200923971 九、發明說明： 【發明所屬之技術領域】 本發明涉及用於透明電極等之導電膜、導電構件及其製 造方法。更詳言之，涉及使用金屬奈米絲之導電膜、導電 構件及其製造方法。 【先前技術】 近年來，液晶顯示器、電漿顯示器之利用增多，這些裝 ( 置之必要構件透明電極膜之需求亦增加。用於習知透明電 極等之透明導電膜係以濺鍍法等乾式被覆爲主。然這起方 法乃批次式故製造成本高’而能連續生產之製造方法受到 期待。因被覆時須係高溫，有塑膠膜等樹脂基板無法便用 之缺點。 作爲解決此問題之方法，有人想出濕式被覆，並有以貴 金屬微粒子用作候選材料之一的網絡構造之提議（專利文 獻1及2)。[Technical Field] The present invention relates to a conductive film for a transparent electrode or the like, a conductive member, and a method of manufacturing the same. More specifically, it relates to a conductive film using a metal nanowire, a conductive member, and a method of manufacturing the same. [Prior Art] In recent years, the use of liquid crystal displays and plasma displays has increased, and the demand for transparent electrode films of these components has increased. The transparent conductive films used for conventional transparent electrodes are dry-type such as sputtering. The coating method is mainly used. However, this method is a batch type, and the manufacturing method of continuous production is expected. The coating method is required to be high-temperature, and there is a disadvantage that the resin substrate such as a plastic film cannot be used. In the method, there has been proposed a wet coating, and there is a proposal for a network structure in which precious metal fine particles are used as one of candidate materials (Patent Documents 1 and 2).
專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 非專利文獻1 667-669 【發明內容】 國際專利申請公開2003/0 1 6209公報 國際專利申請公開2003/068674公報 曰本專利特開2004- 223 693公報 臼本專利特開2002-266007公報 美國專利申請公開2005 -05 6 1 1 8公報 Nano Letters 2003 Vol. 3， No. 5 發明所欲解決之課題 200923971 然而專利文獻1所揭示之方法，須有真空系統內之蒸鍍 步驟’且於金屬之蒸鍍處理前基板須作前處理，而有製造 成本高之問題。 而專利文獻2之方法雖可採旋塗等濕式被覆，係能連續 製作之優良方法’但須煅燒步驟，有不能使用塑膠基板之 問題。 任一方法皆係金屬微粒子以念珠狀連結構成配線，網絡 f 形狀不定。因此，於某2點間構成配線時，不必要部分亦 有配線延伸，仍有不得全光線透射率低之導電膜的問題。 因此本發明之課題係在提供透明性高且表面電阻値低之 導電膜’並提供其能在大氣壓力下，以低溫塗布條件生產 之製造方法。 用以解決課題之手段 爲解決該課題，本發明人得知，使用直線狀金屬奈米絲 可無損於表面電阻特性，格外提升透明性；基於此見解’ / . 完成了本發明。 亦即，解決該課題之本發明係， 具有含直線狀金屬奈米絲之導電層，該直線狀金屬奈# 絲於相互之交點接合形成網目之導電膜。該交點部分之接 合係以經壓合或經電鍍爲佳。 於此，該金屬奈米絲係以粗細在1 〇 n m以上5 0 0 n m以下’ 且縱向長度l//m以上l〇〇#m以下爲佳；縱向長度 以上1 0 0 μ m以下更佳。 該金屬奈米絲以銀奈米絲爲佳。導電層亦可含碳奈米管。 200923971 亦可於該導電層上積層有保護層。 該導電膜之表面電阻値係以0.1Ω/□以上10000Ω/□以 下爲佳’表面電阻値爲1Ώ/□以上ι〇〇〇Ω/□以下更佳。 又’本發明係由基材與該導電膜構成之導電構件，該基 材係玻璃或樹脂製，全光線透射率8 0 %以上。 導電構件之全光線透射率係以6 0 %以上9 9 %以下爲佳， 7 0 %以上9 0 %以下更佳。 解決該課題之本發明導電膜的製造方法，其特徵爲包括 步驟1 :塗布金屬奈米絲於基材上之步驟，與 步驟2 :壓合經該步驟1塗布之金屬奈米絲的交點部分， 得接觸電阻降低之導電層的步驟。 該導電膜之製造方法亦可包括 步驟3 :於經步驟2得之導電層上形成保護層之步驟。 解決課題之本發明係導電膜的製造方法，其特徵爲包括 步驟1 :塗布金屬奈米絲於基材上之步驟，與 步驟4 :電鍍經該步驟1塗布之金屬奈米絲，得接觸電 阻降低之導電層的步驟。 該導電膜的製造方法亦可包括 步驟3(步驟5):於經步驟2(步驟4)得之導電層上形成保 護層之步驟。 發明效果 以本發明得之由直線狀金屬奈米絲構成的導電膜高度透 明，且電阻低；並能在大氣壓力下，以低溫塗布條件生產； 對於基材之密著性良好，具柔軟性。因可簡便低成本製得 200923971 尚性3旨透明導電I吴’非常適用作顯示器、所謂電子紙等之 透明電極’觸控板構件，電磁波遮蔽材。 【實施方式】 本發明係具有含直線狀金屬奈米絲之導電層，該直線狀 金屬奈米絲於相互之交點接合形成網目之導電膜。本發明 並係’形成導電膜於通常基材上，由該基材與該導電膜構 成之導電構件。經接合係表示’於該交點部分，直線狀金 ζ 屬奈米絲呈接觸面積大於僅只物理接觸者之狀態。該交點 部分之接合不論經由何種手段，若係接觸電阻極低之狀態 即可；例如壓合、電鍍皆適用。 基材若係薄片狀、薄膜狀者即無特殊限制，有例如玻璃、 氧化鋁等陶瓷，鐵、鋁 '銅等金屬，聚酯樹脂、纖維素樹 脂、乙烯醇樹脂、氯乙烯樹脂、環烯烴系樹脂、聚碳酸酯 樹脂、丙烯酸樹脂、A B S樹脂等熱塑性樹脂，光硬化性樹 脂、熱硬化性樹脂等；作爲本發明之導電膜使用之際透明 性受重視時，該基材之全光線透射率以係 80%以上爲佳， 具體而言有玻璃、聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂、 纖維素樹脂等。 該基材之較佳厚度隨用途而異，薄片狀者以500 # m以上 10mm以下爲佳，薄膜狀者以10 μ m以上5 00 A m以下爲佳。 直線狀金屬奈米絲指材質係金屬之奈米大小的粒子之中 其形狀爲棒狀者。用於本發明之直線狀金屬奈米絲不包含 分枝狀、球狀粒子連結成念珠狀者。直線狀者形成微細導 電迴路之效率可爲最高。唯金屬奈米絲剛性低’彎曲成香 200923971 蕉狀，折曲者仍包含於直線狀金屬奈米絲。 該直線狀金屬奈米絲之材質係金屬。不含金屬之氧化 物、氮化物等陶瓷。該等之導電性比金屬差，同時難以因 壓合塑性變形，經壓合亦難以降低接觸電阻。可製成金屬 奈米絲之金屬具體有鐵、鈷、鎳、銅、鋅、釕、錢、f巴、 銀、鎘、餓、銦、舶、金，從導電性之觀點係以銅、銀、 鉛、金爲佳，銀更佳。 f 該直線狀金屬奈米絲之粗細以lnm以上1/zm以下爲 佳，1 0 n m以上5 0 0 n m以下更佳。過粗則透射率低，過細則 難以製作。縱向長度以1 # m以上1 mm以下爲佳，1 〇 # m 以上1 0 0 /ζ m以下更佳。過短則導電性差’過長則難以取用。 金屬奈米絲之形狀、粗細可藉掃瞄電子顯微鏡、穿透電 子顯微鏡確認。 該直線狀金屬奈米絲可依習知方法製作。有例如，於溶 液中還原硝酸銀之方法；由探針先端部施加電壓或以電流 ί ： V ; 作用於前驅物表面，於探針先端部拉出金屬奈米絲，連續 形成該金屬奈米絲之方法（專利文獻3)等。於溶液中還原硝 酸銀之方法者具體有，還原金屬複合化肽脂質構成之奈米 纖維的方法（專利文獻4)，於乙二醇中一邊加熱一邊還原之 方法（專利文獻5)，於檸檬酸鈉中還原之方法（非專利文獻 1)等。其中，於乙二醇中一邊加熱一邊還原之方法最容易 製得直線狀金屬奈米絲故較佳。 本發明之導電膜具有該金屬奈米絲互相接合成網目狀的 導電層。該金屬奈米絲形成之網目若無間隔空隙，呈密集 200923971 狀態則不佳；不空出間隔則透射率低。 在無損於本發明效果之範圍內，可於導電層添加金屬奈 米絲以外之成分。具體而言有聚酯樹脂、纖維素樹脂、聚 醚樹脂、乙烯醇樹脂、乙烯類樹脂、環烯烴樹脂、聚碳酸 酯樹脂、丙烯酸樹脂、A B S樹脂、天然高分子等熱塑性樹 脂；丙丨希酸系、環氧丙院系等光硬化性樹脂；環氧系、三 聚氰胺系、矽酮系等熱硬化性樹脂等黏結劑成分，界面活 r . 性劑、顏料等。 I.' 金屬奈米絲與黏結劑等其它成分之配合比率可隨用途任 意變更’而金屬奈米絲之配合比過低則有導電性低之虞， 故金屬奈米絲占全體導電層的重量比係以1 〇質量％以上 1 0 0質量％以下爲佳，3 0質量％以上6 0質量％以下更佳。 金屬奈米絲之生成方法採用，於乙二醇中一邊加熱一邊 還原之方法爲代表的多元醇還原時，基於與其溶劑之適 性，係以醇或水可溶之黏結劑成分爲佳。具體有聚乙烯醇、 ί: 聚乙烯醇縮丁醛、部分水解聚（乙酸乙烯酯/乙烯醇）、聚乙 烯吡咯烷酮、纖維素酯、纖維素醚、聚噚唑啉、聚乙烯乙 醯胺、聚丙烯酸、聚丙烯醯胺、聚丙烯腈、聚甲基丙烯酸 羥乙酯、聚環氧烷、磺醯化或磷酸化聚酯及聚苯乙烯、幾 丁質、聚葡萄胺糖、洋菜、明膠、聚乳酸-聚乙二醇共聚物、 聚乙烯胺、聚乙烯硫酸、聚乙烯磺酸、聚二醇酸、聚乙二 醇等。 本發明之導電膜的樣態係具有，直線狀金屬奈米絲相互 之交點部分經壓合的導電層。交點部分經壓合則起塑性變 -10- 200923971 形，直線狀金屬奈米絲間之接觸電阻下降，導電層之表面 電阻値下降。直線狀金屬奈米絲相互之交點部分指，直線 狀金屬奈米絲從網目狀分散之導電層正上方觀察，直線狀 金屬奈米絲重疊被看見之部分。經壓合則該交點部分變 形，直線狀金屬奈米絲之接觸面積呈變大之狀態。本發明 中，該交點部分未必須全經壓合’有一部分即可。即使是 一部分，亦可得導電層的表面電阻値下降之效果。 ^ 直線狀金屬奈米絲相互之交點部分已否經壓合可藉掃瞄 k 電子顯微鏡、穿透電子顯微鏡’由該交點部分有無變形作 確認。 本發明之導電膜的另一樣態係具有’直線狀金屬奈米絲 相互之交點部分經電鍍的導電層。電鍍交點部分則直線狀 金屬奈米絲間之接觸面積增大’接觸電阻下降，透明導電 層之表面電阻値下降。直線狀金屬奈米絲相互之交點部分 指，從直線狀金屬奈米絲作網目狀分散之導電層正上方觀 t 察’直線狀金屬奈米絲被重疊看到的部分。經電鍍係指， 直線狀金屬奈米絲之交點部分比電鍍前粗，接觸面積增大 之狀態。本發明中’該交點部分未必須全經電鍍，有一部 分即可。即使是一部分’亦可得導電餍的表面電阻値下降 之效果。交點以外之部分亦可經電鍍而加粗。 電鍍材料若係習知金屬即無特殊限制，具體有鉻、鐵、 鎳、銅、鋅 '鈀、銀、鎘、錫、鎢、鉑、金等，以鎳、銅、 銀爲佳，銀更佳。 本發明之導電膜的層構造若具導電層即無特殊限制，在 -11 - 200923971 無損於本發明效果之範圍亦可有保護層 層、抗靜電層、防眩層、反射防止層、 位差膜層等。具體之層構造有，如第1 電層上積層有保護層、反射防止層之層； 於硬被覆層上形成有導電層之層構造，； 層反側設置防眩層之層構造等。 使用與導電層之密著性低的基材時， 低時，以於導電層上設置保護層爲尤佳 料無特殊限制，可用聚酯樹脂、纖維素榜 乙烯類樹脂、環烯烴系樹脂、聚碳酸酯植 ABS樹脂等熱塑性樹脂，光硬化性樹脂 習知被覆材料。從密著性之觀點，保護 材同之材料爲佳，例如基材係聚酯樹脂 酯樹脂爲佳。保護層過厚則導電層之接 不得作爲保護層之效果，故以1 n m以上 10nm以上lOOnm以下更佳。 用於本發明之導電層，可連同直線狀 米管。在必須有比直線狀金屬奈米絲間 提供有效之導電膜。 用於本發明之碳奈米管若係習知碳； 制，所謂多層碳奈米管、二層碳奈米管 皆適用，單層碳奈米管爲最佳。習知碳 碳奈米管導電性最高。其中又以電弧放 奈米管，因結晶性優於以其它方法製作 、底塗層、硬被覆 彩色濾光片層、相 圖及第2圖之於導 ^冓造，如第3圖之 如第4圖之於導電 或導電層之膜強度 。用於保護層之材 ί脂、乙烯醇樹脂、 ί脂、丙烯酸樹脂、 及熱硬化性樹脂等 層之材料係以與基 時保護層以亦係聚 觸電阻大，過薄則 1 # m以下爲佳， 金屬奈米絲含碳奈 更細之配線時，可 奈米管即無特殊限 、單層碳奈米管等 奈米管之中，單層 電法製作之單層碳 之單層碳奈米管而 -12- 200923971 更佳。 於本發明使用碳奈米管時，碳奈米管與直線狀金 絲之質量比係以，該導電層含之金屬奈米絲質量在 管質量的1倍以上1〇〇〇倍以下爲佳，丨0倍以上1〇〇 更佳。該質量比在丨〇〇〇倍以上時碳奈米管之添加 響’ 1倍以下時直線狀金屬奈米絲之添加效果小。 本發明之導電膜，表面電阻値係以〇.丨Ώ /□以上 (s Q/□以下爲佳，ιω/□以上1 000 Ω/□以下更佳，〇 以上100 Ω /□以下尤佳，0.1 Ω /□以上10 Ω /□以下 本發明中透明導電膜之表面電阻値及透光性，與導 直線狀金屬奈米絲之密度有關。直線狀金屬奈米絲 低而表面電阻値過高則難以用作電極等，直線狀金 絲之密度高而表面電阻値過低則反而透射率低，即 用作光學構件。 由基材與導電膜構成之本發明的導電構件，全光 ί ' I 率隨所用之基材而異，而全光線透射率係以60%以 以下爲佳，7 0 %以上9 0 %以下更佳，8 0 %以上9 0 %以Τ 直線狀金屬奈米絲之密度低而表面電阻値過高則 面電阻値過高，難以利用作電極等，直線狀金屬奈 密度高而全光線透射率過低則難以利用作光學構件 本發明係包括以下步驟1及2之導電膜製造方法 步驟1:塗布金屬奈米絲於基材上之步驟 步驟2 :壓合經該步驟1塗布之金屬奈米絲的交點 得導電層之步驟 屬奈米 碳奈米 倍以下 幾無影 100000 • 1 Ω /□ 最佳。 電層中 之密度 屬奈米 難以利 線透射 上 99% ^尤佳。 反而表 米絲之 部分， -13- 200923971 以下說明各步驟。 [步驟1]:塗布金屬奈米絲於基材上之 不含例如物理蒸鍍法、化學蒸鍍法等 電漿產生技術之離子植入法、濺鍍法 發明之濕式被覆指，塗布液體於基板 於本發明之濕式被覆若係習知方法即 噴塗、棒塗、輕塗、模塗、噴墨塗布 f - 印刷法、凹版印刷法、凹輥印刷法等 料之條件，亦可於步驟1後包括，於 之材料、所用之溶劑的程序’或洗淨 之導電層中的雜質之沖洗程序。 步驟1亦可不只1次而重複多次。 次有可能不得所欲膜厚。 於本發明中併用碳奈米管時，可混 絲之分散液與含碳奈米管之分散液一 t 1前或後僅以含碳奈米管之分散液塗才 去除塗布後含於塗膜中之溶劑係採 可使用加熱爐、遠紅外線爐加熱（乾海 用真空乾燥等手法。 [步驟2]:壓合金屬奈米絲之交點部分 指，使從直線狀金屬奈米絲以網目狀 觀察時，使直線狀金屬奈米絲重疊所 線狀金屬奈米絲之互相接觸面積變大 步驟，金屬奈米絲間之接觸電阻降低 步驟係指濕式被覆， 真空蒸鍍法，或使用 等乾式被覆。用於本 上以製膜之程序。用 無特殊限制，可採用 、網塗、沾塗、凸版 。隨塗布之方法、材 基板加熱去除經塗布 分散劑等含於經製膜 依塗布條件，僅只1 合含直線狀金屬奈米 倂塗布，亦可於步驟 用適當手法。例如’ i )去除溶劑。亦可採 ，得導電層的步驟係 分散之導電層正上方 見部分變形’而呈直 的狀態之步驟。經此 。具體有將導電膜面 -14- 200923971 加壓之方法。