TW201244947A

TW201244947A - Transparent conductive film, transparent conductive laminated body, and touch panel

Info

Publication number: TW201244947A
Application number: TW101110944A
Authority: TW
Inventors: Shinichi Iwasaki; Yoshitaka Sakamoto; Shiro Ikuhara
Original assignee: Reiko Kk
Priority date: 2011-05-10
Filing date: 2012-03-29
Publication date: 2012-11-16
Also published as: TWI480164B; JPWO2012153573A1; KR101387705B1; WO2012153573A1; JP5190854B2; KR20130028079A

Abstract

The present invention addresses the issue of providing a transparent conductive film, whereby excellent colorless and transparent characteristics can be maintained even if two transparent conductive films are laminated, and a pattern-shaped electrode section can be easily formed. This transparent conductive film is characterized in that a cerium oxide layer, a transparent low-refractive index layer having a refractive index of 1.4 or higher but below 1.7, and a transparent conductive layer are sequentially formed on one surface of a transparent film base material. The transparent low-refractive index layer is preferably a thin film layer composed of a silicon oxide material, and the transparent conductive layer is preferably a thin film layer composed of an ITO material.

Description

201244947 六、發明說明：【發明所屬之技術領域】本發明係關於一種可用作觸控面板中所用之低電阻梨透明電極之透明導電膜，尤其是關於一種適於用作電容式觸控面板之透明導電膜。又，本發明係關於一種自2片上述透明導電膜構成之透明導電積層體、及具備上述透明導電膜或透明導電積層體之觸控面板。【先前技術】近年來，伴隨觸控面板市場擴大，逐漸推進可用作觸控面板之低電阻型透明電極之透明導電膜之開發。例如，專利文獻1記載有電阻膜型透明觸控面板用電極構件（透明導電臈），其特徵在於：於透明基體（1)上，由透明導電性金屬氧化物構成之電阻膜層（2 )、由二氧化矽構成之薄膜層（3 )及由透明導電性金屬氧化物構成之電阻膜層 (4 ) ’以（1 )、（ 2 )、（ 3 )、（ 4 )之順序積層而成。又’記載有可使用氧化銦薄膜、於氧化銦摻雜有氧化錫之薄膜（ITO薄膜）等作為上述透明導電性金屬氧化物的内容，且亦記載有較佳為於電阻膜層與電阻骐層使用同種之透明導電性金屬氧化物的内容。又’作為適於電容式觸控面板之透明導電膜，於專利文獻2中，揭示有一種透明導電性膜，係於透明膜基材之單面或兩面，自該透明膜基材側，依順序形成有第1透明介電質 201244947 層、第2透明介電質層及透明導電層，且上述透明導電層經圖案化，令上述第1透明介電質層之折射率為nl，令上述第2 透明介電質層之折射率為n2，令上述透明導電層之折射率為n3之情形時，滿足n2 < n3 < 〇1之關係，上述第1透明介電質層之厚度為2 nm以上且小於10 nm » 上述第2透明介電質層之厚度為2〇〜55 nm，上述透明導電層之厚度為15〜3〇 nm。進而揭不：上述第丨透明介電質層較佳為由至少含有氧化銦及氧化鈽之複合氧化物構成；上述第2透明介電質層較佳為由Si〇2形成；作為透明導電層之構成材料，可較佳地使用含有氧化錫之氧化銦（ITO )等。記載有：若使用上述專利文獻電阻膜型透明觸控面板用電極構件（透明導電膜），則尤其是透明性與觸控耐久性得到改良，而可提供更高品f且高性能之觸控面板工。上述專利文獻1之透明導電臈於用作表面電阻率為2〇〇〜250 Ω/□之電阻膜式觸控面板時，電阻膜層（透明導電層）之厚度相對較薄，進而於2片透明導電膜之間存在有空間，故主要因透明導電層引起之黃色感覺不會成為大問二然而，如電容式觸控面板般利用重疊有2片透明導電膜之透明導電積層體時’存在有黃色感覺變強，@無法耐於使用等問題。、不尤其是，若如最近般逐漸推進電容式觸控面板之大面 201244947 積化，則手指觸碰觸控面板來進行操作時之相應性變差。因此’為了防止相應性變差，於將觸控面板之全光線透過率維持於8 5 /。以上狀態，使透明導電層變厚，藉此試圖使表面電阻率降至2〇〇 Ω/□以下，較佳為降至…□左右，但因透明導電層變厚而產生黃色感覺變得更強等問題。士圓5 Α所不，α|利文獻j記載之透明導電膜為代表之先前的透明導電膜係通常於透明膜基材〇,)上積層有複數個透明層’且最表層為透明導電層（4,）。又，如圖5Β所不，電容式觸控面板中使用之透明導電膜係需要藉由局部地去除至少透明導電層（4，），而形成圖案狀電極部（4，ρ)β 匕處所明圖案狀電極部係指透明導電膜最表層之透明導電層形成為格子狀或棋盤模樣等期望之模樣的部分。再者除電極部外之部分係未形成有至少透明導電層等包含導電性物質之層的部分（非電極部右使用圖示有本發明之透明導電膜及透明導電積層體，圖1及2而更具體地進行說明，則電容式觸控面板係如圖1C所示，以透明黏著劑將具有電性連接於x方向之圖案狀電極部（4PX)之透明導電膜（左側）、與具有電性連接於γ方向之圖案狀電極部（4Py)之透明導電膜（右側）加Μ貼合，來用作透明導電積層體。再者，於圖1C中，電性連接於Χ方向之圖案狀電極部（4Ρχ )、與電性連接於γ f向之圖案狀電極部（4Py )係以不同顏色來表示，其係用以於如圓2所示般積層2片透明導電膜而構成透明導電積層體時，用以使電極部彼此位置關係易於掌握之方便的顏 201244947 色區分，材料本身係相同。於圖2中，A 、来。α 4# & Α係透明導電積層體之俯視圖，Β 圖::面圆’C係“中之圓C包圍部分之放大圖。如圖2所不，雷交彳, 中使用之透料電積層體係電：於重疊具有電性連接於X方向之圖案狀之透明導電膜、與具有電性連接於Y方向之圖案狀極。P之透明導電臈時，形成於各個透明導電膜之電極部彼此（即，4Px與4py)基本上不會重#。然而，實際上，於透明導電積層體之構造上，形成於上層之透明導電膜與下層之透明導電膜之電極部彼此（4Ρχ與4Py)會稍微產生下重疊之4为（0)0因此，於自正面目測透明導電積層體之面時’該重疊之部分⑼之黃色感覺會較為顯眼，故成為問題（參照圖2C )。以下’於本說明書中，所謂電極部彼此重疊之部分係指如上述般於透明導電積層體或者使用有其之電容式觸控面板中’形成於上層之透明導電膜與下層之透明導電膜之電極部彼此（4Px與4Py )上下會重疊部分，於本說明書中，所謂黃色感覺係指該電極部彼此重疊部分之黃色感覺。觸控面板係覆蓋顯示畫面上者，故被要求無色透明性高’以便可鮮明地辨識顯示畫面。 