201043470 六、發明說明： 【發明所屬之技術領域】 本發明係關於在透明塑膠薄膜所構成的基材上，將高 ί斤射率層、低折射率層及透明導電性薄膜層依此順序積層 之透明導電性薄膜之發明。特別是關於作爲靜電電容 式觸控面板等經圖案化之電極薄膜來使用時，由於表面電 阻値低、觸控面板可以大型化、且有透明導電性薄膜層的 〇 部分和被除去的部分之光學特性差異小，因此可提高目視 辨認性之透明導電性薄膜。 【先前技術】 在透明塑膠薄膜所構成的基材上，積層有透明且電阻 小的薄膜而成之透明導電性薄膜，係廣泛地被使用在利用 其導電性之用途，例如液晶顯示器或電激發光（有時略記EL) 顯示器等平面顯示器、或電阻膜式觸控面板之透明電極 等，電氣、電子領域之用途。 〇 w 近年來，靜電電容式觸控面板被搭載於攜帶型電話、 攜帶型音樂終端等行動機器的案例逐漸增加。這種靜電電 容式觸控面板，具有在經圖案化之導體上積層介電質層之 構成，並且藉由以手指等觸碰的方式，經由人體的靜電電 容而被接地。此時，圖形電極和接地點之間的電阻値產生 變化，辨識位置輸入。但是使用以往的透明導電性薄膜時， 有透明導電性薄膜層的部分和被除去的部分之光學特性差 異大，因此圖形顯著’當配置在液晶顯示器等顯示體的前 201043470 面時，會有目視辨認性降低的問題。 爲了提升透明導電性薄膜的透過率或色調，而提出積 層反射防止加工等中所使用的折射率相異之層，利用光的 干涉之方法。亦即，提出在透明導電性薄膜層和基材薄膜 之間’設置折射率相異之層，利用光學干涉的方法（專利文 獻 1~3)。 但是，該等專利文獻1 ~3記載的透明導電性薄膜，係 ^ 可改善作爲透明導電性薄膜之目視辨認性，但未經考慮在 將透明導電性薄膜層圖案化時，減少有透明導電性薄膜的 部分和沒有的部分之光學特性差異的問題，因此經圖案化 的部位顯著。 又，近年來，搭載於攜帶型電話等行動機器之觸控面 板，被期望大型化。特別是傾向靜電電容的透明導電性薄 膜，係如上述般地圖案化而被使用，因此若觸控面板大型 化，則各圖案電極的配線電阻將變大，動作速度就降低了。 〇 因此’期望有表面電阻値低、上述圖形不顯著之透明導電 性薄膜。 【專利文獻1】日本特開平1 1 -286066號公報 【專利文獻2】日本特許第3626624號公報 【專利文獻3】日本特開2006-346878號公報 【發明內容】 〔發明所欲解決之課題〕 亦即’本發明之目的爲鑑於上述以往的問題點，而提 201043470 供透明導電性積層薄膜，其係藉由表面電阻値低、有透明 導電性薄膜層的部分和被除去的部分之光學特性差異變小 的方式，使使用在液晶顯示器等時，目視辨認性良好，並 且圖形不顯著。 〔解決課題之手段〕 本發明係鑑於如上述之狀況而硏發者，能解決上述課 題之透明導電性積層，係由以下之構成所形成。 0 1. 一種透明導電性積層薄膜，其特徵爲其係在由透明塑膠 薄膜所構成之基材上，將高折射率層、低折射率層及透明 導電性薄膜層依此順序積層而成之積層薄膜，高折射率層 之折射率爲1.70~2.50，膜厚在4~20nm之範圍，低折射率 層之折射率爲1.30〜1.60，膜厚在20〜50nm之範圍，透明導 電性薄膜層表面之表面電阻値爲50〜300 Ω /□，膜厚爲 10〜30nm 。 2 .如前述1記載之透明導電性積層薄膜，其中透明導電性 〇 薄膜層之比電阻爲1.0~6.0χ10_4Ω . cm。 3, 如前述1或2記載之之透明導電性積層薄膜，其中透明 導電性薄膜層係由平均結晶粒徑爲10~1000nm、且非晶質 部對結晶質部之比爲0.00〜0.90所構成之金屬氧化物薄膜 所構成。 4. 如前述3記載之之透明導電性積層薄膜，其中透明導電 性薄膜層係氧化錫之含有率爲〇.5~8質量％之銦·錫複合氧 化物。 201043470 5. —種透明導電性積層薄膜，其特徵爲在將如前述1至4 中任一項記載之透明導電性積層薄膜的透明導電性薄膜 層，經圖案化後之透明導電性積層薄膜的透明導電性薄膜 層側，積層有折射率爲1.40~1.70的介電質層。 6. —種透明導電性積層薄膜，其特徵爲具有如前述5記載 之透明導電性積層薄膜之圖案化所形成之透明導電性薄膜 層的部分和沒有的部分之光學特性差異，係滿足下述（1)式 及（2)式， 0各 1 T1 - TO 1 ^ 1.0 (1) 0^ I bl - b0 1 ^ 1.0 (2) (T1:有透明導電性薄膜層的部分之薄膜的全部光線透過 率， bl:有透明導電性薄膜層的部分之薄膜的色彩b値， T0 :沒有透明導電性薄膜層的部分之薄膜的全部光線 透過率， G b0:沒有透明導電性薄膜層的部分之薄膜的色彩b値） 〔發明之功效〕 本發明之透明導電性薄膜係於透明塑膠薄膜所構成的 基材上，具有以高折射率層、低折射率層及透明導電性薄 膜層之順序積層而成的構成，並且在將透明導電性薄膜層 圖案化時，有透明導電性薄膜層的部分和沒有的部分之光 學特性差異小，因此即使配置在液晶顯示器等顯示體的前 面，透明導電性薄膜層的圖形亦不顯著，所以可抑制目視 201043470 辨認性之降低。又，表面電阻値低、能對應觸.控面板大型 化。 【實施方式】 本發明之透明導電性薄膜係於透明塑膠薄膜所構成的 基材上，具有將高折射率層、低折射率層及透明導電性薄 膜層依此順序積層而成之構成。 進一步，透明導電性積層薄膜特徵爲，在將上述透明 0 導電性積層薄膜的透明導電性薄膜層，在經圖案化後之透 明導電性積層薄膜的透明導電性薄膜層側，積層有介電質 層。 以下，依各層別詳細地說明。 (透明塑膠薄膜所構成之基材） 本發明中使用的透明塑膠薄膜所構成的基材，係將有 機高分子以薄膜狀熔融壓出或溶液壓出，成形爲薄膜狀， 並且因應必要朝長度方向及/或寬度方向施行延伸、熱固 〇 定、熱鬆弛處理之薄膜。作爲有機高分子，可舉出聚乙烯、 聚丙烯、聚對苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、 聚對苯二甲酸二丙酯、耐綸6、耐綸4、耐綸66、耐綸12、 聚醯亞胺、聚醯胺醯亞胺、聚醚硫、聚醚醚酮、聚碳酸酯、 聚芳酯、丙酸纖維素、聚氯乙烯、聚偏二氯乙烯、聚乙烯 醇、聚醚醯亞胺、聚苯硫醚、聚苯醚、聚苯乙烯、間規聚 苯乙烯、降冰片烯系聚合物等。 該等有機高分子之中，聚對苯二甲酸乙二酯、聚對苯 201043470 二甲酸二丙酯、聚-2,6-萘二甲酸乙二酯、間規聚苯乙烯、 降冰片烯系聚合物、聚碳酸酯、聚芳酯等較適合。且，該 等有機高分子可以和其他有機聚合物的單體少量共聚合， 混合其他有機高分子亦可。 本發明中使用的透明塑膠薄膜所構成的基材之厚度， 爲10~3 00 /zm較佳，更佳爲20〜15Q/zm。塑膠薄膜之厚度 未達10/zm時，機械強度不足，且在透明導電性薄膜的圖 0 案形成步驟中操作困難，因而不佳。另一方面，若厚度超 過3 00 //m，則觸控面板之厚度變成過厚，因而不適用於行 動機器等。 本發明中使用的透明塑膠薄膜所構成的基材只要在無 損於本發明之目的之範圍內，對前述薄膜施行電暈放電處 理、輝光放電處理、火燄處理、紫外線照射處理、電子束 照射處理、臭氧處理等表面活性化處理亦可。 又’在本發明使用的透明塑膠薄膜所構成之基材，以 w 提闻與高折射率層之密合性、賦予耐藥品性、防止寡聚物 等低分子量物之析出爲目的，亦可設置以硬化型樹脂爲主 要構成成分之硬化物層。 前述硬化型樹脂只要是藉由加熱、紫外線照射、電子 束照射等能量施加而硬化之樹脂，則無特別限定，可舉出 聚矽氧樹脂、丙烯酸樹脂、甲基丙烯酸酯樹脂、環氧樹脂、 三聚氰胺樹脂、聚酯樹脂、胺基甲酸酯樹脂等。從生產性 之觀點而言，以紫外線硬化型樹脂爲主成分之硬化型樹脂 201043470 爲佳。 作爲這種紫外線硬化型樹脂，例如可舉出如多元醇之 丙烯酸或甲基丙烯酸酯之多官能性丙烯酸酯樹脂、二異氰 酸酯、多元醇及丙烯酸或甲基丙烯酸之羥基烷基酯等所合 成之多官能性胺基甲酸酯丙烯酸酯樹脂等。因應必要，可 在該等多官能性樹脂加入單官能性單體，例如乙烯吡咯啶 酮、甲基丙烯酸甲酯、苯乙烯等使其共聚合。 0 又，爲了提高高折射率層和硬化物層的附著力，進一 步將硬化物層予以表面處理爲有效。作爲具體方法，可舉 出利用照射輝光放電或電暈放電之放電處理法、增加羰 基、羧基、羥基之方法、利用酸或鹼處理之化學藥品處理 法、增加胺基、羥基、羰基等極性基之方法等。 紫外線硬化型樹脂通常被添加光聚合引發劑而使用。 作爲光聚合引發劑，並可無特別限定地使用吸收紫外線產 生自由基之眾知之化合物，作爲這種光聚合引發劑，例如 ® 可舉出各種苯偶姻類、苯酮類、二苯甲酮類等。相對於紫 外線硬化型樹脂100質量份而言，光聚合引發劑之添加量， 以1~5質量份爲佳。 塗布液中之樹脂成分濃度可以考慮配合塗布法之黏度 等而適當地選擇。例如’塗布液中紫外線硬化型樹脂、光 聚合引發劑之合計量所佔的比例通常爲20~80質量％。且， 在該塗布液中，亦可配合必要添加其他眾知之添加劑，例 如聚矽氧系界面活性劑、氟系界面活性劑等調平劑等。 -10- 201043470 本發明中’經調製之塗布液被塗布於透明塑膠 構成之基材上。對於塗布法並無特別限定，可使用硬 凹版印刷塗布法、逆向輥塗法等習知之方法。 且’硬化物層之厚度爲〇.l~15/zm之範圍較佳 爲0.5~10jam’特佳爲i~8/zm。硬化物層的厚度爲司 β m時，由於無法形成經充分地交聯之構造，因此 性容易降低，也容易引起寡聚物等的低分子量造成 0 性降低。另—方面，硬化物層之厚度爲超過15#m 生產性降低之傾向。 (高折射率層） 本發明可使用的高折射率層之折射率在1.70〜: 範圍，較佳爲1.90〜2.30，更佳爲1.90~ 2.10。若未達 則與低折射率層之折射率差異過小，因此將透明導 膜層圖案化時，難以使有透明導電性薄膜層的部分 的部分之光學特性接近。另一方面，折射率爲超過2 〇 難以使傾斜方向之圖形不顯著，且適合工業方面的 不存在。作爲高折射率層的具體素材，可舉出Ti〇2、 ZrCh、Ta2〇5、ZnO、IiuCh、SnCh 等及該等之複合氧 硫化鋅ZnS。該等之中，從生產性的觀點而言，Zn〇、 SnCh及該等之複合氧化物爲佳。又，爲了對該等氧 硫化物調整折射率，亦可添加任意的氧化物、硫化 高折射率層之膜厚爲4~20nm，較佳爲7〜15nm， 8~13nm。若膜厚爲未達4nm，則成爲不連續之膜， 薄膜所 .塗法、 。更佳 t 達 0 · 1 耐藥品 之密合 時，有 2.50 之 1.70 > 電性薄 和沒有 .50 時， 材料也 N b 2 0 5 ' 化物及 ΙΠ2〇 3 ' 化物或 物。 更佳爲 膜的安 -11- 201043470 定性降低。另一方面，若膜厚爲超過2 0nm，則光反射變強， 因此將透明導電性薄膜層圖案化時，難以使有透明導電性 薄膜層的部分和沒有的部分之光學特性接近，當配置在液 晶顯示器等顯示體的前面時，透明導電性薄膜層的圖形顯 著，目視辨認性降低。但是，與其任意地改變高折射率層 的折射率和膜厚，不如將光學膜厚（折射率X膜厚）控制成一 定爲佳。 0 作爲本發明中的高折射率層之成膜方法，己知有真空 蒸鍍法、濺鍍法、CVD法、離子電鍍法、噴霧法等，可配 合需要之膜厚適當地使用前述方法，但是從減少膜厚不均 的觀點而言，以濺鍍法爲佳。 濺鍍法中，一般有從金屬標靶導入反應性氣體製作金 屬氧化物之反應性濺鍍法、和從氧化物標靶製作金屬氧化 物之方法。反應性濺鍍法中，存在有成膜速度根據反應性 氣體的流量而急遽地變化之遷移區域。因此爲了抑制膜厚 〇 之不均，使用氧化物標靶爲佳。 (低折射率層） 本發明所使用的低折射率層之折射率爲1.30〜1.60,較 佳爲1.40~1.55，更佳爲1.43~1.50。若折射率爲未達1.30, 則形成多孔之膜，因此會使形成在其上方的透明導電性薄 膜層之電特性降低。另一方面，若折射率爲超過1.60，則 與透明導電性薄膜層之光的干涉變成太弱，因此將透明導 電性薄膜層圖案化時，難以使有透明導電性薄膜層的部分 -12- 201043470 和沒有的部分之光學特性接近，當配置在液晶顯示器等顯 示體的前面時，透明導電性薄膜層的圖形顯著，目視辨認 性降低。 作爲低折射率層之具體素材，可舉出Si〇2、Al2〇3等透 明金屬氧化物及SiCh-Al2〇3等複合金屬氧化物、CuF2、 CeF2、MnF2、MgF2等金屬氟化物及該等之複合氟化物。又， 爲了對該等氧化物或氟化物調整折射率，亦可添加任意的 ^ 氧化物、硫化物。 低折射率層之膜厚爲20~50nm，較佳爲25~45nm，更佳 爲30〜40nm。若超過50nm，則因爲與透明導電性薄膜層之 光的干涉，波長依存性變成太強，因此將透明導電性薄膜 層圖案化時，難以使有透明導電性薄膜層的部分和沒有的 部分之光學特性接近。另一方面，未達2 0nm時，難以引起 與透明導電性薄膜層之光的干涉，而無法提高透過率，因 此將透明導電性薄膜層圖案化時，難以使有透明導電性薄 〇 膜層的部分和沒有的部分之光學特性接近，當配置在液晶 顯示器等顯示體的前面時，透明導電性薄膜層的圖形顯 著，目視辨認性降低。 但是，與其任意地改變低折射率層的折射率和膜厚， 不如將光學膜厚（折射率X膜厚）控制成一定爲佳。 作爲本發明中的低折射率層之成膜方法，已知有真空 蒸鑛法、濺鍍法、CVD法、離子電鍍法、噴霧法等’可配 合需要之膜厚適當地使用前述方法，從減少膜厚不均的觀 -13- 201043470 點而言，以濺鍍法爲佳。一般以濺鍍形成時係使用反應性 DC或AC濺鍍法。爲了提高成膜速度，使用控制反應性氣 體流量之電阻控制以使DC或AC電源的電壓値保持爲一 定，或使用控制反應性氣體流量之電漿放射法以使特定元 素之電漿中的發光強度保持爲一定。 (透明導電性薄膜層） 作爲本發明中的透明導電性薄膜，可舉出氧化銦、氧 ^ 化錫、氧化鋅、銦-錫複合氧化物、錫-銻複合氧化物、鋅_ 鋁複合氧化物、銦-鋅複合氧化物等。該等之中，從環境穩 定性和電路加工性之觀點而言，以銦-錫複合氧化物較適 合。 本發明中，積層透明導電性薄膜層，藉由將透明導電 性積層薄膜的表面電阻値較佳設爲50〜300 Ω /□，更佳設爲 100~250 Ω/□，再更佳設爲100~220 Ω/□的方式，可將透 明導電性積層薄膜使用在畫面尺寸大的觸控面板等。表面 〇 電阻値儘量低較佳。但是，因爲未達5 0 Ω /□，透明導電性 薄膜層的厚度變厚，透明導電性薄膜層之圖形容易顯著， 因而不佳。另一方面，超過3 00 Ω/□時，觸控面板的位置 辨識精確度變差，因而不佳。 透明導電性薄膜的膜厚在10〜30nm之範圍爲佳，更佳 爲12〜25nm。透明導電性薄膜的膜厚爲未達i〇nm時，難以 形成表面平坦之薄膜，而難以獲得良好的導電性。另一方 面，透明導電性薄膜的膜厚爲比30nm更厚時，將透明導電 -14 - 201043470 性薄膜層圖案化時，難以使有透明導電性薄膜層的部分和 沒有的部分之光學特性接近，而會有圖形顯著的情形。 透明導電性薄膜層的比電阻爲1.0x1 (Γ 4Ω · cm以上、 6.0χ1(Γ4Ω · cm 以下較佳。更佳爲 2.0χ10_4Ω · cm~4.0xl0 _ 4Ω · cm以下。若比電阻爲未達1.0χ10_ 4Ω · cm，則透明 導電性薄膜層的著色變大，透明性變成容易降低。另一方 面，若比電阻爲超過6.0χ1(Γ4Ω · cm，則將透明導電性薄 0 膜層圖案化時，配線電阻變大，因而不佳。 本發明之透明導電性薄膜層係結晶質薄膜層爲佳，該 結晶質薄膜層係由平均結晶粒徑爲1〇〜lOOOnm，且相對於 結晶質部的非晶質部之比爲0.00〜0.90所構成。 此處，透明導電膜的平均結晶粒徑之定義如下。 在透過型電子顯微鏡下觀察透明導電膜層時，將具有 多角形狀之範圍者，定義爲結晶粒，並找出結晶粒之面積。 將結晶粒面積除以圓周率π所得之値的平方根，乘以2倍 〇 後之値，作爲結晶粒徑。 針對在透過型電子顯微鏡下，在透明導電膜層被觀察 到的結晶粒，算出全部的結晶粒徑。將全部的結晶粒徑之 平均値作爲平均結晶粒徑。 且，估算相對於結晶質部的非晶質部之比的方法，係 從在透過型電子顯微鏡下觀察時的結晶質部和非晶質部的 面積比算出。 本發明的透明導電膜之平均結晶粒徑爲10~i⑽Qnm。 -15- 201043470 特佳爲20〜800nm，更佳爲3〇~500nm。平均結晶粒徑爲小於 1 Onm時，顯示形成透明導電性薄膜時不易引起結晶核生成 的情形。這種不易引起結晶核生成的透明導電性薄膜，意 味著膜中存在有許多缺陷，並且比電阻不會降低。 另一方面，若結晶粒徑爲超過lOOOnm，則耐折曲性惡 化，因此在將透明導電性薄膜層圖案化時，容易產生龜裂。 本發明之透明導電膜中的非晶質部對於結晶質部之比 ^ 爲0.00~0.90，較佳爲0.00〜0.70，更佳爲0.00〜0.50。若前 Ο 述之比大於0.90，則顯示形成透明導電性薄膜時不易引起 結晶核生成的情形。這種不易引起結晶核生成的透明導電 性薄膜，意味著膜中存在有許多缺陷，並且比電阻不會降 透明導電性薄膜層所含有的氧化錫之含有率爲0.5〜8 質量％爲佳。更佳爲質量％。氧化錫含有率爲未達0.5 質量％時，難以使載體濃度提高。另一方面，氧化錫之含 Ο 有率爲超過8質量％時，在In部位不取代之摻雜物量增 加，且載體移動度因爲雜質散亂而降低，因此難以降低比 電阻。 透明導電性薄膜的層構造可以是單層構造，也可以是 2層以上的積層構造。具有2層以上的積層構造之透明導 電性薄膜的情形，構成各層的前述金屬氧化物可以相同， 也可以相異。 作爲本發明中的透明導電性薄膜之成膜方法，已知有 -16- 201043470 真空蒸鍍法、濺鍍法、CVD法、離子電鍍法、噴塗法等’ 配合需要之膜厚可適當地使用前述方法。 例如濺鍍法的情形，係利用使用氧化物標靶之通常的 濺鍍法、或使用金屬標靶之反應性濺鍍法等。此時’作爲 反應性氣體，可導入氧、氮等、或倂用臭氧添加、電漿照 射、離子輔助等手段。且，在無損本發明之目的之範圍， 亦可於基板施加直流、交流、高頻等偏壓。 0 爲了獲得本發明之比電阻低、結晶質之透明導電性薄 膜層，有以下2種有效方法。 •去除成膜大氣中之水、有機物。 •提高蒸鍍粒子之能量。 首先，說明有關上述（1)之方法。 形成透明導電性薄膜層時，於儘量去除水分或有機物 之雜質的成膜大氣下，由於蒸鍍粒子的能量降低較小，基 板（薄膜）表面容易產生遷移。其結果爲容易產生透明導電 〇 性薄膜中含有結晶之透明導電性薄膜。因此，可獲得平均 結晶粒徑大、且非晶質部對於結晶質部之比爲0.00〜0.90的 結晶質透明導電性薄膜層。 具體而言，水分壓對於成膜大氣的惰性氣體（氬等）之 比爲8.0xl(T4〜3.0xl(T3較佳。作爲具體之達成手段，可舉 出①進行成膜前，充分地除去塑膠薄膜中的水分，②在成 膜空間裝設水分吸附用極冷栗（Cryopump)等爲有效方法。 其中①進行成膜前，爲了充分地除去塑膠薄膜中的水分， -17- 201043470 有效的方式爲一面使塑膠薄膜在真空中移行，一面將塑膠 薄膜加溫。有效的加熱溫度爲25~ 80 °C。作爲加熱方法可舉 出加熱輥、紅外線加熱器等。若未達25 °C，則無法有效地 將塑膠薄膜加熱，若超過80°C，則有對塑膠薄膜造成傷痕、 變形之虞。②作爲在成膜空間設置之適合的水分吸附用極 冷泵，可舉出伯東股份有限公司製POL YC OLD。 爲了使水分壓對於惰性氣體（氬等）之比未達8.0X10—4， 0 對於在成膜室内大量地投入透明塑膠薄膜之裝置，必須有 長時間之真空除去時間，用於使水分壓對於惰性氣體之比 降低，或者需要能力非常高的真空泵，因此經濟方面的實 施困難。另一方面，若水分壓對於成膜大氣的惰性氣體之 比爲超過3.0x1 (Γ 3，則因爲蒸鍍粒子之能量降低，而難以 獲得比電阻低、結晶質之透明導電性薄膜層。 成膜時的基板（薄膜）溫度爲-20~80°C較佳。若超過80 °C，因爲來自薄膜的水、有機氣體等雜質氣體大量地產生， 〇 所以堆積粒子的能量降低，難以獲得比電阻低、結晶質之 透明導電性薄膜。又，在小於-20°C之溫度，透明塑膠薄膜 變脆而不佳。基板溫度可藉由溫調輥等進行調整。 接著，說明有關上述（2)之方法。 形成透明導電性薄膜層時，作爲提高蒸鍍粒子的能量 之方法，可舉出離子輔助法、離子電鍍法等活性化支援法 或高功率脈衝磁控濺鍍法。藉由使用該等方法，可提高蒸 鍍原子的能量，使基板（薄膜）表面容易產生遷移。其結果 •18- 201043470 可獲得在透明導電性薄膜中含有結晶質部、比電 明導電性薄膜。 上述方法中，亦有高功率磁控濺鍍法以置換 源的方式，可使用習知之濺鍍裝置。例如，以高 濺鍍法的成膜條件，係導入氧之後，再導入氬氣 膜壓力設定爲0.1~1.0Pa，以充電電壓400〜1000V 率10〜500Hz、脈衝寬度1〇〜200WS進行放電的方 Q 引起電弧現象，可獲得在透明導電性薄膜中含： 部、比電阻小的透明導電性薄膜。 又，爲了進一步減少比電阻，亦可在成膜後藉 紫外線照射等手段賦予能量。該等能量賦予手段 氧大氣下的加熱處理較適合。 加熱處理溫度在80〜20(TC之範圍較佳。未達 度時，難以引起摻雜物的取代，由於難以提高載 而於進一步降低比電阻方面不夠充分。另一方面， 〇 乞之溫度時，較難維持薄膜的平面性，進一步透 薄膜中的結晶尺寸變成過大，而形成脆的透明導霄 又，作爲加熱處理時間，在0.2~120分之範 進一步在0.5~60分之範圍較佳。未達0.2分時， 在22〇°C左右之高溫進行加熱處理，膜質改善的效 而不佳。另一方面，超過120分之加熱處理時間 合工業方面。 又，進行加熱處理之大氣，係以在事先排氣 阻小的透 濺鍍用電 功率磁控 體，將成 、脈衝頻 式，不會 有結晶質 由加熱、 之中，在 8 0 °C之溫 體濃度， 超過200 明導電性 i性薄膜。 圍較佳。 例如即使 果仍不足 時，不適 ，至 0.2Pa -19- 201043470 以下的壓力之後再塡滿氧的空間進行較佳。此時的壓力爲 大氣壓以下較佳。 (折射率爲1.40~1.70之介電質層（保護層）） 本發明中，折射率爲1.40-1.70之介電質層係合倂以下 目的而具有之層，其係在使用透明導電性積層薄膜當作顯 示體的構件時，作爲爲了保護透明導電性薄膜而積層之保 護層之目的，和將以手指等觸壓時的靜電電容變化變大， ^ 提高位置輸入精確度之目的。 Ο 作爲折射率爲1.40〜1.70之介電質層，例如使用 SiCh、AliCh等透明金屬氧化物及Si〇2-Al2〇3等複合金屬氧 化物、丙烯酸、聚矽氧、聚酯系樹脂所構成之有機物等。 本發明之導電性積層薄膜即使在設置有這種介電質層 的狀態下，圖形仍不易顯著，目視辨認性優異。 (透明導電性積層薄膜之光學特性）） 本案之發明中，在將透明導電性積層薄膜的透明導電 〇 性薄膜層圖案化後，於將折射率爲1.40〜1.70的介電質層積 層在透明導電性薄膜層側之狀態下，有透明導電性薄膜層 的部分和沒有的部分之光學特性差異少係屬重要，滿足下 述（1)及（2)式爲佳。 