本步驟若係習知方法即無特殊限制，有將步 驟1得之膜固定於硬質平面上，以硬質棒作點加壓，移動 加壓點作面加壓之方法；於二輥間夾入步驟1得之膜作線 加壓，使輥迴轉將面全體加壓之方法。 加壓時之壓力若係金屬奈米絲可變形之程度者即無特殊 限制，以輥壓合時，線壓以 1 kgf/cm(980Pa · m)以上 100kgf/cm(98kPa· m)以下爲佳，10kgf/cm(9.8kPa· m)以上 f·' 50kgf/cm(49kPa · m)以下更佳。基材輸送速度（線速）可適當 \ .. 選於實用範圍，一般係以10mm/分鐘以上1 0000mm/分鐘以 下爲佳，10mm/分鐘以上100mm/分鐘以下更佳。過快則加 壓時間不足。然而，亦可藉增加輥數以增加壓合次數、增 加施壓時間。 本發明係包括以下步驟1及步驟4之導電膜製造方法。 步驟1 :塗布金屬奈米絲於基材上之步驟 步驟4:電鍍經該步驟1塗布之金屬奈米絲，得導電層的 I 步驟 以下說明各步驟。 [步驟4 ]:步驟4之電鍍步驟係指，於金屬奈米絲之交點部 分以金屬被覆的步驟。所使用之金屬若係習知金屬即無特 殊限制，具體有鉻、鐵、鎳、銅、鋅、鈀、銀、鎘、錫、 鎢、鈾、金寺’以鏡、銅、銀爲佳，銀更佳。 電鍍方法可係電鍍、無電解電鍍中任一。其中無電解電 鍍因更簡便而較佳。 本發明之導電膜製造方法並可包括 -15- 200923971 步驟3或5:於該步驟2或4中得之導電層上形成保護層之 步驟。 本步驟係以使用在，當所用之材料與導電層的密著性低 時，或用於導電層之膜強度低時爲佳。形成保護層之方法 若係習知方法即無特殊限制，以濕式被覆爲佳。如上’保 護層多係有機物’乾式程序一般難爲有機物之製膜。具體 而言，可採噴塗、棒塗、輥塗、模塗、噴墨塗布、網塗、 沾塗等。本步驟因係於導電層上施行，以塗布裝置不接觸 基板之塗布方法爲佳。具體而言可列舉噴塗、模塗、噴墨 塗布、沾塗等。 隨塗布方法、材料條件，亦可於步驟3或4後採行將基 板加熱’去除經塗布之材料所用的溶劑之程序。 本發明可依上述方法製造導電膜。例如於步驟1及2後 施行歩·驟3或於步驟丨及4後施行步驟5可得第1圖之積 層體°於用在步驟1之基材積層有硬被覆層時，於硬被覆 層上施行步驟1可得第3圖之積層體。使用有防眩層之基 材’於基材的防眩層反面施行步驟1可得第4圖之積層體。 實施例 <實施例1 > [銀奈米絲分散液之調製] 於 1L 三口燒瓶饋入乙二醇（和光純藥工業公司 製）3 3 3.9 g、氯化鈉（和光純藥工業公司製）48ng及參（2,4-戊 二_根）鐵（III)(Aldrich 公司製）41ng，加熱至 160°C。 於該混合溶液中以乙二醇（和光純藥工業公司製）2〇〇g、氯 -16- 200923971 化鈉（和光純藥工業公司製）291^、參（2,4-戊二酮根）鐵 (III)(Aldrich公司製）25ng及硝酸銀（和光純藥工業公司 製）2.8 8g構成之混合溶液與乙二醇（和光純藥工業公司 製）20(^、氯化鈉（和光純藥工業公司製）2.111^、參（2,4-戊二 酮根）鐵（IIIHAldrich公司製）128ng及聚乙烯吡咯烷酮（Mw. 5 5 000，Aldrich公司製）3. lg構成之溶液經6分鐘滴入，攪 捽3小時得銀奈米絲之分散液。 得到之銀奈米絲以掃瞄電子顯微鏡觀察，結果如第5圖 及第6圖。由此結果知，用於本實施例之銀奈米絲縱向長 度爲以上20//m以下，短軸方向長度爲l〇〇nm以上 300nm以下。 [導電膜之製作及評估] 得到之混合溶液經離心分離（裝置名稱：高速冷卻離心機 CR22GII日立工機公司製3 000Gx5分鐘），將殘渣分散於 水與2-丙醇之混合溶液（5 0/5 0 vol%) l〇ml。分散液中固體成 分濃度爲1 . 3 w t %。 棒塗得到之銀奈米絲分散液於PET薄膜（商品名： COSMOSHINE A4100，東洋紡公司製，全光線透射率92%) 上使濕膜厚達3 /2 m。於8 0 °C乾燥3分鐘得積層膜。 於積層膜上以附有脫模層之PET薄膜（商品名： COSMOSHINE K 1 57 2’東洋紡公司製）疊合使脫模層接觸導 電層’如第7圖由附有脫模層之ρ Ε τ薄膜側以瑪瑙製乳棒 擦拭，於導電層面施以壓力。 得到之導電膜的表面電阻値係5 0 〇 Ω /□(裝置名稱： -17- 200923971Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Non-Patent Document 1 667-669 [Summary of the Invention] International Patent Application Publication No. 2003/0 1 6 209, International Patent Application Publication No. 2003/068674, Japanese Patent Application Publication No. 2004 - 223 693 臼 专利 专利 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 There must be a vapor deposition step in the vacuum system' and the substrate must be pretreated before the metal evaporation treatment, which has the problem of high manufacturing cost. On the other hand, the method of Patent Document 2 can be wet-coated such as spin coating, and is an excellent method capable of continuous production. However, the calcination step is required, and there is a problem that the plastic substrate cannot be used. In either method, the metal particles are connected in a beaded shape to form a wiring, and the shape of the network f is indefinite. Therefore, when wiring is formed between two points, there is a problem that the unnecessary portion also has a wiring extension, and there is still a conductive film which does not have a low total light transmittance. Therefore, an object of the present invention is to provide a conductive film which has high transparency and low surface resistance and provides a production method which can be produced under low temperature coating conditions under atmospheric pressure. Means for Solving the Problem In order to solve the problem, the inventors have found that the use of a linear metal nanowire can impart a surface acoustic resistance characteristic and particularly improve transparency; based on this finding, the present invention has been completed. That is, the present invention for solving the problem has a conductive layer containing a linear metal nanowire, and the linear metal wire is joined to form a conductive film of a mesh at the intersection of each other. The joining of the intersection portions is preferably by pressing or plating. Here, the metal nanowire is preferably 1 μm or more and 500 nm or less in thickness, and a longitudinal length of l//m or more l〇〇#m or less is preferable; and a longitudinal length of 1 0 0 μm or less is more preferable. . The metal nanowire is preferably silver nanowire. The conductive layer may also contain a carbon nanotube. 200923971 A protective layer may also be laminated on the conductive layer. The surface resistance of the conductive film is preferably 0.1 Ω / □ or more and 10000 Ω / □ or less. The surface resistance 値 is preferably 1 Ώ / □ or more and ι Ω / □ or less. Further, the present invention relates to a conductive member comprising a substrate and a conductive film made of glass or resin and having a total light transmittance of 80% or more. The total light transmittance of the conductive member is preferably 60% or more and 99% or less, more preferably 70% or more and 90% or less. A method for producing a conductive film of the present invention, which is characterized in that it comprises the steps of: coating a metal nanowire on a substrate, and step 2: pressing a portion of the intersection of the metal nanowire coated by the step 1. , the step of contacting the conductive layer with reduced resistance. The method for manufacturing the conductive film may further include the step of: forming a protective layer on the conductive layer obtained in the step 2. The present invention is a method for producing a conductive film, which comprises the steps of: coating a metal nanowire on a substrate, and step 4: plating a metal nanowire coated by the step 1, to obtain a contact resistance. The step of lowering the conductive layer. The method for producing the conductive film may further include the step of forming a protective layer on the conductive layer obtained in the step 2 (step 4) in the step 3 (step 5). Advantageous Effects of Invention The conductive film composed of the linear metal nanowire obtained by the present invention is highly transparent and has low electrical resistance; and can be produced under low temperature coating conditions under atmospheric pressure; and has good adhesion to the substrate and has flexibility. . It is easy and low-cost. 200923971 The 3rd transparent conductive I-W is very suitable for use as a transparent electrode for display, so-called electronic paper, and a touch panel member, electromagnetic shielding material. [Embodiment] The present invention has a conductive layer containing linear metal nanowires which are joined at the intersections of each other to form a conductive film of a mesh. The present invention is also a conductive member formed of a conductive film on a usual substrate and composed of the substrate and the conductive film. The joined system indicates that, in the intersection portion, the linear ruthenium nanowire has a contact area larger than that of only the physical contact. The joint of the intersection portion may be in a state in which the contact resistance is extremely low regardless of the means; for example, press-bonding or plating is applicable. The substrate is not particularly limited as long as it is in the form of a sheet or a film. Examples thereof include