on 為了使觸控面板（尤其是，經大面積化之電容式觸控面板）於黃色感覺之方面禁得住實際使用，較理想的是觸控面板中電極部彼此重疊部分之b*為+2.5以下，更理想的是為+2.0 以下（b* 係於 CIE (International Commission 6 201244947201244947 VI. Description of the Invention: [Technical Field] The present invention relates to a transparent conductive film which can be used as a low-resistance pear transparent electrode used in a touch panel, and more particularly to a suitable capacitive touch panel. Transparent conductive film. Further, the present invention relates to a transparent conductive laminated body comprising two transparent conductive films, and a touch panel comprising the transparent conductive film or the transparent conductive laminated body. [Prior Art] In recent years, with the expansion of the touch panel market, development of a transparent conductive film which can be used as a low-resistance transparent electrode of a touch panel has been gradually advanced. For example, Patent Document 1 discloses an electrode member (transparent conductive iridium) for a resistive film type transparent touch panel, characterized in that a resistive film layer made of a transparent conductive metal oxide on a transparent substrate (1) (2) The thin film layer (3) composed of cerium oxide and the resistive film layer (4) composed of a transparent conductive metal oxide are laminated in the order of (1), (2), (3), and (4). . Further, as the transparent conductive metal oxide, an indium oxide thin film or a thin film (ITO thin film) doped with tin oxide in indium oxide is described, and it is also preferable to describe the resistive film layer and the resistor 骐. The layer uses the same type of transparent conductive metal oxide. Further, as a transparent conductive film suitable for a capacitive touch panel, Patent Document 2 discloses a transparent conductive film which is applied to one side or both sides of a transparent film substrate, from the side of the transparent film substrate. Forming a first transparent dielectric layer 201244947, a second transparent dielectric layer, and a transparent conductive layer, and the transparent conductive layer is patterned such that the refractive index of the first transparent dielectric layer is nl, When the refractive index of the second transparent dielectric layer is n2 and the refractive index of the transparent conductive layer is n3, the relationship of n2 < n3 < 〇1 is satisfied, and the thickness of the first transparent dielectric layer is 2 nm or more and less than 10 nm » The thickness of the second transparent dielectric layer is 2 〇 to 55 nm, and the thickness of the transparent conductive layer is 15 to 3 〇 nm. Further, the second transparent dielectric layer is preferably composed of a composite oxide containing at least indium oxide and antimony oxide; the second transparent dielectric layer is preferably formed of Si〇2; as a transparent conductive layer As the constituent material, indium oxide (ITO) containing tin oxide or the like can be preferably used. It is described that when the electrode member (transparent conductive film) for a resistive film type transparent touch panel of the above patent document is used, transparency and touch durability are improved, and a higher quality and high performance touch can be provided. Panel worker. When the transparent conductive material of the above Patent Document 1 is used as a resistive film type touch panel having a surface resistivity of 2 〇〇 to 250 Ω/□, the thickness of the resistive film layer (transparent conductive layer) is relatively thin, and further, 2 pieces There is a space between the transparent conductive films, so the yellow feeling caused by the transparent conductive layer is not a big problem. However, when a transparent conductive laminated body having two transparent conductive films is overlapped as in a capacitive touch panel, it exists. There is a feeling that yellow is getting stronger, and @ can't be used. In particular, if the large surface of the capacitive touch panel is gradually advanced in 201244947, the correspondingness of the finger when the touch panel is touched is deteriorated. Therefore, in order to prevent the deterioration of the correspondence, the total light transmittance of the touch panel is maintained at 8 5 /. In the above state, the transparent conductive layer is thickened, thereby attempting to lower the surface resistivity to 2 〇〇 Ω / □ or less, preferably to about □, but the yellowing feeling becomes thicker due to the thickening of the transparent conductive layer. Strong and other issues. The previous transparent conductive film represented by the transparent conductive film described