0^ | T1 - T0 | ^ 1.0 (1) 0 ^ | bl — b0 1 ^ 1.0 (2) (T1:有透明導電性薄膜層的部分之薄膜的全部光線透 過率， -20- 201043470 bl:有透明導電性薄膜層的部分之薄膜的色彩b値， TO :沒有透明導電性薄膜層的部分之薄膜的全部光線 透過率， bO :沒有透明導電性薄膜層的部分之薄膜的色彩b値） T1爲90%以上較佳，更佳爲90.5%以上，bl爲-2〜2 較佳，更佳爲-1.0〜1.5，再更佳爲〇~1.5。201043470 VI. Description of the Invention: [Technical Field] The present invention relates to laminating a high-strength layer, a low-refractive-index layer, and a transparent conductive film layer in a sequence on a substrate made of a transparent plastic film. The invention of a transparent conductive film. In particular, when used as a patterned electrode film such as a capacitive touch panel, the surface resistance is low, the touch panel can be enlarged, and the defective portion of the transparent conductive thin film layer and the removed portion are Since the difference in optical characteristics is small, the transparent conductive film which is visually identifiable can be improved. [Prior Art] A transparent conductive film in which a transparent and low-resistance film is laminated on a substrate made of a transparent plastic film is widely used for its use in conductivity, such as liquid crystal display or electric excitation. Light (sometimes slightly EL) A flat panel display such as a display or a transparent electrode of a resistive touch panel, used in the electrical and electronic fields. 〇 w In recent years, the number of cases in which capacitive touch panels are mounted on mobile phones such as portable phones and portable music terminals has increased. Such an electrostatic capacitive touch panel has a structure in which a dielectric layer is laminated on a patterned conductor, and is grounded via an electrostatic capacitance of a human body by a finger or the like. At this time, the resistance 値 between the pattern electrode and the ground point changes, and the position input is recognized. However, when a conventional transparent conductive film is used, the difference in optical characteristics between the portion having the transparent conductive film layer and the removed portion is large, so that the pattern is remarkably 'when placed on the front surface of the display body such as a liquid crystal display, the front 201043470 surface is visually observed. The problem of reduced visibility. In order to increase the transmittance or color tone of the transparent conductive film, a layer having a refractive index different from that used in the laminated reflection preventing processing or the like is used, and a method of interference by light is used. Namely, it is proposed to provide a layer having a refractive index difference between the transparent conductive film layer and the base film, and to use optical interference (Patent Documents 1 to 3). However, the transparent conductive film described in the above Patent Documents 1 to 3 can improve the visibility of the transparent conductive film, but it is not considered to reduce the transparent conductivity when the transparent conductive film layer is patterned. The problem of the difference in optical characteristics between the portion of the film and the portion of the film is not significant, so that the patterned portion is remarkable. In recent years, the touch panel mounted on mobile devices such as mobile phones has been expected to increase in size. In particular, the transparent conductive film which tends to have a capacitance is patterned and used as described above. Therefore, when the touch panel is enlarged, the wiring resistance of each pattern electrode is increased, and the operation speed is lowered. 〇 Therefore, it is desirable to have a transparent conductive film in which the surface resistance is low and the above pattern is not remarkable. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. That is, the object of the present invention is to provide a transparent conductive laminated film by a low surface resistance, a portion having a transparent conductive film layer, and an optical property of a removed portion in view of the above conventional problems. When the difference is small, the visibility is good when used in a liquid crystal display or the like, and the pattern is not conspicuous. [Means for Solving the Problems] The present invention has been made in view of the above circumstances, and the transparent conductive laminate capable of solving the above problems is formed by the following constitution. 0 1. A transparent conductive laminated film characterized in that a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order on a substrate composed of a transparent plastic film. The laminated film, the high refractive index layer has a refractive index of 1.70 to 2.50, the film thickness is in the range of 4 to 20 nm, the low refractive index layer has a refractive index of 1.30 to 1.60, and the film thickness is in the range of 20 to 50 nm, and the transparent conductive film layer The surface resistance 値 of the surface is 50 to 300 Ω / □, and the film thickness is 10 to 30 nm. The transparent conductive laminated film according to the above 1, wherein the transparent conductive ruthenium film layer has a specific resistance of 1.0 to 6.0 χ 10 4 Ω·cm. 3. The transparent conductive laminated film according to the above 1 or 2, wherein the transparent conductive thin film layer is composed of an average crystal grain size of 10 to 1000 nm and a ratio of the amorphous portion to the crystal portion of 0.000 to 0.90. It is composed of a metal oxide film. 4. The transparent conductive laminated film according to the above 3, wherein the transparent conductive thin film layer has an indium-tin composite oxide having a tin oxide content of 5% to 8% by mass. A transparent conductive laminated film which is a transparent conductive thin film layer of the transparent conductive laminated film according to any one of the above 1 to 4, which is patterned by a transparent conductive laminated film. On the side of the transparent conductive thin film layer, a dielectric layer having a refractive index of 1.40 to 1.70 is laminated. 6. A transparent conductive laminated film characterized by having a difference in optical characteristics between a portion of the transparent conductive thin film layer formed by patterning the transparent conductive laminated film according to the above 5 and a portion which is not present, and satisfying the following (1) Formula and (2), 0 each 1 T1 - TO 1 ^ 1.0 (1) 0^ I bl - b0 1 ^ 1.0 (2) (T1: Total light of a film having a portion of a transparent conductive film layer Transmittance, bl: color of film of a portion having a transparent conductive film layer, T0: total light transmittance of a film having no transparent conductive film layer, G b0: portion having no transparent conductive film layer Color of film b値) [Effect of the invention] The transparent conductive film of the present invention is formed on a substrate composed of a transparent plastic film, and has a layer of a high refractive index layer, a low refractive index layer, and a transparent conductive film layer. In the case of patterning the transparent conductive thin film layer, since the difference in optical characteristics between the portion having the transparent conductive thin film layer and the portion having no transparent conductive layer is small, it is transparent even when disposed in front of the display body such as a liquid crystal display. Pattern of electrically conductive thin layer nor significant, can be suppressed to reduce the visibility of the visual 201,043,470. In addition, the surface resistance is low, and the control panel can be enlarged. [Embodiment] The transparent conductive film of the present invention is formed on a substrate made of a transparent plastic film, and has a structure in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order. Further, the transparent conductive laminated film is characterized in that a dielectric layer is laminated on the transparent conductive thin film layer of the transparent conductive multilayer film which is patterned by the transparent conductive thin film layer of the transparent transparent conductive laminated film. Floor. Hereinafter, each layer will be described in detail. (Substrate composed of a transparent plastic film) The substrate made of the transparent plastic film used in the present invention is obtained by melt-extruding or extruding an organic polymer in the form of a film, forming a film, and depending on the length. A film that is stretched, thermoset, or thermally relaxed in the direction and/or width direction. Examples of the organic polymer include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polypropylene terephthalate, nylon 6, and resistant. Polyester 4, nylon 66, nylon 12, polyimine, polyamidamine, polyether sulfur, polyetheretherketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, poly Dichloroethylene, polyvinyl alcohol, polyether phthalimide, polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, norbornene-based polymer, and the like. Among these organic polymers, polyethylene terephthalate, polyparaphenyl 201043470 dipropyl dicarboxylate, polyethylene-2,6-naphthalenedicarboxylate, syndiotactic polystyrene, norbornene Polymers, polycarbonates, polyarylates and the like are suitable. Further, the organic polymers may be copolymerized with a small amount of monomers of other organic polymers, and other organic polymers may be mixed. The thickness of the substrate composed of the transparent plastic film used in the present invention is preferably