ceramics such as glass and alumina, metals such as iron and aluminum, copper, polyester resins, vinyl resins, vinyl alcohol resins, vinyl chloride resins, and cycloolefins. a thermoplastic resin such as a resin, a polycarbonate resin, an acrylic resin, or an ABS resin, a photocurable resin, a thermosetting resin, or the like; and when the transparency of the conductive film of the present invention is emphasized, the total light transmission of the substrate The rate is preferably 80% or more, and specifically, glass, polyester resin, polycarbonate resin, acrylic resin, cellulose resin, or the like. The preferred thickness of the substrate varies depending on the application, and the flaky shape is preferably 500 # m or more and 10 mm or less, and the film shape is preferably 10 μm or more and 500 Å or less. The linear metal nanowire refers to a material in which the material is a nanometer-sized particle. The linear metal nanowire used in the present invention does not contain branched or spherical particles which are joined to form a bead. The efficiency of forming a fine conductive loop in a straight line can be the highest. Only metal nanowires have low rigidity and bend into incense 200923971 The shape of the banana is still included in the linear metal nanowire. The material of the linear metal nanowire is metal. Non-metallic oxides, nitrides and other ceramics. These electrical conductivity is inferior to that of the metal, and it is difficult to plastically deform by press-bonding, and it is difficult to reduce the contact resistance by press-bonding. Metals that can be made into metal nanowires are specifically iron, cobalt, nickel, copper, zinc, antimony, money, f, silver, cadmium, hungry, indium, foreign, gold, from the point of view of conductivity, copper, silver Lead, gold is better, silver is better. f The thickness of the linear metal nanowire is preferably 1 nm or more and 1/zm or less, more preferably 1 0 n m or more and 5 0 0 n m or less. If it is too thick, the transmittance is low, and it is difficult to make it by the details. The longitudinal length is preferably 1 # m or more and 1 mm or less, and 1 〇 # m or more is more preferably 1 0 0 /ζ m or less. If it is too short, the conductivity is poor. If it is too long, it is difficult to obtain. The shape and thickness of the metal nanowire can be confirmed by a scanning electron microscope or a penetrating electron microscope. The linear metal nanowire can be produced by a known method. For example, a method of reducing silver nitrate in a solution; applying a voltage from a tip end portion of the probe or a current ί: V; acting on the surface of the precursor, pulling out the metal nanowire at the tip end portion of the probe, and continuously forming the metal nanowire Method (Patent Document 3) and the like. In the method of reducing the silver nitrate in the solution, the method of reducing the metal-complexed peptide-formed nanofibers (Patent Document 4) is a method of reducing while heating in ethylene glycol (Patent Document 5), in citric acid A method of reducing in sodium (Non-Patent Document 1) or the like. Among them, a method of reducing while heating in ethylene glycol is most preferable because a linear metal nanowire is most easily produced. The electroconductive film of the present invention has a conductive layer in which the metal nanowires are joined to each other in a mesh shape. The mesh formed by the metal nanowire is inferior in the state of 200923971 if there is no gap, and the transmittance is low when the space is not vacant. The components other than the metal nanowires may be added to the conductive layer within the range not impairing the effects of the present invention. Specifically, there are thermoplastic resins such as polyester resin, cellulose resin, polyether resin, vinyl alcohol resin, vinyl resin, cycloolefin resin, polycarbonate resin, acrylic resin, ABS resin, and natural polymer; Photocurable resin such as epoxy resin, epoxy resin, etc.; a binder component such as an epoxy resin, a melamine-based or an anthrone-based thermosetting resin, and an interface agent, a pigment, and the like. I. The mixing ratio of metal nanowires and other components such as binders can be arbitrarily changed according to the use, and the low ratio of metal nanowires has low conductivity, so the metal nanowires occupy the entire conductive layer. The weight ratio is preferably 1% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 60% by mass or less. The method for producing a metal nanowire is preferably a polyol or water-soluble binder component based on the suitability of the solvent in the case where the polyol is reduced by heating while being heated. Specifically, there are polyvinyl alcohol, ί: polyvinyl butyral, partially hydrolyzed poly(vinyl acetate/vinyl alcohol), polyvinyl pyrrolidone, cellulose ester, cellulose ether, polyoxazoline, polyethylene acetamide, Polyacrylic acid, polypropylene decylamine, polyacrylonitrile, polyhydroxyethyl methacrylate, polyalkylene oxide, sulfonated or phosphorylated polyester and polystyrene, chitin, polyglucosamine, agar, Gelatin, polylactic acid-polyethylene glycol copolymer, polyvinylamine, polyvinylsulfuric acid, polyvinylsulfonic acid, polyglycolic acid, polyethylene glycol, and the like. The conductive film of the present invention has a conductive layer in which portions of the linear metal nanowires are bonded to each other. When the intersection is pressed, the plasticity changes. -10-200923971 The contact resistance between the linear metal nanowires decreases, and the surface resistance of the conductive layer decreases. The intersection point of the linear metal nanowires means that the linear metal nanowires are observed from the front side of the mesh-like dispersed conductive layer, and the linear metal nanowires overlap the portion to be seen. When the pressure is combined, the intersection portion is deformed, and the contact area of the linear metal nanowire becomes large. In the present invention, the intersection portion does not have to be fully pressed and has a part. Even in part, the surface resistance of the conductive layer is reduced. ^ Whether the intersection of the linear metal nanowires has been pressed or not can be scanned by k electron microscopy and penetrating electron microscope, and the presence or absence of deformation at the intersection is confirmed. Another aspect of the electroconductive film of the present invention has a conductive layer in which portions of the linear metal nanowires are plated at the intersection. When the plating intersection portion is linear, the contact area between the metal nanowires increases. The contact resistance decreases, and the surface resistance of the transparent conductive layer decreases. The intersection of the linear metal nanowires refers to the portion where the linear metal nanowires are overlapped and viewed from the upper side of the conductive layer in which the linear metal nanowires are