.〇1 比較例2-2 85 30dB以上 導電性層破壞 4.5 產業上利用可能性 本發明之透明樹脂箔具有優良的電磁波遮蔽性及光學 性透過性’且無需先前構造之基材，因此適用爲裝置小型 化、輕量化所使用的電磁波防護材料用透明樹脂箱。 【圖式簡單說明】 圖1爲，本發明1之透明樹脂箔及電磁波防護材料的 製造方法流程圖。 圖2爲，本發明5之透明樹脂箔及電磁波防護材料的 製造方法流程圖。 圖3爲，本發明9之電磁波防護材料的形態圖。 【主要元件符號說明】 金屬微粒子所構成的網目狀構造物（導電性層） 2 :基材 3 :透明樹脂層 -27- 201108254 4:內包金屬微粒子所構成的網目狀構造物之透明樹 脂箔 4’：內包雙層金屬微粒子所構成的網目狀構造物之透 明樹脂箔 5:內包三層金屬微粒子所構成的網目狀構造物之透 明樹脂箔 6:形成含有金屬微粒子所構成的網目狀構造物之透 明樹脂層的基材 7 :層合導電性層之基材 8:另外準備的形成含有金屬微粒子所構成的網目狀 構造物之透明樹脂層的基材 -28-The protection characteristic has a full-density rate of more than 40 dB at 1 MHz to 1 GHz, but the total light transmittance is 0% completely ignorant. Comparative Example 1 - 2 : A mesh-like structure containing silver fine particles was formed on a PET film (thickness: 100 μm) as an electromagnetic wave protective material according to Example 1-1, and the characteristics of the electromagnetic wave protective material were measured, and as a result, the protective property was 1 MHz to 1 GHz. The rate of decline is more than 30 dB. The total light transmittance is 85%, and the visibility is also excellent. However, after the scratch resistance test, the conductive layer was broken and the durability was low. The evaluation results of the samples obtained in Examples 1 to 1 to 3 and Comparative Examples 1 to 1 to 2 are shown in Table 1. [Table 1] Total light transmittance (%) Electromagnetic wave decay rate _ Corrosion resistance test surface resistance 値 (Ω / □) Example 1-1 85 30 dB or more without damage 4.5 Example 1-2 86 30 dB or more without damage 4.6 Implementation Example 1-3 85 No damage above 30 dB 4.5 Comparative Example 1-1 0 No damage above 40 dB 0.01 Comparative Example 1-2 85 Conductive layer breakage of 30 dB or more 4.5 Example 2 -1 : -23- 201108254 The following transparent resin layer The coating liquid 2-1 was applied to the polyethylene terephthalate substrate containing the silver fine particle-like structure produced by the above method after being dried to a thickness of 1, and was looted for 5 minutes. A substrate A containing a mesh-like structural transparent resin layer composed of silver fine particles was formed. Next, a base of a transparent resin layer having a mesh-like structure composed of silver fine particles was separately produced in the same manner as described above. After the surface of the substrate A and the substrate B on which the transparent resin layer was formed was superposed on each other, the film was laminated at 170 ° C using a thermal laminator (large layer laminator, VA II-700), and then peeled off. Two polyethylene terephthalate substrates were obtained by a transparent resin foil containing a mesh structure composed of two layers of silver fine particles. The obtained transparent resin foil had a total light transmission of 71% and a surface resistance 値 of 4.5 Ω/1 Ι]. <Transparent Resin Layer Coating Liquid 2-1 > 15 g of a polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 85 g of n-butanol to obtain a transparent resin layer coating liquid 2 - Example 2-2 : In addition to the transparent resin layer coating liquid used, the transparent resin layer was coated 2-2, and the thickness of the transparent resin layer after coating and drying was 20 /zm. A grease-permeable foil of a mesh-like structure of microparticles. <Transparent resin layer coating liquid 2 - 2 > 5 β m mesh dry matter into a material B is the same as the fast benzene dimorphism rate BX-1 1 ° cloth liquid application example Mingshu-24- 201108254 - Vinyl acetate copolymerized resin (manufactured by Nissin Chemical Co., Ltd., Solube CN) 20 g was dissolved in 8 g of methyl ethyl ketone to obtain a transparent resin layer coating liquid 2-2. Example 2 - 3 : A substrate A formed by forming a transparent resin layer containing a mesh-like structure composed of silver fine particles, and a mesh formed by forming silver fine particles prepared in the same manner as in Example 2-1 were produced. The substrate B of the transparent resin layer of the structure. Next, the following adhesive layer coating liquid 1 was applied onto the surface of the transparent resin layer of the substrate A in a dry film thickness of 15 / zm, and dried at a temperature of 1 ° C for 5 minutes to form an adhesive layer. Cooperating with the surface of the transparent resin layer of the substrate A, and then overlapping the transparent resin layer of the substrate B with the adhesive layer, using a laminator (large lamination mechanism, Dacheng rapid