in the document j is usually laminated on the transparent film substrate, a plurality of transparent layers are formed, and the outermost layer is a transparent conductive layer. (4,). Moreover, as shown in FIG. 5, the transparent conductive film used in the capacitive touch panel needs to be formed by partially removing at least the transparent conductive layer (4,) to form the patterned electrode portion (4, ρ) β 匕The pattern electrode portion refers to a portion in which the transparent conductive layer on the outermost layer of the transparent conductive film is formed into a desired pattern such as a lattice shape or a checkerboard pattern. Further, a portion other than the electrode portion is a portion in which at least a layer containing a conductive material such as a transparent conductive layer is not formed (the non-electrode portion is formed by using the transparent conductive film of the present invention and the transparent conductive laminate), and FIGS. 1 and 2 More specifically, the capacitive touch panel has a transparent conductive film (left side) electrically connected to the patterned electrode portion (4PX) in the x direction, and has a transparent adhesive as shown in FIG. 1C. The transparent conductive film (right side) electrically connected to the pattern electrode portion (4Py) in the γ direction is bonded and used as a transparent conductive laminate. Further, in FIG. 1C, the pattern is electrically connected to the Χ direction. The electrode portion (4Ρχ) and the patterned electrode portion (4Py) electrically connected to γ f are represented by different colors, and are formed by laminating two transparent conductive films as shown by the circle 2 to form a transparent layer. In the case of a conductive laminated body, the color of the color is different from that of the electrode layer 201244947, and the material itself is the same. In Fig. 2, A, 。, α 4# & 俯视-type transparent conductive laminated body top view , Β Picture:: Face circle 'C series' A magnified view of the encircling portion of the circle C. As shown in Fig. 2, the cross-linked electrical system used in the crossover is electrically connected to a transparent conductive film having a pattern electrically connected to the X direction. When the transparent conductive 臈 is connected to the Y-direction, the electrode portions formed on the respective transparent conductive films are substantially not heavy to each other (ie, 4Px and 4py). However, actually, the transparent conductive layer is formed. In the structure of the body, the electrode portions of the transparent conductive film formed on the upper layer and the transparent conductive film of the lower layer (4Ρχ and 4Py) are slightly overlapped by 4 (0). Therefore, the transparent conductive laminate is visually observed from the front. In the case of the surface, the yellow sensation of the overlapping portion (9) is conspicuous, which is a problem (see FIG. 2C). Hereinafter, in the present specification, the portion where the electrode portions overlap each other means a transparent conductive laminated body as described above or used. In the capacitive touch panel of the capacitive touch panel, the electrode portions formed by the transparent conductive film on the upper layer and the transparent conductive film on the lower layer overlap each other (4Px and 4Py), and in the present specification, the so-called yellow feeling It refers to the yellow sensation of the overlapping portions of the electrode portions. The touch panel covers the display screen, so it is required to have high colorless transparency so that the display screen can be clearly recognized. On the touch panel (especially, large The capacitive touch panel of the area can not be used for practical use in terms of the yellow feeling. It is preferable that the b* of the overlapping portion of the electrode portions in the touch panel is +2.5 or less, and more desirably +2.0 or less (b*) Attached to CIE (International Commission 6 201244947