mesh-likely dispersed. By electroplating, the intersection portion of the linear metal nanowire is thicker than that before plating, and the contact area is increased. In the present invention, the intersection portion does not have to be completely plated, and a part is sufficient. Even a part of it can also have the effect of lowering the surface resistance of the conductive crucible. Parts other than the intersection may also be thickened by electroplating. Electroplating materials are not subject to special restrictions, such as chromium, iron, nickel, copper, zinc 'palladium, silver, cadmium, tin, tungsten, platinum, gold, etc., preferably nickel, copper, silver, silver good. The layer structure of the conductive film of the present invention is not particularly limited as long as it has a conductive layer, and may have a protective layer, an antistatic layer, an antiglare layer, an antireflection layer, and a difference in the range of -11 - 200923971 without impairing the effects of the present invention. Film layer, etc. The specific layer structure includes, for example, a layer in which a protective layer and an antireflection layer are laminated on the first electric layer, a layer structure in which a conductive layer is formed on the hard coating layer, and a layer structure in which an antiglare layer is provided on the opposite side of the layer. When a substrate having low adhesion to a conductive layer is used, when a substrate is provided at a low level, a protective layer is preferably provided on the conductive layer, and a polyester resin, a cellulose-based vinyl resin, a cycloolefin resin, or the like may be used. Polycarbonate is a thermoplastic resin such as ABS resin, and a photocurable resin is a conventional coating material. From the viewpoint of adhesion, the protective material is preferably the same as the material, for example, a substrate-based polyester resin ester resin. When the protective layer is too thick, the connection of the conductive layer is not required as a protective layer, so it is preferably 1 n m or more and 10 nm or more and 100 nm or less. The conductive layer used in the present invention may be combined with a linear rice tube. An effective conductive film must be provided between the linear metal nanowires. The carbon nanotubes used in the present invention are conventional carbons; the so-called multilayer carbon nanotubes and the two-layer carbon nanotubes are suitable, and the single-layer carbon nanotubes are preferred. Conventional carbon carbon nanotubes have the highest conductivity. Among them, the arc is placed on the nano tube, because the crystallinity is better than that produced by other methods, the undercoat layer, the hard-coated color filter layer, the phase diagram and the second figure, as shown in Fig. 3, as shown in Fig. 3. Figure 4 is a graph showing the film strength of a conductive or conductive layer. The material used for the protective layer is a material such as a gluten, a vinyl alcohol resin, a gluten resin, an acrylic resin, or a thermosetting resin, and the base protective layer has a large contact resistance, and is too thin to be 1 # m or less. Preferably, when the metal nanowire has a finer carbon wire, the nano tube is a single layer carbon single carbon layer produced by a single layer electric method, such as a special tube, a single layer carbon nanotube tube or the like. Nano tube and -12- 200923971 is better. When the carbon nanotube is used in the present invention, the mass ratio of the carbon nanotube to the linear gold wire is such that the quality of the metal nanowire contained in the conductive layer is preferably 1 time or more and 1 or less times the tube mass. , 丨 0 times more than 1 〇〇 better. When the mass ratio is 丨〇〇〇 or more, the addition effect of the linear metal nanowire is small when the addition of the carbon nanotubes is less than 1 time. In the conductive film of the present invention, the surface resistance is preferably 〇.丨Ώ /□ or more (s Q/□ or less is preferable, ιω/□ or more is preferably 1 000 Ω/□ or less, and more preferably 100 Ω/□ or less. 0.1 Ω /□ or more and 10 Ω /□ or less The surface resistance 値 and light transmittance of the transparent conductive film of the present invention are related to the density of the linear metal nanowire. The linear metal nanowire is low and the surface resistance is too high. It is difficult to use as an electrode or the like, and the density of the linear gold wire is high and the surface resistance is too low, but the transmittance is low, that is, it is used as an optical member. The conductive member of the present invention composed of a substrate and a conductive film, The I ratio varies depending on the substrate used, and the total light transmittance is preferably 60% or less, more preferably 70% or more and 90% or less, and 80% or more and 90% of the linear metal nanowires. When the density is low and the surface resistance is too high, the sheet resistance is too high, and it is difficult to use it as an electrode. The linear metal density is high and the total light transmittance is too low, so that it is difficult to use it as an optical member. The present invention includes the following steps 1 and 2 Conductive film manufacturing method Step 1: Coating metal nanowire on the substrate Step 2: The step of pressing the intersection of the metal nanowires coated by the step 1 to obtain the conductive layer is a nanocarbon phase with a minimum of 100000 • 1 Ω / □. The density in the electric layer is nanometer. It is difficult to transmit 99% of the line. Especially the part of the meter, -13- 200923971 The following steps are explained. [Step 1]: The coated metal nanowire is not contained on the substrate, for example, physical vapor deposition. The ion implantation method of the plasma generation technique such as the chemical vapor deposition method, and the wet coating method of the sputtering method, the coating liquid is applied to the substrate in the wet coating of the present invention, that is, the conventional method of spraying, bar coating, light coating, The conditions of the die coating, the inkjet coating f-printing method, the gravure printing method, the concave roll printing method, etc. may also be included in the procedure of the material, the solvent used, or the washed conductive layer after the step 1. The rinsing procedure of the impurities. Step 1 may be repeated more than once. The film thickness may be undesired. When the carbon nanotubes are used in the present invention, the mixed liquid of the mixed wire and the carbon-containing nanotubes may be used. The dispersion is only coated with a dispersion containing carbon nanotubes before or after the t1 The solvent which is removed in the coating film after coating can be heated by a heating furnace or a far-infrared furnace (vacuum drying by dry sea, etc. [Step 2]: Pressing the intersection point of the metal nanowire to make it linear When the metal nanowire is