from 10 to 300 / zm, more preferably from 20 to 15 Q/zm. When the thickness of the plastic film is less than 10/zm, the mechanical strength is insufficient, and it is difficult to operate in the step of forming the transparent conductive film, which is not preferable. On the other hand, if the thickness exceeds 300 pm, the thickness of the touch panel becomes too thick, and thus it is not suitable for a traveling machine or the like. The substrate made of the transparent plastic film used in the present invention is subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and the like, as long as the object of the present invention is not impaired. Surface activation treatment such as ozone treatment is also possible. Further, the substrate made of the transparent plastic film used in the present invention has the purpose of improving the adhesion to the high refractive index layer, imparting chemical resistance, and preventing the precipitation of low molecular weight substances such as oligomers. A cured layer containing a hardening type resin as a main component is provided. The curable resin is not particularly limited as long as it is cured by energy application such as heating, ultraviolet irradiation, or electron beam irradiation, and examples thereof include polyfluorene oxide resin, acrylic resin, methacrylate resin, and epoxy resin. Melamine resin, polyester resin, urethane resin, and the like. From the viewpoint of productivity, a hardening type resin 201043470 mainly composed of an ultraviolet curable resin is preferred. Examples of such an ultraviolet curable resin include a polyfunctional acrylate resin of acrylic acid or methacrylic acid ester of a polyhydric alcohol, a diisocyanate, a polyhydric alcohol, and a hydroxyalkyl ester of acrylic acid or methacrylic acid. A polyfunctional urethane acrylate resin or the like. If necessary, a monofunctional monomer such as vinylpyrrolidone, methyl methacrylate, styrene or the like may be added to the polyfunctional resin to be copolymerized. 0 Further, in order to improve the adhesion of the high refractive index layer and the cured layer, it is effective to surface-treat the cured layer. Specific examples of the method include a discharge treatment method using a glow discharge discharge or a corona discharge, a method of increasing a carbonyl group, a carboxyl group, and a hydroxyl group, a chemical treatment method using an acid or a base treatment, and a polar group such as an amine group, a hydroxyl group, or a carbonyl group. Method and so on. The ultraviolet curable resin is usually used by adding a photopolymerization initiator. As the photopolymerization initiator, a known compound which absorbs ultraviolet rays to generate a radical is used, and as such a photopolymerization initiator, for example, various benzoin, benzophenone, benzophenone may be mentioned. Classes, etc. The amount of the photopolymerization initiator added is preferably from 1 to 5 parts by mass based on 100 parts by mass of the ultraviolet curable resin. The concentration of the resin component in the coating liquid can be appropriately selected in consideration of the viscosity of the coating method and the like. For example, the ratio of the total amount of the ultraviolet curable resin and the photopolymerization initiator in the coating liquid is usually 20 to 80% by mass. Further, in the coating liquid, other well-known additives such as a polyfluorene-based surfactant or a leveling agent such as a fluorine-based surfactant may be added as necessary. -10-201043470 In the present invention, the prepared coating liquid is applied onto a substrate made of a transparent plastic. The coating method is not particularly limited, and a conventional method such as a hard gravure coating method or a reverse roll coating method can be used. Further, the thickness of the hardened layer is preferably in the range of 〇.l~15/zm, preferably 0.5~10jam', especially preferably i~8/zm. When the thickness of the cured layer is in the range of β m , the structure which is sufficiently crosslinked cannot be formed, so that the property is liable to be lowered, and the low molecular weight of the oligomer or the like is likely to be lowered. On the other hand, the thickness of the hardened layer is more than 15#m, and the productivity is lowered. (High refractive index layer) The refractive index of the high refractive index layer which can be used in the present invention is in the range of 1.70 to 1:, preferably 1.90 to 2.30, more preferably 1.90 to 2.10. If it is not reached, the difference in refractive index from the low refractive index layer is too small. Therefore, when the transparent conductive film layer is patterned, it is difficult to make the optical characteristics of the portion having the transparent conductive thin film layer close. On the other hand, when the refractive index is more than 2 〇, it is difficult to make the pattern in the oblique direction inconspicuous, and it is suitable for industrial non-existence. Specific examples of the high refractive index layer include Ti〇2, ZrCh, Ta2〇5, ZnO, IiuCh, SnCh, and the like, and these composite zinc sulfide ZnS. Among these, from the viewpoint of productivity, Zn 〇, SnCh and the composite oxides thereof are preferred. Further, in order to adjust the refractive index of the oxysulfide, an oxide may be added, and the thickness of the vulcanized high refractive index layer may be 4 to 20 nm, preferably 7 to 15 nm, and 8 to 13 nm. When the film thickness is less than 4 nm, it becomes a discontinuous film, a film coating method, and a coating method. Better t = 0 · 1 When the drug is in close contact, there is 2.50 of 1.70 > Electrical thinness and when there is no .50, the material is also N b 2 0 5 ' and ΙΠ2〇 3 ' compound or substance. More preferably, the membrane is safely reduced by -11-201043470. On the other hand, when the film thickness exceeds 20 nm, the light reflection becomes strong. Therefore, when the transparent conductive thin film layer is patterned, it is difficult to make the optical characteristics of the portion having the transparent conductive thin film layer and the non-existing portion close to each other. When the front surface of a display body such as a liquid crystal display is used, the pattern of the transparent conductive thin film layer is remarkable, and the visibility is lowered. However, it is preferable to control the refractive index and film thickness of the high refractive index layer arbitrarily, as it is preferable to control the optical film thickness (refractive index X film thickness). 0. As a film forming method of the high refractive index layer in the present invention, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the required film thickness. However, from the viewpoint of reducing film thickness unevenness, sputtering is preferred. In the sputtering method, there are generally a reactive sputtering method in which a reactive gas is introduced from a metal target to form a metal oxide, and a method of producing a metal oxide from an oxide target. In the reactive sputtering method, there is a transition region in which the film formation rate rapidly changes depending on the flow rate of the reactive gas. Therefore, in order to suppress the unevenness of the film thickness, an oxide target is preferably used. (Low Refractive Index Layer) The refractive index of the low refractive index layer used in the present invention is 1.30 to 1.60, preferably 1.40 to 1.55, more preferably 1.43 to 1.50. If the refractive index is less than 1.30, a porous film is formed, so that the electrical properties of the transparent conductive thin film layer formed thereon are lowered. On the other hand, when the refractive index is more than 1.60, the interference with the light of the transparent conductive thin film layer becomes too weak. Therefore, when the transparent conductive thin film layer is patterned, it is difficult to make the portion of the transparent conductive thin film layer -12- 201043470 is similar to the optical characteristics of the non-existent part. When disposed in front of a display such as a liquid crystal display, the pattern of the transparent conductive film layer is remarkable, and the visibility is lowered. Specific examples of the low refractive index layer include transparent metal oxides such as Si〇2 and Al2〇3, and composite metal oxides such as SiCh-Al2〇3, and metal fluorides such as CuF2, CeF2, MnF2, and MgF2, and the like. Composite fluoride. Further, in order to adjust the refractive index of the oxide or the fluoride, any oxide or sulfide may be added. The film thickness of the low refractive index layer is 20 to 50 nm, preferably 25 to 45 nm, more preferably 30 to 40 nm. When the thickness exceeds 50 nm, the wavelength dependence becomes too strong due to interference with the light of the transparent conductive thin film layer. Therefore, when the transparent conductive thin film layer is patterned, it is difficult to make the transparent conductive thin film layer portion and the non-existing portion. The optical properties are close. On the other hand, when it is less than 20 nm, it is difficult to cause interference with light of the transparent conductive thin film layer, and the transmittance cannot be improved. Therefore, when the transparent conductive thin film layer is patterned, it is difficult to form a transparent conductive thin film layer. The optical characteristics of the portion which is not in the vicinity of the display body such as a liquid crystal display are remarkable, and