laminate VAII-700) at room temperature After the bonding, the two polyethylene terephthalate substrates were peeled off to obtain a transparent resin foil having a mesh-like structure composed of two layers of silver fine particles. <Adhesive layer coating liquid 1> 3 g of a copolymer of butyl acrylate and hydroxybutyl acrylate and a trimeric isocyanate lg of benzyl diisocyanate were dissolved in 69 g of ethyl acetate to obtain an adhesive layer coating. Cloth solution 1. ^Example 2-4: A transparent resin foil containing a double-layered structure containing silver fine particles-25-201108254 was produced by the same method as in Example 2-1, followed by the same method as in Example 2-1 Further, a substrate C which forms a transparent resin layer containing a mesh-like structure composed of silver fine particles is produced. The transparent resin foil containing the double-layered mesh structure containing the silver fine particles and the surface of the substrate C forming the transparent resin layer are superposed, and a thermal laminator is used (large-layer lamination mechanism, large-speed rapid laminate VAII-7〇) 0) After press-bonding at 170 ° C, the polyethylene terephthalate substrate of the substrate C was peeled off to form a transparent resin foil having a mesh-like structure composed of three layers of silver fine particles. Comparative Example 2-1: The electromagnetic wave protective material used was a PET film (thickness 12 a m ) in which copper having a thickness of 0.15 jim was deposited, and electromagnetic wave protection characteristics were measured. The protection characteristic has a decay rate of more than 50 dB from 1 MHz to 1 GHz' but the total light transmittance is 0% completely unrecognizable. Comparative Example 2 - 2 : The protective property of the PET film (the mesh-like structure containing silver fine particles formed on the thickness of 1 μμπ〇 as an electromagnetic wave protective material for measuring electromagnetic wave protection characteristics) was carried out according to Example 2-1. 1 防护 Η ζ The decay rate to 1 G Ζ is more than 3 OdB. The total light transmittance is 85 %, and the visibility is also excellent. However, as a result of the scratch resistance test, the conductive layer is broken and the durability is low. The evaluation results of the samples prepared in the samples -1 to 2-4 and the comparative examples 2-1 to 2-2 are shown in Table 1. -26- 201108254 [Table 2] Total light transmittance (%) Electromagnetic wave decay rate (dB) Corrosion resistance test surface resistance 値 (Ω / □) Example 2-1 71 40dB or more without damage 4.5 Example 2-2 70 40dB or more without damage 4.7 Example 2-3 69 40dB or more without damage 4.6 Example 2-4 62 45 dB or more without damage 4.6 Comparative Example 2-1 0 50 dB or more without damage 〇. 〇 1 Comparative Example 2-2 85 30 dB or more of conductive layer destruction 4.5 Industrial Applicability The transparent resin foil of the present invention has excellent electromagnetic shielding properties. And optically transmissive 'and without the need for a previously constructed substrate, This is a transparent resin case for electromagnetic wave protection materials used for miniaturization and weight reduction of the device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method for producing a transparent resin foil and an electromagnetic wave protective material according to the present invention. Fig. 3 is a view showing a form of a method for producing a transparent resin foil and an electromagnetic wave protective material according to the present invention. Fig. 3 is a view showing a form of an electromagnetic wave shielding material according to the present invention. [Description of main element symbols] A mesh-like structure composed of metal fine particles (conductive (2): base material 3: transparent resin layer -27-201108254 4: transparent resin foil 4' of a mesh-like structure composed of metal fine particles: a mesh-like structure composed of double-layered metal fine particles Transparent resin foil 5: transparent resin foil 6 containing a mesh-like structure composed of three layers of metal fine particles: base material 7 forming a transparent resin layer containing a mesh-like structure composed of metal fine particles: laminated conductive layer Substrate 8: Substrate 28- separately prepared to form a transparent resin layer containing a mesh-like structure composed of metal fine particles