observed in a mesh shape, the contact area of the linear metal nanowires in which the linear metal nanowires are overlapped is increased, and the contact resistance reduction step between the metal nanowires refers to wet coating, vacuum Evaporation method, or use of dry coating, etc. It is used for the film forming process. It can be used, mesh coating, dip coating, and relief. Unless it is coated, the coating substrate is heated to remove the coated dispersant. It is also applied to the film-forming coating according to the coating conditions, and only one type of linear metal nano-coated is used, and the appropriate method can also be used in the step. For example, ' i ) removes the solvent. Alternatively, the step of obtaining the conductive layer is a step in which the partially deformed conductive layer is partially deformed and in a straight state. Through this. Specifically, there is a method of pressurizing the conductive film surface -14 - 200923971. If the method is a conventional method, there is no particular limitation, and the film obtained in the step 1 is fixed on a hard surface, the hard rod is used as a point pressure, and the pressure point is moved as a surface pressure method; The film obtained in the step 1 is subjected to line pressurization, and the roll is rotated to press the entire surface. The pressure at the time of pressurization is not particularly limited as long as the metal nanowire is deformable. When the roll is pressed, the line pressure is 1 kgf/cm (980 Pa·m) or more and 100 kgf/cm (98 kPa·m) or less. Preferably, it is more preferably 10 kgf/cm (9.8 kPa·m) or more and f·' 50 kgf/cm (49 kPa·m) or less. The substrate transport speed (wire speed) can be appropriately selected from the range of 10 mm/min or more and 1 0000 mm/min or less, preferably 10 mm/min or more and 100 mm/min or less. If it is too fast, the pressure is insufficient. However, it is also possible to increase the number of presses to increase the number of presses and increase the pressing time. The present invention includes the following steps 1 and 4 of the method for producing a conductive film. Step 1: Step of coating metal nanowire on the substrate Step 4: Plating the metal nanowire coated by the step 1 to obtain a conductive layer I. The respective steps are explained below. [Step 4]: The electroplating step of the step 4 refers to a step of coating the metal at the intersection of the metal nanowires. The metal to be used is not limited to conventional metals, and specifically chromium, iron, nickel, copper, zinc, palladium, silver, cadmium, tin, tungsten, uranium, and gold temples are preferably mirrors, copper, and silver. Silver is better. The plating method may be any of electroplating and electroless plating. Among them, electroless plating is easier and better. The method for producing a conductive film of the present invention may include the step of forming a protective layer on the conductive layer obtained in the step 2 or 4, step -15-200923971. This step is preferably used when the adhesion between the material used and the conductive layer is low, or when the film strength for the conductive layer is low. Method of forming a protective layer If there is no particular limitation on the conventional method, wet coating is preferred. The above-mentioned 'protective layer multi-organic matter' dry procedure is generally difficult to form a film of organic matter. Specifically, it can be sprayed, bar coated, roll coated, die coated, ink jet coated, screen coated, dip coated, and the like. This step is preferably performed on the conductive layer, and the coating means is not applied to the substrate. Specific examples thereof include spraying, die coating, inkjet coating, and coating. Depending on the coating method and material conditions, the procedure for heating the substrate to remove the solvent used for the coated material may be employed after step 3 or 4. The present invention can produce a conductive film in accordance with the above method. For example, after the steps 1 and 2 are performed, the step 3 is performed, or the step 5 is performed after the steps 丨 and 4, and the layered body of the first embodiment is obtained. When the hard coat layer is laminated on the substrate layer used in the step 1, the hard coat layer is applied. The step 1 of the above can be carried out to obtain the layered body of Fig. 3. The laminate of Fig. 4 can be obtained by performing the step 1 on the reverse side of the antiglare layer of the substrate using the substrate having the antiglare layer. Example <Example 1 > [Preparation of silver nanofilament dispersion] Into a 1 L three-necked flask, ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was fed 3 3 3.9 g, sodium chloride (Wako Pure Chemical Industries Co., Ltd.) 48 ng and 48 g of ginseng (2,4-pentanyl) iron (III) (manufactured by Aldrich Co., Ltd.) were heated to 160 °C. In the mixed solution, ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 2〇〇g, chloro-16-200923971 sodium (made by Wako Pure Chemical Industries, Ltd.) 291^, ginseng (2,4-pentanedione) Iron (III) (manufactured by Aldrich Co., Ltd.) 25 ng and silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) 2.8 8 g of a mixed solution and ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 20 (^, sodium chloride (Wako Pure Chemical Industries, Ltd.) Manufactured by Industrial Co., Ltd., 2.111^, ginseng (2,4-pentanedione) iron (manufactured by IIIHAldrich Co., Ltd.), 128 ng, and polyvinylpyrrolidone (Mw. 5 5 000, manufactured by Aldrich Co., Ltd.) 3. The solution of lg was dropped for 6 minutes. The dispersion of silver nanowires was obtained by stirring for 3 hours. The obtained silver nanowires were observed by a scanning electron microscope, and the results are as shown in Fig. 5 and Fig. 6. From the results, the silver used in the present example was obtained. The longitudinal length of the nanowire is 20//m or less, and the length in the short axis direction is l〇〇nm or more and 300 nm or less. [Production and evaluation of conductive film] The obtained mixed solution is centrifuged (device name: high-speed cooling centrifuge CR22GII) Hitachi Machine Co., Ltd. made 3 000 Gx 5 minutes), dispersing the residue in a mixture of water and 2-propanol Solution (5 0/5 0 vol%) l〇ml. The solid content concentration in the dispersion is 1.3 wt%. The silver nanofilament dispersion obtained by bar coating is applied to PET film (trade name: COSMOSHINE A4100, manufactured by Toyobo Co., Ltd. , the total light transmittance is 92%), the wet film thickness is 3 /2 m, and the laminate film is dried at 80 ° C for 3 minutes. The PET film with the release layer is attached to the laminate film (trade name: COSMOSHINE K) 1 57 2 'Toyobo Co., Ltd.) superimposes the release layer to contact the conductive layer'. As shown in Fig. 7, the film is wiped with an agate bar by the side of the film with the release layer, and the pressure is applied to the conductive layer. The surface resistance of the film is 5 〇 Ω / □ (device name: -17- 200923971