the pattern of the transparent conductive film layer is remarkable, and the visibility is lowered. However, it is preferable to control the refractive index and film thickness of the low refractive index layer arbitrarily, and it is preferable to control the optical film thickness (refractive index X film thickness) to be constant. As a film forming method of the low refractive index layer in the present invention, a vacuum distillation method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known. To reduce the uneven thickness of the film -13,43,470 points, the sputtering method is preferred. Reactive DC or AC sputtering is generally used when forming by sputtering. In order to increase the film formation speed, resistance control for controlling the flow rate of the reactive gas is used to keep the voltage 値 of the DC or AC power source constant, or plasma irradiation method for controlling the flow rate of the reactive gas is used to cause luminescence in the plasma of a specific element. The strength is kept constant. (Transparent Conductive Thin Film Layer) Examples of the transparent conductive film in the present invention include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-bismuth composite oxide, and zinc-aluminum composite oxidation. Matter, indium-zinc composite oxide, and the like. Among these, indium-tin composite oxide is suitable from the viewpoints of environmental stability and circuit processability. In the present invention, the surface of the transparent conductive film layer is preferably 50 to 300 Ω / □, more preferably 100 to 250 Ω / □, and more preferably set to 100 to 250 Ω / □. In the case of 100 to 220 Ω/□, a transparent conductive laminated film can be used for a touch panel having a large screen size. The surface 〇 resistance 値 is as low as possible. However, since the thickness of the transparent conductive thin film layer is increased to less than 50 Ω / □, the pattern of the transparent conductive thin film layer is likely to be conspicuous, which is not preferable. On the other hand, when the value exceeds 300 Ω/□, the position recognition accuracy of the touch panel is deteriorated, which is not preferable. The film thickness of the transparent conductive film is preferably in the range of 10 to 30 nm, more preferably 12 to 25 nm. When the film thickness of the transparent conductive film is less than 〇nm, it is difficult to form a film having a flat surface, and it is difficult to obtain good conductivity. On the other hand, when the thickness of the transparent conductive film is thicker than 30 nm, when the transparent conductive-14 - 201043470 thin film layer is patterned, it is difficult to make the optical characteristics of the portion having the transparent conductive thin film layer and the non-existing portion close to each other. And there will be a significant situation in the graphics. The specific resistance of the transparent conductive thin film layer is 1.0 x 1 (Γ 4 Ω · cm or more, 6.0 χ 1 (Γ 4 Ω · cm or less is preferable. More preferably 2.0 χ 10 _ 4 Ω · cm to 4.0 x 10 _ 4 Ω · cm or less. If the specific resistance is not reached) When 1.0 χ 10_4 Ω · cm, the color of the transparent conductive thin film layer is increased, and the transparency is easily lowered. On the other hand, when the specific resistance is more than 6.0 χ 1 (Γ4 Ω · cm, the transparent conductive thin film layer is patterned). In the case of the transparent conductive film layer of the present invention, it is preferred that the crystalline film layer has an average crystal grain size of from 1 Å to 100 Åm, and is relative to the crystalline portion. The ratio of the amorphous portion of the transparent conductive film is defined as follows. When the transparent conductive film layer is observed under a transmission electron microscope, the polygonal conductive film layer has a polygonal shape. It is defined as a crystal grain, and the area of the crystal grain is found. The square root of the grain obtained by dividing the area of the crystal grain by the pi π is multiplied by the 値 of the 〇 値 as the crystal grain size. Under the transmission electron microscope, Transparent conductive The crystal grain of the film layer was observed, and the total crystal grain size was calculated. The average 値 of all the crystal grain sizes was taken as the average crystal grain size. The method of estimating the ratio of the amorphous portion to the crystal portion was The area ratio of the crystalline portion to the amorphous portion when observed under a transmission electron microscope is calculated. The average crystal grain size of the transparent conductive film of the present invention is 10 to i (10) Q nm. -15- 201043470 is particularly preferably 20 to 800 nm. More preferably, it is from 3 Å to 500 nm. When the average crystal grain size is less than 1 Onm, it is shown that formation of a transparent conductive film is less likely to cause crystal nucleation. This transparent conductive film which does not easily cause crystal nucleation means that it is in the film. On the other hand, when the crystal grain size exceeds 100 nm, the bending resistance is deteriorated, so that cracking is likely to occur when the transparent conductive thin film layer is patterned. The ratio of the amorphous portion to the crystalline portion in the transparent conductive film is 0.00 to 0.90, preferably 0.00 to 0.70, more preferably 0.00 to 0.50. If the ratio described above is greater than 0.90, it is shown to form a transparent guide. In the case of a film, it is difficult to cause formation of a crystal nucleus. This transparent conductive film which does not easily cause crystal nucleation means that there are many defects in the film, and the specific resistance does not fall under the tin oxide contained in the transparent conductive film layer. The content is preferably 0.5 to 8% by mass, more preferably % by mass. When the content of tin oxide is less than 0.5% by mass, it is difficult to increase the carrier concentration. On the other hand, the content of antimony containing tin oxide is more than 8 mass. In the case of %, the amount of dopant which is not substituted at the In site is increased, and the degree of carrier mobility is lowered due to scattering of impurities, so that it is difficult to lower the specific resistance. The layer structure of the transparent conductive film may be a single layer structure or a laminated structure of two or more layers. In the case of a transparent conductive film having a laminated structure of two or more layers, the metal oxides constituting each layer may be the same or different. As a method of forming a transparent conductive film in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, etc., which are required for the blending method, can be suitably used. The aforementioned method. For example, in the case of the sputtering method, a usual sputtering method using an oxide target or a reactive sputtering method using a metal target is used. At this time, as the reactive gas, oxygen, nitrogen, or the like may be introduced, or ozone, ozone irradiation, plasma irradiation, or ion assist may be used. Further, a bias voltage such as a direct current, an alternating current, or a high frequency may be applied to the substrate without departing from the object of the present invention. In order to obtain the transparent conductive thin film layer having a low specific resistance and a crystalline form of the present invention, the following two effective methods are available. • Remove water and organic matter from the film formation atmosphere. • Increase the energy of the vapor deposited particles. First, the method related to the above (1) will be explained. When the transparent conductive thin film layer is formed, the surface of the substrate (film) is likely to migrate due to a small decrease in energy of the vapor-deposited particles in the film formation atmosphere where impurities of moisture or organic matter are removed as much as possible. As a result, it is easy to produce a transparent conductive film containing crystals in a transparent conductive film. Therefore, a crystalline transparent conductive thin film layer having a large average crystal grain size and a ratio of the amorphous portion to the crystal portion of 0.00 to 0.90 can be obtained. Specifically, the ratio of the water pressure to the inert gas (argon or the like) in the film formation atmosphere is 8.0 x 1 (T4 to 3.0 x 1 (T3 is preferable. As a specific means, 1 is sufficient to remove the film before film formation). Moisture in the plastic film, 2 is an effective method for attaching cold water (Cryopump) for moisture adsorption in the film formation space. 1 In order to sufficiently remove moisture in the plastic film before film formation, -17-201043470 is effective. The method is to heat the plastic film while the plastic film is moving in a vacuum. The effective heating temperature is 25 to 80 ° C. As the heating method, a heating roller, an infrared heater, etc. may be mentioned. If it is less than 25 ° C, However, the plastic film cannot be effectively heated. If it exceeds 80 ° C, the plastic film may be scratched or deformed. 2 As a suitable cold-water pump for moisture adsorption provided in the film formation space, Bodong Co., Ltd. POL YC OLD made by the company. In order to make the ratio of water pressure to inert gas (argon, etc.) less than 8.0X10-4, 0, a device that puts a large amount of transparent plastic film into the film forming chamber must have a long time vacuum removal. The time is used to reduce the ratio of the water pressure to the inert gas, or the vacuum pump with a very high capacity is required, so that the economic implementation is difficult. On the other hand, if the ratio of the water pressure to the inert gas of the film forming atmosphere is more than 3.0x1 ( Γ 3, since the energy of the vapor deposition particles is lowered, it is difficult to obtain a transparent conductive thin film layer having a low specific resistance and a crystalline quality. The substrate (film) temperature at the time of film formation is preferably -20 to 80 ° C. °C, because a large amount of impurity gases such as water and organic gases from the film are generated, so that the energy of the deposited particles is lowered, and it is difficult to obtain a transparent conductive film having a low specific resistance and a crystalline quality. Further, at a temperature of less than -20 ° C The transparent plastic film is less brittle. The substrate temperature can be adjusted by a temperature adjustment roller, etc. Next, the method of the above (2) will be described. When the transparent conductive film layer is formed, the method of increasing the energy of the vapor deposition particles is used. Examples of the activation support method such as ion assist method and ion plating method or high-power pulse magnetron sputtering method can be used to increase the energy of vapor deposition atoms by using these methods. The surface of the substrate (film) is likely to migrate. As a result, 18-201043470, it is possible to obtain a crystalline portion and a specific conductive film in the transparent conductive film. In the above method, there is also a high-power magnetron sputtering method. As a method of replacing the source, a conventional sputtering apparatus can be used. For example, a film formation condition by a high sputtering method is followed by introduction of oxygen, and an argon gas film pressure is set to 0.1 to 1.0 Pa at a charging voltage of 400 to 1000 V. 10 to 500 Hz, and a pulse width of 1 〇 to 200 WS, the square Q of the discharge causes an arc phenomenon, and a transparent conductive film having a small portion and a small specific resistance can be obtained in the transparent conductive film. Further, in order to further reduce the specific resistance, After the film formation, energy is imparted by means of ultraviolet irradiation or the like. These energy imparting means are suitable for heat treatment under an oxygen atmosphere. The heat treatment temperature is in the range of 80 to 20 (the range of TC is preferable. When the degree is not reached, it is difficult to cause substitution of the dopant, and it is difficult to increase the load, and the specific resistance is further insufficient. On the other hand, when the temperature is 〇乞It is difficult to maintain the planarity of the film, and further, the crystal size in the film becomes too large, and a brittle transparent guide is formed. Further, as the heat treatment time, it is preferably in the range of 0.5 to 60 minutes in the range of 0.2 to 120 minutes. When the temperature is less than 0.2, the heat treatment is carried out at a high temperature of about 22 ° C, and the effect of improving the film quality is not good. On the other hand, the heat treatment time exceeding 120 minutes is industrial. It is an electric power magnetron for sputtering with a small pre-exhaust resistance, which is formed into a pulse frequency type. There is no crystal quality by heating, and at a temperature concentration of 80 °C, more than 200 For example, even if the fruit is still insufficient, it is preferable to use a space of 0.2 Pa -19 to 201043470 and then to fill the space of oxygen. The pressure at this time is preferably at most atmospheric pressure. A dielectric layer (protective layer) having a refractive index of 1.40 to 1.70. In the present invention, a dielectric layer having a refractive index of 1.40 to 1.70 is bonded to the following purpose, and a transparent conductive laminated film is used. When it is used as a member of a display body, it is used as a protective layer for protecting a transparent conductive film, and the change in electrostatic capacitance when a finger or the like is pressed is increased, and the accuracy of position input is improved. The dielectric layer having a ratio of 1.40 to 1.70, for example, a transparent metal oxide such as SiCh or AliCh, a composite metal oxide such as Si〇2-Al2〇3, or an organic material composed of acrylic acid, polyfluorene oxide or polyester resin. In the conductive laminated film of the present invention, the pattern is not easily noticeable even in the state in which such a dielectric layer is provided, and the visibility is excellent. (Optical characteristics of the transparent conductive laminated film) In the invention of the present invention, After the transparent conductive thin film layer of the transparent conductive laminated film is patterned, the dielectric laminated layer having a refractive index of 1.40 to 1.70 is transparently conductive in the state of the transparent conductive thin film layer side. A small portion of the film layer and the portion of the optical properties no significant differences based metal, said satisfies the following (1) and (2) being preferred. 0^ | T1 - T0 | ^ 1.0 (1) 0 ^ | bl — b0 1 ^ 1.0 (2) (T1: total light transmittance of a film having a transparent conductive film layer, -20- 201043470 bl: Yes The color of the film of the portion of the transparent conductive film layer, ie, the total light transmittance of the film of the portion having no transparent conductive film layer, bO: the color of the film of the portion having no transparent conductive film layer, b)) More preferably, it is 90% or more, more preferably 90.5% or more, and bl is preferably -2 to 2, more preferably -1.0 to 1.5, still more preferably 〇~1.5.
Tl、bO、TO、bO係於考慮到各層間的反射光的干涉之 0 下，藉由將各層的光學厚度在高折射率層的折射率爲 1_70~2.50、高折射率層的膜厚爲4〜20nm、低折射率層的折 射率爲1.30~1.60、低折射率層的膜厚爲20~50nm之範圍内 進行調整，即可達成。 又’ b値係於上述調整之中，將分光透過率的峰値設 定在450〜5 30nm之範圍，即可進行調整。更佳的分光透過 率之峰値爲470~510nm。 〔實施例〕 〇 以下根據實施例進一步詳細地說明本發明，但本發明 並非受該等實施例限定者。此外，透明導電性積層薄膜之 性能係藉由下述方法測量。 (1)全部光線透過率Tl, bO, TO, and bO are based on the interference of the reflected light between the layers, and the refractive index of each layer is 1 to 70 to 2.50 in the high refractive index layer, and the film thickness of the high refractive index layer is The refractive index of 4 to 20 nm, the low refractive index layer is 1.30 to 1.60, and the film thickness of the low refractive index layer is adjusted to be in the range of 20 to 50 nm. Further, b 値 is adjusted in the above adjustment, and the peak of the spectral transmittance is set in the range of 450 to 5 30 nm. The peak of the better spectral transmittance is 470 to 510 nm. [Embodiment] The present invention will be described in further detail below based on examples, but the present invention is not limited by the examples. Further, the properties of the transparent conductive laminated film were measured by the following methods. (1) total light transmittance
根據JIS-K7136,利用曰本電色工業（股）製NDH-1001DP 測量全部光線透過率。 此外，（1)式中的T1、T0 ’係於經圖案化後的透明導電 性積層薄膜’將折射率爲1.52之介電質層，積層於透明導 21 - 201043470 電性薄膜層側之狀態下，經測量之有透明導電性薄膜層的 部分及沒有透明導電性薄膜層的部分之値。 (2) 表面電阻値 根據Π S -K7 1 94，以4端子法測量表面電阻値°測量 器係使用三菱油化（股）製Lotest AMCP-T400。 (3) 色彩b値 根據JIS-K7105，利用色差計（日本電色工業製、 ^ ZE-2000)，以標準光C/2測量色彩b値。 Ο 此外，（2)式中的b 1、b 0，係於經圖案化後的透明導 電性積層薄膜，將折射率爲1.52之介電質層，積層於透明 導電性薄膜層側之狀態下，經測量之有透明導電性薄膜層 的部分及沒有透明導電性薄膜層的部分之値。 (4) 目視辨認性評價 將抗蝕劑印刷在透明導電性積層薄膜後，浸漬在1 N 鹽酸中，藉由鹼浸漬，形成1x3 cm的圖案。將具有折射率 Ο 1.52之丙烯酸系黏合層之二軸配向聚對苯二甲酸乙二酯 (以下略記PET)薄膜，貼合在透明導電性薄膜側作爲保護薄 膜。使用富士通公司製FMV-BIBLOLOOX T70M/T，將畫面 設定成白色顯示，再將貼合有保護薄膜的薄膜放置在其前 面，從各種角度評價圖形的觀感。 〇： 大致看不到圖形。 △: 圖形少。 X . 看見圖形。 -22- 201043470 (5) 高折射率層、低折射率層、透明導電性薄膜層之膜厚 將積層有高折射率層、低折射率層、透明導電性薄膜 層之薄膜試料片切成ImmxlOniin之大小，包埋於電子顯微鏡 用環氧樹脂。將其固定在超薄切片機（Ultramicrotome)的試 料保持具，製作平行於經包埋的試料片之短邊的斷面薄切 片。接著’在該切片之薄膜沒有顯著損傷的部位，利用透 過型電子顯微鏡（IEOL公司製、；TEM-2010)，以加速電壓 0 2〇〇kV、在明視野觀察倍率1萬倍進行照片攝影，從所獲得 的照片求出膜厚。 (6) 高折射率層、低折射率層、透明導電性薄膜層之折射率 針對在矽晶圓上將各層分別以相同的成膜條件製作 而成的試料，利用分光光譜儀（Ellipsometer)(大塚電子股份 有限公司製、FE-5000)，評價5 5 0nm之折射率。且，利用 光學模擬軟體對設有各層之薄膜的分光透過率測量資料進 行擬合（Fitting)，算出折射率。此時，各層之膜厚係使用前 Ο 述膜厚評價方法所評價之値。再者，確認如此地算出之各 層折射率和矽晶圓上各層折射率沒有太大的差異。 (7) 透明導電性薄膜的比電阻 利用前述表面電阻値和透明導電性薄膜層的膜厚，算 出比電阻。 (8) 平均結晶粒徑 將積層有透明導電性薄膜層之薄膜試料片切成1 mmx 10 nun之大小，將導電性薄膜面朝外，貼附在適當的樹脂塊 -23- 201043470 之上面。將其修整後，藉由一般的超薄切片機之技法，製 作大致平行於薄膜表面的超薄切片。 藉由透過型電子顯微鏡（JEOL公司製、JEM-2010)觀察 該切片，選出沒有顯著損傷的導電性薄膜表面部分，以加 速電壓200kV、直接倍率40000倍進行照像攝影。 在透過型電子顯微鏡下觀察透明導電膜層時，將具有 多角形狀之範圍者，定義爲結晶粒，並找出結晶粒之面積。 0 將結晶粒面積除以圓周率；r所得之値的平方根，乘以2倍 後之値，作爲結晶粒徑。 針對在透過型電子顯微鏡下，在透明導電膜層被觀察 到的氧化銦之結晶粒，算出全部的結晶粒徑。將全部的結 晶粒徑之平均値作爲平均結晶粒徑。 (9)非晶部對結晶質部之比例 從在透過型電子顯微鏡下觀察時的結晶質部和非晶 質部的面積比算出。 〇 〔實施例1〕 在含有光聚合引發劑之100質量份紫外線硬化型丙烯 酸系樹脂（大日精化工業公司製、Seikabeam EXF-01 J)，加 入作爲溶劑的甲苯/MEK(80/20 :質量比）之混合溶劑，至固 體分濃度成爲50質量％，攪拌且均等地溶解，調製成塗布 液。 在兩面具有易接合層之二軸配向透明PET薄膜（東洋 紡織公司製、A4300、厚度lOOy m)，使用邁耶棒（Meyer Bar) -24- 201043470 塗布經調製之塗布液形成塗膜厚度5# m。以8(TC進行1 分鐘乾燥後’利用紫外線照射裝置（Eye Graphics公司製、 UB042-5AM-W型）照射紫外線（光量：300mJ/cm 2)，使塗膜 硬化。接著，針對反面也同樣地塗設塗膜後，以1 8 0。(：施行 1分鐘加熱處理，進行減少揮發成分。 且’在製膜前’以去除薄膜中的水分爲目的，爲了將 積層有該硬化物層之二軸配向透明PET薄膜進行真空暴 0 露’而在真空處理室中進行反捲處理。此時的壓力爲 0_002Pa，暴露時間爲20分鐘。且，中央輥的溫度爲40°C， 薄膜通過該中央輥。 接著，在該硬化物層上將銦-錫複合氧化物所構成的透 明導電性薄膜成膜，作爲高折射率層。此時，將濺鏟前的 壓力設定爲0.000 1 Pa，利用含有36質量％氧化錫之氧化銦 (住友金屬鑛山公司製、密度6.9g/cm 3)作爲標靶，施加2W/ cm 2之DC電力。且，將Ar氣體以130sccm、〇2氣體以表面 〇 電阻値爲最小時之〇2流量的3倍流速流過，在〇.4Pa之大 氣下利用DC磁控濺鍍法成膜。 且，以濺鍍製程監視器（LEYBOLD INFICON公司製、 Transpector XPR3)長時觀測大氣之氧分壓，反饋到氧氣之 流量計及D C電源，使銦-錫複合氧化物薄膜中的氧化度成 爲一定。如以上方式，堆積成厚度l〇nm、折射率1.93之銦 -錫複合氧化物所構成的高折射率層。如此地獲得之高折射 率層之表面電阻値爲1x1 /□以上。 -25- 201043470 再者，爲了在前述高折射層上形成Si〇2薄膜作爲低折 射率層，而用矽作爲標靶，利用直流磁控濺鍍法、真空度 爲0.27Pa、作爲氣體之Ar氣體爲500sccm、〇2氣體爲80sccm 之流速流過。 