Loresta EP ’ DIA INSTRUMENTS公司製），全光線透射率及 霧度値各係8 4 6 %及7 . 1 % (裝置名稱：直接讀取霧度計， SUGA試驗機公司製）。 於導電膜施加壓力前，導電層以掃瞄電子顯微鏡觀察之 結果如第8圖’於導電膜施加壓力後之同觀察結果如第9 圖。 <實施例2 > 將實施例1中得之銀奈米絲分散液塗布至濕膜厚6 // m以 外，進行如同實施例1之操作。 得到之薄膜的表面電阻値係1 0 Ω / □，全光線透射率 8 1 . 6 %，霧度値 1 2.5 %。 得到之導電膜的導電層單獨以分光光度計測定透射率’ 結果如第1 0圖。由此結果知，本發明之導電膜透射率的波 長倚賴性低，適用作顯示器之透明電極。 <實施例3 > 將實施例丨中得之銀奈米絲分散液塗布至濕膜厚1 4 μ m 以外，進行如同實施例1之操作。 得到之薄膜的表面電阻値係1.6 Ω / □，全光線透射率 7 7 . 5 %，霧度値 1 5.7 %。 〈實施例4 > 將實施例1中得之銀奈米絲分散液稀釋5倍後’塗布g 濕膜厚6 v m以外，進行如同實施例1之操作。 得到之薄膜的表面電阻値係1 .4 X 1 Ο5 Ω /□’全光線透射率 8 8 · 6 %，霧度値 1 . 5 %。 -18- 200923971 <實施例5> 於實施例1中得之導電膜上噴塗聚酯樹脂（商品名 VYLON UR-4800 >東洋紡公司製）至膜厚達10nm。 以得到之薄膜供作交切試驗（ns K 5 400)，爲1 00/ 1 00，不 見剝落。 得到之導電膜的表面電阻値係5 3 0 Ω /□，全光線透射率 8 4 . 1 %，霧度値 6.3 %。 <實施例6 > 實施例1中得之混合溶液經離心分離（裝置名稱：高速冷 卻離心機CR22GII，日立工機公司製，3000GX5分鐘），將 殘渣分散於2 -丙醇1 0 m 1。分散液中固體成分濃度爲1. 5 w t %。 於得到之銀奈米絲分散液添加聚乙烯醇縮丁醛樹脂（商 品名MOWITAL B60H，KSE公司製）至固體成分中銀奈米絲 之濃度爲 3 7.5質量％，塗布於 P E T薄膜（商品名·· COSMOSHINE A4100，東洋紡公司製，全光線透射率92%) 上至濕膜厚30/zm，於80°C乾燥3分鐘得積層膜。 得到之積層膜使用壓合積層機（商品名 MH-300型， MCK(股）製）以線速 25mm/分鐘，線壓 30kgf/cm(29.4kPa. m) 壓合得導電膜。 得到之導電膜的表面電阻値係30 Ω /□，全光線透射率 74.5% > 霧度値 22.5%。 以得到之薄膜供作交切試驗（Π S K 5 4 0 0)，爲1 〇 〇 Π 0 0，不 見剝落。 <實施例7 > -19- 200923971 添加至固體成分中銀奈米絲之濃度爲5 4.5質量％以外， 進行如同實施例6之操作。 胃@ &透明導電膜的表面電阻値係22 Ω /□，全光線透射 率8 3 · 6 % ’霧度値1 3.0 %。 以得到之薄膜供作交切試驗UIS K5400),爲1 00/1 00，不 見剝落。 <實施例8 > 方令實施例6中得之銀奈米絲分散液添加聚乙烯吡咯烷酮 iMw· 55 000 ’ Aidrich公司製）至固體成分中銀奈米絲之濃度 爲 54·5質量％，塗布於 PET薄膜（商品名：COSMOSHINE A4 10Q ’東洋紡公司製，全光線透射率92%)上至濕膜厚3〇 # m ’於80°C乾燥3分鐘得積層膜。 得到之積層膜使用壓合積層機（商品名 MH- 3 00型， MCK(股）製）以線速 25mm/分鐘，線壓 30kgf/cm(29.4kPa. m) 壓合得導電膜。 得到之透明導電膜的表面電阻値係2 8 Ω /□，全光線透射 率78.3%’霧度値20.6%。 以得到之薄膜供作交切試驗UIS K5 400)，爲1 00/ 1 00，不 見剝落。 <實施例9 > 於實施例6中得之銀奈米絲分散液添加乙酸丁酸纖維素 (商品名 CAB-551-0.2, EASTMAN CHEMICAL 公司製）至固體 成分中銀奈米絲之濃度爲80質量％，塗布於PET薄膜（商品 名：COSMOSHINE A4100，東洋紡公司製，全光線透射率 -20- 200923971 92%)上至濕膜厚30 # m，於8(TC乾燥3分鐘得積層膜。 得到之積層膜使用壓合積層機（商品名 MH- 3 00型， MCK(股）製）以線速 25mm/分鐘，線壓 10kgf/cm(9.8kPa. m) 壓合得透明導電膜。 得到之透明導電膜的表面電阻値係1 3〇 Ω /□，全光線透 射率7 2 · 6 %，霧度値2 5 . 1 %。 以得到之薄膜供作交切試驗（Π S K 5 4 0 0 )，爲1 0 0 / 1 0 0，不 見剝落。 \ <實施例1 0 > 於實施例6中得之銀奈米絲分散液添加聚N -乙烯乙醯胺 (商品名PNVA GE191-000，昭和電工公司製）至固體成分中 銀奈米絲之濃度爲54.5質量％，塗布於PET薄膜（商品名： COSMOSHINE A4100 -東洋紡公司製，全光線透射率9 2 %) 上至濕膜厚3 0 μ m，於8 0 °C乾燥3分鐘得積層膜。 得到之積層膜使用壓合積層機（商品名 MH- 300型 V MCK(股）製）以線速 25mm/分鐘，線壓 1 0 k g f / c m (9 · 8 k P a · m) 壓合得透明導電膜。 得到之透明導電膜的表面電阻値係1 40 Ω /□，全光線透 射率73.7%，霧度値26.1%。 <實施例1 1 > [碳奈米管分散液之調製] 於2L分離式燒瓶混合經電弧放電法得之粗單層碳奈米 管 10g、蒸餾水 100ml及 69%硝酸（和光純藥工業公司 製）90 0ml後，於85 °C攪拌48小時。 -21 - 200923971 將反應液冷卻至室溫後，經離心分離（裝置名稱：高速冷 卻離心機CR22GII，日立工機公司製，4 8 000Gx20分鐘）回 收殘渣，並水洗。 於2L之水投入得到之單層碳奈米管，以錐型超音波照射 機（裝置名稱：ULTRASONIC HOMOGENIZER MODEL UH-600SR，SMT公司製）照射超音波5分鐘。 將反應液離心分離（裝置名稱：高速冷卻離心機 / CR22GII，日立工機公司製，1 0000Gx60分鐘），回收上澄液， 爲粗純化液。 於粗純化液（2L)投入聚乙二醇一辛苯醚（東京化成公司 製）1 g及氫氧化鈉0.1 g，供作交流過濾。所使用之中空絲膜 模組係孔徑 200nm，膜面積 5 800cm2者（SPECTRUM公司 製），洗淨液係於0.005M氫氧化鈉水溶液以成爲〇.2wt%的 方式添加聚乙二醇一辛苯醚之弱鹼性水溶液。以20.0L之 洗淨液將粗純化液洗淨，得純化單層碳奈米管之水分散液。 I 於得到之水分散液添加等量之2 -丙醇使凝集後’離心分 離（48000Gx20分鐘）回收純化單層碳奈米管。 得到之純化單層碳奈米管與氫氧化富勒烯（商品名nan〇m spectra D-100，Frontier Carbon 公司製）150mg、氫氧化鈉 1 5 m g、水5 0 0 g及2 -丙醇5 0 0 g混合’以錐型超首波照射機 照射超音波3分鐘。 得到之分散液經離心分離（1 8 8 0 0 G X 2 0分鐘）’回收上澄 液，爲純化單層碳奈米管分散液。 得到之純化單層碳奈米管分散液的單層碳奈米管濃度係 -22- 200923971 5 3 0 p p m。 [導電膜之製作與評估] 混合實施例1中得之銀奈米絲分散液1 .0 m 1與單層碳奈 米管分散液2.0mL·棒塗於PET薄膜（商品名：COSMOSHINE A4100東洋紡公司製）上至濕膜厚27//m，於80°C乾燥3分 鐘。 以甲醇洗淨塗布面，再於80°C乾燥3分鐘。 f- 於積層膜上疊合附有脫模層之 PET薄膜（商品名： COSMOSHINE K1572，東洋紡公司製）使脫模層接觸導電 層，如第7圖由附有脫模層之PET薄膜側以瑪瑙製乳棒擦 拭，於導電層面施以壓力。 含於導電層之金屬奈米絲的質量係碳奈米管質量之12 倍，得到之導電膜的表面電阻値係20 Ω /□，全光線透射率 75.7%，霧度値12.4%。得到之薄膜的表面以電子顯微鏡觀 察，結果如第1 1圖。可確認金屬奈米絲間形成有碳奈米管 構成之配線。 <比較例1 > 實施例1中得之積層體於壓合前欲予測定表面電阻値時 因係1.0χ10όΩ /□以上（〇_ L.) ’無法測定。全光線透射率 8 5 . 1 %，霧度値 5 . 6 %。 實施例1〜1 1以及比較例1之結果如表1。 -23- 200923971 表1 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 表面電阻値(Ω/D) 500 10 1.6 140000 530 30 全光線透射率(％) 84.6 81.6 77.5 88.6 84.1 74.5 霧度値(％) 7.1 12.5 15.7 1.5 6.3 22.5 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 表面電阻値(Ω〇) 22 28 130 140 20 0. L. 全光線透射率(％) 83.6 78.3 72.6 73.7 75.7 85.1 霧度値(％) 13.0 20.6 25.1 26.1 12.4 5.6 由此可知，較之僅具有單以直線狀金屬奈米絲塗布的導 電層之導電膜，本發明的導電膜之導電性顯注地提升，透 光性、導電性俱優。 <實施例1 2 > 於 1L 三口燒瓶饋入乙二醇（和光純藥工業公司 製）333.9g、氯化鈉（和光純藥工業公司製）48ng及參（2,4-戊 二酮根）鐵（III)(Aldrich公司製）41ng，加熱至！60°C。 於該混合溶液中以乙二醇（和光純藥工業公司製）20〇g、氯 化鈉（和光純藥工業公司製）29ng、參（2,4-戊二酮根）鐵 (111) (A1 d r 1 c h公司製）2 5 n g及硝酸銀（和光純藥工業公司 製）2.8 8g構成之混合溶液與乙二醇（和光純藥工業公司 製）200g、氯化鈉（和光純藥工業公司製）2.lmS、參（2,4_戊二 酮根）鐵（III)(Aldrich公司製）128ng及聚乙烯啦略院酮（Mw. -24- 200923971 55000，Aldrich公司製）3.1g構成之溶液經6分鐘滴入’攪 拌3小時得粗銀奈米絲。 得到之混合溶液經離心分離（裝置名稱：高速冷卻離心機 CR22GII，日立工機公司製’ 3000Gx5分鐘），將殘渣分散於 2 -丙醇，得固體成分濃度3 w t %之銀奈米絲分散液。 得到之銀奈米絲以掃瞄電子顯微鏡觀察的結果如第5及 6圖。由此結果知，用於本實施例之銀奈米絲縱向長度係3 以上30#m以下。 棒塗得到之銀奈米絲分散液於 PET薄膜（商品名： COSMOSHINEA4100，東洋紡公司製）上。於80°C乾燥3分 鐘得積層體。 此時的導電膜其表面電阻値係1 〇〇〇 Ω / □(裝置名稱： LorestaEP，DIA INSTRUMENTS公司製），全光線透射率及 霧度値各係77%及19% (裝置名稱：直接讀取霧度計，SUG A 試驗機公司製）。 浸泡於硝酸銀（和光純藥工業公司製）10mg、25%氨水（和 光純藥工業公司製）6 0 m g、3 6 %甲醛水溶液（和光純藥工業公 司製）100mg及水l〇〇g構成之無電解銀鍍液1分鐘後，以水 洗淨表面，於8 0 °C乾燥3分鐘得導電膜。 得到之導電膜以掃瞄電子顯微鏡觀察之結果如第12 圖。由此結果可確認，銀奈米絲的交點部分已經電鍍而變 粗。 得到之導電膜的表面電阻値係20 Ω / □(裝置名稱：The total light transmittance and haze of the Loresta EP' DIA INSTRUMENTS company are 864% and 7.1% (device name: direct reading haze meter, manufactured by SUGA Testing Machine Co., Ltd.). Before the pressure is applied to the conductive film, the result of observation of the conductive layer by a scanning electron microscope is as shown in Fig. 8 after the pressure is applied to the conductive film as shown in Fig. 8. <Example 2> The silver nanowire dispersion obtained in Example 1 was applied to a wet film thickness of 6 // m, and the operation as in Example 1 was carried out. The surface resistance of the obtained film was 10 Ω / □, the total light transmittance was 81.6 %, and the haze was 12.5 %. The conductive layer of the obtained conductive film was measured by a spectrophotometer alone. The result is shown in Fig. 10. From this result, it is understood that the conductive film of the present invention has low wavelength dependence and is suitable as a transparent electrode of a display. <Example 3> The operation of Example 1 was carried out by applying the silver nanofilament dispersion obtained in Example 至 to a wet film thickness of 14 μm. The surface resistance of the obtained film was 1.6 Ω / □, the total light transmittance was 77.5 %, and the haze was 5.7 %. <Example 4> The operation as in Example 1 was carried out except that the silver nanofilament dispersion obtained in Example 1 was diluted 5 times and then coated with a wet film thickness of 6 v m. The surface resistance of the obtained film was 11·4 X 1 Ο5 Ω /□' total light transmittance 8 8 · 6 %, haze 値 1.5%. -18-200923971 <Example 5> A polyester resin (trade name: VYLON UR-4800 > manufactured by Toyobo Co., Ltd.) was sprayed on the conductive film obtained in Example 1 to a film thickness of 10 nm. The obtained film was used for the cross-cut test (ns K 5 400), which was 1 00 / 1 00, and no peeling was observed. The surface resistance of the obtained conductive film was 530 Ω / □, the total light transmittance was 84. 