且，一面長時觀測成膜中的電壓値，一面反饋到氧氣 之流量計，使電壓値成爲一定。如以上方式，堆積成厚度 3 5 nm、折射率1 · 46之低折射率層。 ^ 接著，在該低折射率層上將銦-錫複合氧化物所構成的 〇 透明導電性薄膜成膜。此時，將濺鍍前的壓力設定爲 0.0 00 1 Pa，利用含有3質量％氧化錫之氧化銦（住友金屬鑛 山公司製、密度7.1g/cm 3)作爲標靶，施加2W/cm 2之DC電 力。且，以Ar氣體爲130sccm、〇2氣體以表面電阻値爲最 小時之流速流過、在0.4Pa之大氣下利用DC磁控濺鍍法成 膜。且，調整成中央輥溫度爲10°C、薄膜溫度爲大約l〇°C。 且，利用濺鍍製程監視器（LEY BOLD INFICON公司製、 〇 Transpector XPR3)觀測相對於成膜大氣中的氬之水分壓， 並堆積厚度20nm、折射率1.96之銦-錫複合氧化物所構成 的透明導電性薄膜，製作透明導電性積層薄膜。 〔實施例2〕 除了作爲形成透明導電性薄膜時的標靶變更爲含有1 質量％氧化錫的氧化銦（住友金屬鑛山社製、密度7.1 g/cm 3) 以外，與實施例1同樣地製作透明導電性積層薄膜。 〔實施例3〕 -26- 201043470 除了作爲形成透明導電性薄膜時的標靶變更爲含有5 質量％氧化錫的氧化銦（住友金屬鑛山社製、密度7.1 g/cm 3)以外，與實施例1同樣地製作透明導電性積層薄膜。 〔實施例4〕 除了作爲形成透明導電性薄膜時的標靶變更爲含有 7.5質量％氧化錫的氧化銦（住友金屬鑛山社製、密度7.1 g/ cm 3)以外，與實施例1同樣地製作透明導電性積層薄膜。 0 〔實施例5〕 除了實施例1中，將真空處理室中進行反捲處理時的 中央輥的溫度設定爲70°C以外，與實施例1同樣地形成爲 透明導電性積層薄膜。 〔實施例6〕 除了實施例1中，將真空處理室中進行反捲處理時的 中央輥的溫度設定爲30°C以外，與實施例1同樣地形成爲 透明導電性積層薄膜。 Ο 〔實施例7〕 實施例1中，將銦-錫複合氧化物所構成之透明導電性 薄膜，成膜在低折射率層上時，不是用通常的脈衝DC電 源，而是用高功率脈衝磁控濺鍍用的電源（HMP2/3、 HUETTINGER公司製）。此時，將濺鍍前的壓力設定爲 0.0001 Pa，利用含有3質量％氧化錫之氧化銦（住友金屬鑛 山公司製、密度7.1g/cm 3)作爲標靶，以充電電壓500V、脈 衝頻率5 00 Hz、脈衝寬度150//S進行。且，將Ar氣體以 -27- 201043470 13 0sccm、〇2氣體以表面電阻値爲最小時之流速流過，在 0.4Pa之大氣下，將中央輥溫度設定爲10°C，進行濺鍍。 且，利用濺鍍製程監視器（LEYBOLD INFICON公司製、 Transpector XPR3)觀測相對於成膜大氣中的氬之水分壓， 並堆積厚度20nm、折射率2.01之銦-錫複合氧化物所構成 的透明導電性薄膜。其他則與實施例1同樣地形成爲透明 導電性積層薄膜。 0 〔實施例8〕 除了實施例1中，在硬化物層上將作爲高折射率層之 由鉻-矽複合氧化物（Zr〇2 - SiCh)所構成之薄膜成膜以 外，與實施例1同樣地形成爲透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲0.000 1 Pa，使用ZrSh(三 井金屬製）作爲標靶，施加2W/cm 2之DC電力，利用直流磁 控濺鍍法、真空度爲0.27 Pa、作爲氣體之 Ar氣體係以 500sccm、〇2氣體係以80sccm之流速流過，進行成膜。且， G 長時觀測成膜中的電壓値，並反饋到氧氣的流量計使電壓 値成爲一定。如以上方式，堆積成厚度12 nm、折射率1.75 之高折射率層。 〔實施例9〕 除了實施例1中，在硬化物層上將作爲高折射率層之 由鈦氧化物（TiCh)所構成之薄膜成膜以外，與實施例1同樣 地製作成透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲O.OOOlPa，使用Ti(三井 -28- 201043470 金屬製）作爲標靶，施加2W/cm 2之DC電力，利用直流磁控 濺鍍法、真空度爲〇.27Pa、作爲氣體之Ar氣體係以 500sccm、〇2氣體係以80sccm之流速流過，進行成膜。且， 長時觀測成膜中的電壓値，並反饋到氧氣的流量計使電壓 値成爲一定。如以上方式，堆積成厚度8nm、折射率2.29 之高折射率層。 〔實施例1 0〕 0 除了實施例1中，在硬化物層上將作爲高折射率層之 由硫化鋅（ZnS)所構成之薄膜成膜以外，與實施例1同樣地 製作成透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲O.OOOlPa，使用硫化鋅（三 井金屬製）作爲標靶，施加2W/cm 2之13.5 6MHz之高頻電 力，利用磁控濺鍍法、真空度爲0.27 Pa、作爲氣體之Ar氣 體係以500sccm、〇2氣體係以80sccm之流速流過，進行成 膜。且，長時觀測成膜中的電壓値，並反饋到氧氣的流量 Ο 計使電壓値成爲一定。如以上方式，堆積成厚度7.5nm、折 射率2.43之高折射率層。 〔實施例1 1〕 除了實施例1中，在硬化物層上將作爲低折射率層之 由氟化鎂（MgF2)所構成的薄膜成膜以外，與實施例1同樣 地製作成透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲0.0001 Pa，使用氟化鎂（三 井金屬製）作爲標靶，施加2W/cm 2之13.5 6M Hz之高頻電 -29- 201043470 力，利用磁控濺鍍法、真空度爲0.27Pa、作爲氣體之Ar 體係以500sccm之流速流過，進行成膜。且，長時觀測 膜中的電壓値，並反饋到氧氣的流量計使電壓値成爲 定。如以上方式，堆積成厚度40nm、折射率1.36之低折 率層。 〔實施例1 2〕 除了實施例1中，在硬化物層上將作爲低折射率層 0 由鋁-矽複合氧化物（Al2〇3-Si〇2)所構成之薄膜成膜以外， 實施例1同樣地製作成透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲 〇.〇〇〇lPa，使 APSiOO : 50wt% )(三井金屬製）作爲標靶，施力□ 2W/cm 2 DC電力，利用磁控濺鏟法、真空度爲〇.27Pa、作爲氣體 Ar氣體係以500sccm、〇2氣體係以80 seem之流速流過 進行成膜。且，長時觀測成膜中的電壓値，並反饋到氧 的流量計使電壓値成爲一定。如以上方式，堆積成厚 〇 3 5 m、折射率1.5 5之低折射率層。 〔實施例1 3〕 將與實施例1同樣地獲得之透明導電性積層薄膜， 120°C進行60分鐘加熱處理。加熱處理係事先減壓至〇. 後，置換氧再進行。 〔比較例1〕 除了不設高折射率層、低折射率層，將透明導電牲 膜層的膜厚設定爲22nm以外，與實施例1同樣地製作拭 氣 成 射 之 與 用 之 之 I 氣 度 以 IPa 薄 透 -30- 201043470 明導電性積層薄膜。 〔比較例2〕 除了不設高折射率層以外，與實施例1同樣地製作成 透明導電性積層薄膜。 〔比較例3〕 除了將低折射率層的膜厚設定爲l〇nm以外，與實施 例1同樣地製作成透明導電性積層薄膜。 0 〔比較例4〕 除了將低折射率層的膜厚設定爲lOOnm以外，與實施 例1同樣地製作成透明導電性積層薄膜。 〔比較例5〕 除了作爲形成透明導電性薄膜時的標靶變更爲含有1〇 質量％氧化錫的氧化銦（住友金屬鑛山社製、密度7.1 g/cm 3) 以外，與實施例1同樣地製作成透明導電性積層薄膜。 〔比較例6〕 〇 除了作爲形成透明導電性薄膜時的標靶變更爲不含 氧化錫的氧化銦（住友金屬鑛山社製、密度7.1 g/cm 3)以外， 與實施例1同樣地製作成透明導電性積層薄膜。 〔比較例7〕 除了實施例1中，將真空處理室中進行反捲處理時的 中央輥的溫度設定爲20 °C以外，與實施例1同樣地形成爲 透明導電性積層薄膜。 〔比較例8〕 -31 - 201043470 除了實施例1中，在硬化物層上將作爲高折射率層之 由鋁-矽複合氧化物（Al2Ch-Si〇2)所構成之薄膜成膜以外，與 實施例1同樣地形成爲透明導電性積層薄膜。 此時，將濺鍍前的壓力設定爲 O.OOOlPa，使用 Al-Si(50: 50wt%)(三井金屬製）作爲標靶，施加2W/cm 2之 DC電力，利用磁控濺鍍法、真空度爲〇.27Pa、作爲氣體之 Ar氣體係以500sccm、〇2氣體係以80sccm之流速流過，進 ^ 行成膜。且，長時觀測成膜中的電壓値，並反饋到氧氣的 流量計使電壓値成爲一定。如以上方式，堆積成厚度22 m、 折射率1.55之高折射率層。 〔比較例9〕 除了實施例1中，在硬化物層上將作爲低折射率層之 由鉻-矽複合氧化物（Zr〇2- SiO〇所構成之薄膜成膜以外， 與實施例1同樣地形成爲透明導電性積層薄膜。 此時，將濺鏟前的壓力設定爲O.OOOlPa，使用ZrSi2(三 〇 井金屬製）作爲標靶，施加2W/cm 2之DC電力，利用直流磁 控濺鍍法、真空度爲0.27 Pa、作爲氣體之 Ar氣體係以 500sccm、〇2氣體係以80sccm之流速流過，進行成膜。且， 長時觀測成膜中的電壓値，並反饋到氧氣的流量計使電壓 値成爲一定。如以上方式，堆積成厚度29nm、折射率1.75 之低折射率層。 -32- 201043470According to JIS-K7136, the total light transmittance was measured using the NDH-1001DP manufactured by Sakamoto Electric Co., Ltd. Further, T1 and T0' in the formula (1) are based on the patterned transparent conductive laminated film 'a dielectric layer having a refractive index of 1.52, and laminated on the side of the transparent conductive layer 21 - 201043470. Next, the portion having the transparent conductive film layer and the portion having no transparent conductive film layer were measured. (2) Surface resistance 値 According to Π S - K7 1 94, the surface resistance is measured by the 4-terminal method. The measuring device is a Lotest AMCP-T400 manufactured by Mitsubishi Petrochemical Co., Ltd. (3) Color b値 According to JIS-K7105, color b値 is measured with a standard light C/2 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000). Further, b 1 and b 0 in the formula (2) are a patterned transparent conductive laminated film, and a dielectric layer having a refractive index of 1.52 is laminated on the side of the transparent conductive thin film layer. The portion having the transparent conductive film layer and the portion having no transparent conductive film layer were measured. (4) Evaluation of visual recognition The resist was printed on a transparent conductive laminated film, immersed in 1 N hydrochloric acid, and impregnated with alkali to form a pattern of 1 x 3 cm. A biaxially oriented polyethylene terephthalate (hereinafter abbreviated as PET) film having an acrylic pressure-sensitive adhesive layer having a refractive index of 2 1.52 was bonded to the transparent conductive film side as a protective film. The FMV-BIBLOLOOX T70M/T manufactured by Fujitsu Co., Ltd. was used to set the screen to a white display, and the film to which the protective film was attached was placed on the front side, and the look and feel of the pattern was evaluated from various angles. 〇: You can't see the graph. △: There are few graphics. X . See the graphic. -22- 201043470 (5) Thickness of high refractive index layer, low refractive index layer, and transparent conductive thin film layer Thin film sample sheets with high refractive index layer, low refractive index layer, and transparent conductive thin film layer are cut into ImmxlOniin The size is embedded in an epoxy resin for electron microscopy. This was fixed to a sample holder of an ultramicrotome, and a thin section of a section parallel to the short side of the embedded sample piece was produced. Then, a photograph was taken by a transmission electron microscope (manufactured by IEOL Co., Ltd.; TEM-2010) at a portion where the film of the slice was not significantly damaged at an acceleration voltage of 0 2 〇〇 kV and a magnification of 10,000 times in a bright field observation period. The film thickness was determined from the obtained photograph. (6) The refractive index of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer is determined by using a spectroscopic spectrometer (Ellipsometer) for a sample prepared by subjecting each layer to the same film formation conditions on a tantalum wafer. Manufactured by Electronics Co., Ltd., FE-5000), and evaluated the refractive index of 550 nm. Further, the optical transmittance software was used to fit the spectral transmittance measurement data of the film provided with each layer, and the refractive index was calculated. At this time, the film thickness of each layer was evaluated by using the film thickness evaluation method before use. Further, it was confirmed that the refractive index of each layer thus calculated and the refractive index of each layer on the germanium wafer were not greatly different. (7) Specific resistance of transparent conductive film The specific resistance was calculated from the film thickness of the surface resistance 値 and the transparent conductive film layer. (8) Average crystal grain size The film sample sheet in which the transparent conductive film layer was laminated was cut into a size of 1 mm x 10 nun, and the conductive film was faced outward, and attached to an appropriate resin block -23-201043470. After trimming, ultra-thin sections substantially parallel to the surface of the film are produced by the technique of a general ultra-thin slicer. The section was observed by a transmission electron microscope (JE-2010, JEM-2010), and the surface portion of the conductive film having no significant damage was selected, and photographing was performed at an acceleration voltage of 200 kV and a direct magnification of 40,000 times. When the transparent conductive film layer is observed under a transmission electron microscope, a range having a polygonal shape is defined as a crystal grain, and the area of the crystal grain is found. 0 The area of the crystal grain is divided by the pi, and the square root of 値 obtained by r is multiplied by 2 times to obtain the crystal grain size. The crystal grain size of all the indium oxide crystals observed in the transparent conductive film layer under a transmission electron microscope was calculated. The average enthalpy of all the crystal grain sizes was taken as the average crystal grain size. (9) Ratio of amorphous portion to crystalline portion The area ratio of the crystalline portion to the amorphous portion when observed under a transmission electron microscope was calculated.