1%, and the haze was 6.3 %. <Example 6> The mixed solution obtained in Example 1 was centrifuged (device name: high-speed cooling centrifuge CR22GII, manufactured by Hitachi Kogyo Co., Ltd., 3000 GX for 5 minutes), and the residue was dispersed in 2 -propanol 10 m 1 . 5 重量。 The solid concentration of the dispersion was 1. 5 w t %. A polyvinyl butyral resin (trade name: MOWITAL B60H, manufactured by KSE) was added to the obtained silver nanofilament dispersion to a concentration of 37.5 mass% of silver nanowire in a solid component, and it was applied to a PET film (trade name). · COSMOSHINE A4100, manufactured by Toyobo Co., Ltd., with a total light transmittance of 92%). The film was applied to a wet film thickness of 30/zm and dried at 80 ° C for 3 minutes. The obtained laminated film was pressure-bonded to obtain a conductive film by a press laminator (trade name: MH-300, manufactured by MCK Co., Ltd.) at a line speed of 25 mm/min and a linear pressure of 30 kgf/cm (29.4 kPa.m). The surface resistance of the obtained conductive film was 30 Ω / □, the total light transmittance was 74.5% > haze 値 22.5%. The obtained film was used for the cross-cut test (Π S K 5 4 0 0), which was 1 〇 〇 Π 0 0, and no peeling was observed. <Example 7> -19-200923971 The operation as in Example 6 was carried out except that the concentration of silver nanowire in the solid content was 5 4.5% by mass. The surface resistance of the stomach @ & transparent conductive film is 22 Ω / □, and the total light transmittance is 8 3 · 6 % 'haze 値 1 3.0 %. The obtained film was used for the cross-cut test UIS K5400), which was 1 00/1 00, and no peeling was observed. <Example 8> The silver nanofilament dispersion obtained in Example 6 was added with polyvinylpyrrolidone iMw·55 000 'Aidrich Co., Ltd.) to a concentration of 54.5% by mass of the silver nanowire in the solid content. It was applied to a PET film (trade name: COSMOSHINE A4 10Q 'Toyobo Co., Ltd., total light transmittance 92%) up to a wet film thickness of 3 〇 #m ' at 80 ° C for 3 minutes to obtain a laminate film. The obtained laminated film was pressure-bonded to obtain a conductive film at a line speed of 25 mm/min and a linear pressure of 30 kgf/cm (29.4 kPa.m) using a press laminator (product name: MH-300 type, manufactured by MCK Co., Ltd.). The surface resistivity of the obtained transparent conductive film was 28 Ω / □, and the total light transmittance was 78.3% 'haze 値 20.6%. The obtained film was used for the cross-cut test UIS K5 400), which was 1 00/1 00, and no peeling was observed. <Example 9> The silver nanofilament dispersion obtained in Example 6 was added with cellulose acetate butyrate (trade name: CAB-551-0.2, manufactured by EASTMAN CHEMICAL Co., Ltd.) to a concentration of silver nanowire in the solid content. 80% by mass, coated on a PET film (trade name: COSMOSHINE A4100, manufactured by Toyobo Co., Ltd., total light transmittance -20-200923971 92%) up to a wet film thickness of 30 #m, at 8 (TC dried for 3 minutes to obtain a laminated film. The obtained laminated film was pressure-bonded to obtain a transparent conductive film at a line speed of 25 mm/min and a linear pressure of 10 kgf/cm (9.8 kPa.m) using a press laminator (trade name: MH-300 type, manufactured by MCK Co., Ltd.). The surface resistance of the transparent conductive film is 1 3 Ω / □, the total light transmittance is 7 2 · 6 %, and the haze is 25.1 %. The obtained film is used for the cross-cut test (Π SK 5 4 0 0), 1 0 0 / 1 0 0, no peeling was observed. \ <Example 1 0 > The silver nanofilament dispersion obtained in Example 6 was added with poly N-ethyleneacetamide (trade name PNVA GE191 -000, manufactured by Showa Denko Co., Ltd.) to a solid content of silver nemesis at a concentration of 54.5 mass%, coated on a PET film (trade name: COSMOSHINE A4100) -Toyobo Co., Ltd., total light transmittance (92%) Up to a wet film thickness of 30 μm, dried at 80 °C for 3 minutes to obtain a laminate film. The laminated film obtained was a press laminator (trade name MH-300). The type V MCK (manufactured by the company) is pressed at a line speed of 25 mm/min and a linear pressure of 10 kgf / cm (9 · 8 k P a · m) to obtain a transparent conductive film. The surface resistance of the obtained transparent conductive film is 1 40 Ω / □, total light transmittance 73.7%, haze 値 26.1%. <Example 1 1 > [Modification of carbon nanotube dispersion] Mixed by arc discharge method in 2L separation flask 10 g of a layer of carbon nanotubes, 100 ml of distilled water, and 90% of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred at 85 ° C for 48 hours. -21 - 200923971 After cooling the reaction solution to room temperature, it was centrifuged ( Device name: CR22GII high-speed cooling centrifuge, manufactured by Hitachi Engineering Co., Ltd., 4 8 000 Gx 20 minutes) Residues were recovered and washed with water. The single-layer carbon nanotubes were charged in 2 L of water to make a cone-shaped ultrasonic irradiation machine (device name) :ULTRASONIC HOMOGENIZER MODEL UH-600SR, manufactured by SMT Co., Ltd.) Irradiated for 5 minutes. Centrifugation (apparatus name: high speed cooling centrifuge / CR22GII, Hitachi Koki Co., Ltd., 1 0000Gx60 min), the supernatant is recovered as crude purified liquid. To the crude purified solution (2 L), 1 g of polyethylene glycol monooctyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 g of sodium hydroxide were placed for AC filtration. The hollow fiber membrane module used is a membrane having a pore diameter of 200 nm and a membrane area of 5 800 cm 2 (manufactured by SPECTRUM), and the washing liquid is added to a 0.005 M aqueous sodium hydroxide solution to form polyethylene glycol monooctylbenzene in a manner of 0.2 wt%. A weakly basic aqueous solution of ether. The crude purified solution was washed with a 20.0 L of a washing solution to obtain an aqueous dispersion of a purified single-layer carbon nanotube. I An equivalent amount of 2-propanol was added to the obtained aqueous dispersion to recover the purified single-layer carbon nanotubes by centrifugation (48000 Gx for 20 minutes) after agglutination. The obtained purified single-layer carbon nanotube and the fullerene hydroxide (trade name: nan〇m spectra D-100, manufactured by Frontier Carbon Co., Ltd.) 150 mg, sodium hydroxide 15 mg, water 500 g, and 2-propanol 5 0 0 g mixing 'irradiation with a cone-shaped super first wave illuminator for 3 minutes. The obtained dispersion was subjected to centrifugation (1 8 8000 G X 20 minutes) to recover the supernatant, which was a purified single-layer carbon nanotube dispersion. The obtained single-layer carbon nanotube concentration of the purified single-layer carbon nanotube dispersion is -22-200923971 5 3 0 p p m. [Preparation and Evaluation of Conductive Film] The silver nanofilament dispersion obtained in Example 1 was mixed with a 1.0 m m 1 and a single-layer carbon nanotube dispersion 2.0 mL·rod coated on a PET film (trade name: COSMOSHINE A4100 Toyobo The company made a wet film thickness of 27/m and dried at 80 ° C for 3 minutes. The coated surface was washed with methanol and dried at 80 ° C for 3 minutes. F- A PET film (trade name: COSMOSHINE K1572, manufactured by Toyobo Co., Ltd.) with a release layer was laminated on the laminate film to bring the release layer into contact with the conductive layer, as shown in Fig. 7 from the side of the PET film with the release layer. Wipe the agate bar and apply pressure on the conductive surface. The mass of the metal nanowire contained in the conductive layer is 12 times the mass of the carbon nanotube, and the surface resistance of the conductive film obtained is 20 Ω / □, the total light transmittance is 75.7%, and the haze is 12.4%. The surface of the obtained film was observed by an electron microscope, and the results are as shown in Fig. 11. It was confirmed that wirings made of carbon nanotubes were formed between the metal nanowires. <Comparative Example 1 > When the laminated body obtained in Example 1 was to be subjected to measurement of surface resistance 压 before press-bonding, it was impossible to measure by 1.0 χ 10 ό Ω / □ or more (〇 _ L.). The total light transmittance is 8 5 . 1 %, and the haze is 5.6 %. The results of Examples 1 to 1 1 and Comparative Example 1 are shown in Table 1. -23- 200923971 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Surface resistance 値 (Ω/D) 500 10 1.6 140000 530 30 Total light transmittance (%) 84.6 81.6 77.5 88.6 84.1 74.5 Haze 値 (%) 7.1 12.5 15.7 1.5 6.3 22.5 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Surface resistance 値 (Ω〇) 22 28 130 140 20 0. L. Total light transmission Rate (%) 83.6 78.3 72.6 73.7 75.7 85.1 Haze 値 (%) 13.0 20.6 25.1 26.1 12.4 5.6 It is understood that the conductive film of the present invention is more conductive than the conductive film having only a conductive layer coated with a linear metal nanowire. The conductivity of the film is markedly improved, and the light transmittance and conductivity are excellent. <Example 1 2> Into a 1 L three-necked flask, 333.9 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 48 ng, and ginseng (2,4-pentanedione) were fed. Root) Iron (III) (made by Aldrich) 41ng, heated to! 60 ° C. In the mixed solution, 20 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 29 ng, ginseng (2,4-pentanedione) iron (111) ( A1 dr 1 ch company made 2 5 ng and silver nitrate (made by Wako Pure Chemical Industries, Ltd.) 2.8 8g of a mixed solution and ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 200g, sodium chloride (made by Wako Pure Chemical Industries, Ltd.) ) 2.lmS, ginseng (2,4-pentanedione) iron (III) (made by Aldrich), 128 ng, and polyethylene lysone (Mw. -24-200923971 55000, manufactured by Aldrich) 3.1 g The solution was added dropwise for 6 minutes and stirred for 3 hours to obtain crude silver nanowire. The obtained mixed solution was centrifuged (device name: high-speed cooling centrifuge CR22GII, manufactured by Hitachi Kogyo Co., Ltd., 3000 Gx for 5 minutes), and the residue was dispersed in 2-propanol to obtain a silver nanowire dispersion having a solid concentration of 3 wt%. . The obtained silver nanowires were observed by a scanning electron microscope as shown in Figs. 5 and 6. From this result, it is understood that the longitudinal length of the silver nanowire used in the present embodiment is 3 or more and 30 #m or less. The silver nanofilament dispersion obtained by the bar coating was applied to a PET film (trade name: COSMOSHINEA 4100, manufactured by Toyobo Co., Ltd.). The laminate was dried at 80 ° C for 3 minutes. At this time, the surface resistance of the conductive film was 1 〇〇〇Ω / □ (device name: LorestaEP, manufactured by DIA INSTRUMENTS), and the total light transmittance and haze were 77% and 19%, respectively (device name: direct reading) Take the haze meter, manufactured by SUG A Testing Machine Co., Ltd.). Soaked in silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) 10 mg, 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), 60 mg, 3 6 % formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mg, and water l〇〇g. After electroless silver plating solution for 1 minute, the surface was washed with water and dried at 80 ° C for 3 minutes to obtain a conductive film. The obtained conductive film was observed by a scanning electron microscope as shown in Fig. 12. From this result, it was confirmed that the intersection portion of the silver nanowire has been plated to become thick. The surface resistance of the obtained conductive film is 20 Ω / □ (device name:
Loresta EP ’ DIA INSTRUMENTS公司製），全光線透射率及 -25- 200923971 霧度値各係70 %及32 % (裝置名稱：直接讀取霧度計，SUGA 試驗機公司製）。結果如表2。 表2 表面電阻値 透射率 霧度 (Ω〇 (%) (%) 電鍍前 1000 77 19 電鍍後 20 70 32 f'N 由實施例之結果知，由於電鍍，表面電阻値大幅降低； 因此，本發明之導電膜可得良好之導電性及透射率。 【圖式簡單說明】 第1圖係用於本發明之層構造的一例之圖。 第2圖係用於本發明之層構造的一例之圖。 第3圖係用於本發明之層構造的一例之圖。 第4圖係用於本發明之層構造的一例之圖。 第5圖係實施例1中得之銀奈米絲的掃瞄電子顯微鏡觀 I /察結果。 第6圖係實施例1中得之銀奈米絲的掃瞄電子顯微鏡觀 察結果。 第7圖係實施例1中施行之加壓方法的示意圖。 第8圖係實施例1中於導電層施加壓力前的掃瞄電子顯 微鏡觀察結果。 第9圖係實施例1中於導電層施加壓力後的掃瞄電子顯 微鏡觀察結果。 第1 0圖係實施例2中得之導電層的分光透射率結果圖。 -26- 200923971 第1 1圖係實施例6中得之導電膜的掃瞄電子顯微鏡觀察 結果。 第1 2圖係實施例7中得之導電膜的掃瞄電子顯微鏡觀察 結果。 【主要元件符號說明】 te 。Loresta EP' DIA INSTRUMENTS, Inc., full light transmittance and -25- 200923971 haze 70 70% and 32% each (device name: direct reading haze meter, manufactured by SUGA Testing Machine Co., Ltd.). The results are shown in Table 2. Table 2 Surface resistance 値 Transmittance haze (Ω〇(%) (%) 1000 77 before plating 20 70 32 f'N after plating. It is known from the results of the examples that the surface resistance 値 is greatly reduced due to electroplating; therefore, this The conductive film of the invention can provide good conductivity and transmittance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a layer structure of the present invention. Fig. 2 is an example of a layer structure used in the present invention. Fig. 3 is a view showing an example of a layer structure used in the present invention. Fig. 4 is a view showing an example of a layer structure used in the present invention. Fig. 5 is a view showing a silver nanowire obtained in Example 1. The aim of the electron microscope observation I / inspection results. Fig. 6 is a scanning electron microscope observation result of the silver nanowire obtained in the embodiment 1. Fig. 7 is a schematic view showing the pressing method performed in the embodiment 1. The results of scanning electron microscope observation before applying pressure to the conductive layer in Example 1. Fig. 9 is a scanning electron microscope observation result after applying pressure to the conductive layer in Example 1. Fig. 10 is a second embodiment The result of the spectral transmittance of the conductive layer obtained. -26- 200923971 The scanning electron microscope observation results of the conductive film obtained in Example 6 are shown in Fig. 2 as a scanning electron microscope observation of the conductive film obtained in Example 7. [Description of main component symbols] te .
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