实施 [Example 1] Toluene/MEK (80/20: mass) as a solvent was added to 100 parts by mass of an ultraviolet curable acrylic resin (Seikabeam EXF-01 J, manufactured by Daisei Seiki Co., Ltd.) containing a photopolymerization initiator. The mixed solvent of the ratio was 50% by mass of the solid content, and the mixture was stirred and uniformly dissolved to prepare a coating liquid. A two-axis alignment transparent PET film (made by Toyobo Co., Ltd., A4300, thickness lOOy m) having an easy-to-bond layer on both sides, and coating the prepared coating liquid to form a coating film thickness 5# using Meyer Bar -24-201043470 m. The coating film was cured by irradiating ultraviolet rays (light quantity: 300 mJ/cm 2) with an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UB042-5AM-W type) at 8 (the TC was dried for 1 minute). After the coating film is applied, it is 1800 (1: heat treatment is performed for 1 minute to reduce the volatile component. And before the film formation, the purpose of removing moisture in the film is to remove the layer of the cured layer. The shaft alignment transparent PET film was vacuum-expanded and subjected to a rewinding treatment in a vacuum processing chamber. The pressure at this time was 0_002 Pa, and the exposure time was 20 minutes. Moreover, the temperature of the center roller was 40 ° C, and the film passed through the center. Next, a transparent conductive film made of an indium-tin composite oxide is formed on the cured layer to form a high refractive index layer. In this case, the pressure before the shovel is set to 0.000 1 Pa, and the content is included. As a target of 36% by mass of tin oxide indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 6.9 g/cm 3 ), DC power of 2 W/cm 2 was applied, and Ar gas was surface-treated with 130 sccm and 〇2 gas. 〇2 flow when the resistance 値 is minimum 3 times the flow rate was flowed, and the film was formed by DC magnetron sputtering in an atmosphere of 〇.4 Pa. Further, the oxygen partial pressure of the atmosphere was observed for a long time by a sputtering process monitor (manufactured by LEYBOLD INFICON, Transpector XPR3), and feedback was given. The oxygen flow rate and the DC power supply make the degree of oxidation in the indium-tin composite oxide film constant. As described above, the high refractive index of the indium-tin composite oxide deposited to a thickness of l〇nm and a refractive index of 1.93 is formed. The surface resistivity of the high refractive index layer thus obtained is 1×1 /□ or more. -25- 201043470 Further, in order to form a Si〇2 film as a low refractive index layer on the high refractive layer, The target is flown by a DC magnetron sputtering method, a vacuum degree of 0.27 Pa, a gas gas of 500 sccm, and a helium gas of 80 sccm. The temperature is observed in a film for a long period of time. To the flowmeter of oxygen, the voltage 値 is made constant. As in the above manner, a low refractive index layer having a thickness of 35 nm and a refractive index of 1.46 is deposited. ^ Next, the indium-tin composite oxidation is performed on the low refractive index layer. Transparent and transparent The conductive film was formed into a film. At this time, the pressure before sputtering was set to 0.000 Pa, and indium oxide containing 3% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) was used as a target. A DC power of 2 W/cm 2 was applied, and a flow rate of 130 sccm of Ar gas and a minimum of surface resistance 〇 of the 〇 2 gas was flowed, and a film was formed by DC magnetron sputtering at an atmosphere of 0.4 Pa. The temperature of the central roll was adjusted to 10 ° C and the film temperature was about 10 ° C. Further, a sputtering process monitor (manufactured by LEY BOLD INFICON Co., Ltd., Transpector XPR3) was used to observe the water pressure of argon in the film formation atmosphere, and to deposit an indium-tin composite oxide having a thickness of 20 nm and a refractive index of 1.96. A transparent conductive film is used to form a transparent conductive laminated film. [Example 2] The same procedure as in Example 1 was carried out, except that the target was changed to indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) containing 1% by mass of tin oxide as a target for forming a transparent conductive film. A transparent conductive laminated film was produced. [Example 3] -26-201043470 In addition to the indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) containing 5% by mass of tin oxide as a target for forming a transparent conductive film, In the same manner as in Example 1, a transparent conductive laminated film was produced. [Example 4] In the same manner as in Example 1, except that the target was changed to indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) containing 7.5 mass% of tin oxide. A transparent conductive laminated film was produced. [Example 5] A transparent conductive laminated film was formed in the same manner as in Example 1 except that the temperature of the center roll in the vacuum processing chamber was set to 70 °C in the vacuum processing chamber. [Example 6] A transparent conductive laminated film was formed in the same manner as in Example 1 except that the temperature of the center roll in the vacuum processing chamber was 30 °C.实施 [Embodiment 7] In the first embodiment, when a transparent conductive film made of an indium-tin composite oxide is formed on a low refractive index layer, it is not a normal pulsed DC power source but a high power pulse. Power supply for magnetron sputtering (HMP2/3, manufactured by HUETTINGER). In this case, the pressure before the sputtering was set to 0.0001 Pa, and indium oxide containing 3% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) was used as a target, and the charging voltage was 500 V, the pulse frequency. 5 00 Hz, pulse width 150 / / S. Further, Ar gas was flown at a flow rate of -27 - 201043470 13 0 sccm and 〇 2 gas at a minimum surface resistance ,, and the center roll temperature was set to 10 ° C under an atmosphere of 0.4 Pa to perform sputtering. Further, a transparent conductive material composed of an indium-tin composite oxide having a thickness of 20 nm and a refractive index of 2.01 was observed by a sputtering process monitor (manufactured by LEYBOLD INFICON Co., Ltd., Transpector XPR3) to observe the water pressure of argon in the film formation atmosphere. Film. Others were formed into a transparent conductive laminated film in the same manner as in the first embodiment. [Example 8] Example 1 except that a film composed of a chromium-bismuth composite oxide (Zr〇2-SiCh) as a high refractive index layer was formed on the cured layer, and Example 1 The same is formed as a transparent conductive laminated film. In this case, the pressure before the sputtering was set to 0.000 1 Pa, and ZWSh (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied, and the DC magnetron sputtering method was used, and the degree of vacuum was 0.27 Pa. The gas Ar gas system was flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and a helium gas system to form a film. Moreover, G long-term observation of the voltage 値 in the film formation, and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a high refractive index layer having a thickness of 12 nm and a refractive index of 1.75 was deposited. [Example 9] A transparent conductive laminate was produced in the same manner as in Example 1 except that a film made of titanium oxide (TiCh) as a high refractive index layer was formed on the cured layer. film. At this time, the pressure before the sputtering was set to 0.000 lPa, and Ti (manufactured by Mitsui-28-201043470 metal) was used as a target, and DC power of 2 W/cm 2 was applied, and DC magnetron sputtering was used, and the degree of vacuum was 27. 27Pa, an Ar gas system as a gas was flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and a helium gas system to form a film. Moreover, the flow rate 値 in the film formation for a long time and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a high refractive index layer having a thickness of 8 nm and a refractive index of 2.29 was deposited. [Example 1 0] 0 In the same manner as in Example 1, except that a film made of zinc sulfide (ZnS) as a high refractive index layer was formed on the cured layer, transparent conductivity was produced. Laminated film. At this time, the pressure before the sputtering was set to 0.000 lPa, and zinc sulfide (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and a high frequency power of 13.56 MHz of 2 W/cm 2 was applied, and the degree of vacuum was measured by magnetron sputtering. 0.27 Pa and an Ar gas system as a gas were flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and a helium gas system to form a film. Moreover, the voltage 値 in the film formation is observed for a long time, and the flow rate of oxygen is fed back to make the voltage 値 constant. As described above, a high refractive index layer having a thickness of 7.5 nm and a refractive index of 2.43 was deposited. [Example 1 1] A transparent conductive film was produced in the same manner as in Example 1 except that a film made of magnesium fluoride (MgF2) as a low refractive index layer was formed on the cured product layer. Laminated film. At this time, the pressure before sputtering was set to 0.0001 Pa, and magnesium fluoride (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and a high frequency electric -29-201043470 force of 13.5 6 Hz of 2 W/cm 2 was applied, and magnetron sputtering was performed. The plating method and the degree of vacuum were 0.27 Pa, and the Ar system as a gas was flowed at a flow rate of 500 sccm to form a film. Moreover, a long-term observation of the voltage 値 in the membrane and a flow meter fed back to the oxygen causes the voltage 値 to be constant. As described above, a low-refractive layer having a thickness of 40 nm and a refractive index of 1.36 was deposited. [Example 1 2] In addition to Example 1, a thin film composed of an aluminum-niobium composite oxide (Al2〇3-Si〇2) as a low refractive index layer 0 was formed on a cured layer, and Examples 1 A transparent conductive laminated film was produced in the same manner. At this time, the pressure before sputtering is set to 〇.〇〇〇lPa, and APSiOO: 50wt%) (made of Mitsui Metals Co., Ltd.) is used as a target, and □ 2W/cm 2 DC power is applied, using a magnetron splashing method. The degree of vacuum was 27.27 Pa, and a film was formed as a gas Ar gas system at a flow rate of 80 seem at 500 sccm and a helium gas system. Further, the voltage 値 in the film formation is observed for a long period of time, and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a low refractive index layer having a thickness of 〇 3 5 m and a refractive index of 1.5 5 was deposited. [Example 1 3] The transparent conductive laminated film obtained in the same manner as in Example 1 was subjected to heat treatment at 120 ° C for 60 minutes. The heat treatment is carried out until the pressure is reduced to 〇. [Comparative Example 1] In the same manner as in Example 1, except that the high refractive index layer and the low refractive index layer were not provided, and the film thickness of the transparent conductive film layer was changed to 22 nm, the I gas to be used for the formation of the gas was produced. Conductive laminated film with IPa thin -30- 201043470. [Comparative Example 2] A transparent conductive laminated film was produced in the same manner as in Example 1 except that the high refractive index layer was not provided. [Comparative Example 3] A transparent conductive laminated film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was changed to 10 nm. [Comparative Example 4] A transparent conductive laminated film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was changed to 100 nm. [Comparative Example 5] The same as in Example 1, except that indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) containing 1% by mass of tin oxide was used as the target for forming a transparent conductive film. A transparent conductive laminated film was produced. [Comparative Example 6] A sample was produced in the same manner as in Example 1 except that the target of the transparent conductive film was changed to indium oxide containing no tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ). A transparent conductive laminated film. [Comparative Example 7] A transparent conductive laminated film was formed in the same manner as in Example 1 except that the temperature of the center roll in the vacuum processing chamber was set to 20 °C. [Comparative Example 8] -31 - 201043470 In addition to the first embodiment, a film composed of an aluminum-bismuth composite oxide (Al2Ch-Si〇2) as a high refractive index layer was formed on the cured layer, and Example 1 was similarly formed as a transparent conductive laminated film. At this time, the pressure before the sputtering was set to 0.000 lPa, and Al-Si (50: 50 wt%) (manufactured by Mitsui Steel Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied by magnetron sputtering. The degree of vacuum was 〇.27 Pa, and the Ar gas system as a gas was passed through a 500 sccm, 〇2 gas system at a flow rate of 80 sccm, and film formation was carried out. Moreover, the voltage 値 in the film formation is observed for a long time, and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a high refractive index layer having a thickness of 22 m and a refractive index of 1.55 was deposited. [Comparative Example 9] In the same manner as in Example 1, except that a film composed of a chromium-rhenium composite oxide (Zr〇2-SiO〇) which is a low refractive index layer was formed on the cured layer. The topography is a transparent conductive laminated film. At this time, the pressure before the shovel is set to 0.0000 PaPa, and ZrSi2 (made of Sanchai Metal) is used as a target, and DC power of 2 W/cm 2 is applied, and DC magnetron sputtering is used. The plating method, the degree of vacuum was 0.27 Pa, the Ar gas system as a gas was flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and a helium gas system, and the voltage 値 in the film formation was observed for a long time, and the oxygen was fed back. The flowmeter makes the voltage 値 constant. As described above, it is deposited into a low refractive index layer having a thickness of 29 nm and a refractive index of 1.75. -32- 201043470
實施例13 〇 1 < 91.4 91.5 ι 1 〇 ο cn oo cn 實施例12 窆 «—Μ 91.0 oq t-H CO 〇 ο rn 00 實施例11 S f—Η CO Os 91,4 ΓΟ r 4 C<J 〇 ο ro co cn 實施例10 § ι——1 CN ON VO CN 92.2 O) ! < Γ-; 〇 ο cn oo 實施例9 冢 91.9 cn 92.0 oo 1 < in 〇 ο CO oo 實施例8 冢 90.8 p_H r· o\ CO ΓΟ ι—H 〇 ο rn oo 實施例7 沄 ι—Η 91.2 91.3 ι—H «—H 〇 ο CN 實施例6 Ο CO CS 90.9 vq 91.3 ι 1 〇 vq κο CN 實施例5 g 1 91.2 ' VO 91.3 VO 1 ) 〇 ο m CN 0.05 oo Ο 實施例4 o cs CO 90.7 寸· 〇 0.45 oo 實施例3 <N \q P_H σί l〇 CS r~—l 〇 寸· 實施例2 s 卜 cn 91.3 v〇 vq OO 〇 ο > ·4 cs cs r-j 實施例1 o ON T-H 91.2 \a 91.3 W-J r-< P—< 〇 ο (ΤΊ OO r-j 表面電阻値（Ω/口） T1 (%) i-W r〇 TO (%) 〇 rQ o 卜 1 i—i 卜 〇 I r—< 百視辨認性 平均結晶粒徑（nm) 非晶質部比例 比電阻 (xl 〇~4Ω - cm) 水分壓（Xl (T4) 201043470Example 13 〇1 <91.4 91.5 ι 1 〇ο cn oo cn Example 12 窆«—Μ 91.0 oq tH CO 〇ο rn 00 Example 11 S f—Η CO Os 91,4 ΓΟ r 4 C<J 〇 ο ro co cn Example 10 § ι——1 CN ON VO CN 92.2 O) ! <Γ-; 〇ο cn oo Example 9 冢91.9 cn 92.0 oo 1 < in 〇ο CO oo Example 8 冢90.8 p_H r· o\ CO ΓΟ ι—H 〇ο rn oo Example 7 沄ι—Η 91.2 91.3 ι—H «—H 〇ο CN Example 6 Ο CO CS 90.9 vq 91.3 ι 1 〇vq κο CN Example 5 g 1 91.2 ' VO 91.3 VO 1 ) 〇ο m CN 0.05 oo Ο Example 4 o cs CO 90.7 inch · 〇 0.45 oo Example 3 <N \q P_H σί l〇CS r~-l ·· Example 2 s 卜 91.3 v〇vq OO 〇ο > ·4 cs cs rj Example 1 o ON TH 91.2 \a 91.3 WJ r-<P-< 〇ο (ΤΊ OO rj Surface resistance 値 (Ω/口) T1 (%) iW r〇TO (%) 〇rQ o 卜1 i-i 〇I r—< Vision-recognized average crystal grain size (nm) Amorphous portion ratio specific resistance (xl 〇~4Ω - cm) Moisture pressure (Xl (T4) 2 01043470
比較例9 >—Η 90.7 CO 〇4 91.5 OO oo in X ο CO oo c-i 比較例8 ι__4 89.8 oo 〇ά *—H CN ON m <m r4 X ο CO oo cn 比較例7 另 CO 91.2 vq J 91.3 〇 0.95 2 比較例6 ο 91.2 cn VO 1 ) 1 t 〇 8 t—Η 0.15 § r-j 比較例5 CO 90,3 so 90.7 | 寸· r-H 〇 Ο 0.99 \D vd 比較例4 s Η 90.1 cs to 91.3 O) CS cn cn X ο cn OO cn 比較例3 沄 «—Η 口 91.3 | O) CO CN X ο cn oo cn 比較例2 g L 9i^i cn oo ?™*4 X cn oo 比較例1 Ο 1''< 89.5 CO 91.8 J ro wo CN 卜· X ο CO 表面電阻値（Ω/〇) T1 (%) 1~I TO (%) 〇 X> o H 1 1—H o 尸 1 r-H rO 百視辨認性 平均結晶粒徑（ηm) 非晶質部比例 比電阻 (xl 0~4Ω - cm) 水分壓（Xl (Γ4) 201043470 根據表1之結果，滿足本申請案發明的範圍之實施例 1 ~ 1 2記載的透明導電性積層薄膜，係即使將透明導電性薄 膜層圖案化，經圖案化的部分亦不顯著，因此配置在液晶 顯示器等顯示體的前面使用時，係屬目視辨認性優異者。 又，因爲表面電阻値低，故能將畫面尺寸大型化。 另一方面，高折射率層、低折射率層未被適當地配置、 或爲不適當膜厚之比較例1 ~4、8、9記載的透明導電性積層 Λ 薄膜，係因看得到其經圖案化的部分和未形成的部分，所 〇 以目視辨認性差。又，SnCh含有率、水分壓不適當之比較 例5~7記載的透明導電性積層薄膜，係熱處理後的表面電阻 値高，無法使用在畫面尺寸大型化。 [產業上之可利用性] 本發明的透明導電性積層薄膜，表面電阻値低，且因 透明導電性薄膜層之圖形部和非圖形部的光學特性差異 小’所以配置在液晶顯示器等顯示體的前面時，目視辨認 〇 性優異。因此，特別適於作爲靜電電容式觸控面板用的電 極薄膜。 【圖式簡單說明】 第1圖係本發明之透明導電性積層薄膜之說明圖。 【主要元件符號說明】 10 透明導電性薄膜 11 透明塑膠薄膜（基材） 12 硬化物層 -35- 201043470Comparative Example 9 > - Η 90.7 CO 〇 4 91.5 OO oo in X ο CO oo ci Comparative Example 8 ι__4 89.8 oo 〇ά *—H CN ON m <m r4 X ο CO oo cn Comparative Example 7 Another CO 91.2 vq J 91.3 〇0.95 2 Comparative Example 6 ο 91.2 cn VO 1 ) 1 t 〇8 t—Η 0.15 § rj Comparative Example 5 CO 90,3 so 90.7 | inch · rH 〇Ο 0.99 \D vd Comparative Example 4 s Η 90.1 cs To 91.3 O) CS cn cn X ο cn OO cn Comparative Example 3 沄«—Η 口 91.3 | O) CO CN X ο cn oo cn Comparative Example 2 g L 9i^i cn oo ?TM*4 X cn oo Comparative Example 1 Ο 1''< 89.5 CO 91.8 J ro wo CN Bu· X ο CO Surface resistance 値(Ω/〇) T1 (%) 1~I TO (%) 〇X> o H 1 1—H o Corpse 1 rH rO 百 辨 辨 平均 平均 辨 非晶 非晶In the transparent conductive laminated film of the examples 1 to 2, even if the transparent conductive thin film layer is patterned, the patterned portion is not conspicuous. Therefore, when it is disposed in front of a display such as a liquid crystal display, In addition, since the surface resistance is low, the screen size can be increased. On the other hand, the high refractive index layer and the low refractive index layer are not properly disposed, or are compared with an inappropriate film thickness. In the transparent conductive laminated ruthenium film described in Examples 1 to 4, 8, and 9, the patterned portion and the unformed portion were observed, and the visibility was poor. Further, the SnCh content rate and the water pressure were not appropriate. The transparent conductive laminated film described in Comparative Examples 5 to 7 has a high surface resistance after heat treatment and cannot be used to increase the size of the screen. [Industrial Applicability] The transparent conductive laminated film of the present invention has surface resistance. Since the difference in optical characteristics between the pattern portion and the non-pattern portion of the transparent conductive film layer is small, it is excellent in visual recognition when disposed on the front surface of a display such as a liquid crystal display. Therefore, it is particularly suitable as a capacitive type. Electrode thin film for touch panel. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view of a transparent conductive laminated film of the present invention. [Description of main component symbols] 10 Transparent Plastic film 11 Transparent electrically film (base material) layer 12 cured -35-201043470
13 高折射率層 14 低折射率層 15 透明導電性薄膜層 20 介電質層 -36-13 High refractive index layer 14 Low refractive index layer 15 Transparent conductive thin film layer 20 Dielectric layer -36-