Illumination，國際照明委員會）L*a*b*色彩空間内，表示黃色與藍色間之位置的值，負值表示偏藍色’正值表示偏黃色）。為了達成該要求，於構成透明導電膜之各層使用之材料’基本上使用無色透明之物質’但仍然會使特定波長之光被吸收，故存在變為黃色等問題。專利文獻2之發明係提供適於電容式觸控面板之透明導電膜’且記载有•於透明導電層經圖案化之透明導電膜中，圖案部（電極部）與圖案開口部（非電極部）之差異得到抑制，而可獲得外觀良好之透明導電膜，故尤其適於如電谷式觸控面板般將經圖案化之透明導電層（圖案狀電極。卩）升> 成於顯示器之顯示部整面之觸控面板。 d而，即便藉由專利文獻2之透明導電膜，亦未能消除於積層2片臈時，黃色感覺變強等問題。 ,又，專利文獻1及專利文獻2中揭示之透明導電膜均係於膜基材上形成3層而成者，但根據實施例揭示之構成，於第一層（上述三層中最接近膜基材之層）與第三層（最表層）中均含有IT0，故即便藉由触刻僅去除第三層之⑽ 層而形成圖案狀電極部，亦存在經由含ΙΤ〇之第一層來通電等問題。因此’冑了防止不期望之通電，需要去除所有第層〜第二層，而存在需要特殊之飯刻技術且等問題》買战本專利文獻1 :日本專利第4 1 32 1 9 1號公報專利文獻2 :曰本特開20 10-23282號公報 7 201244947 【發明内容】因此本發明之課題在於提供一種不僅於以時:可維持⑴以下之b*值，而且於重疊2片使用二使 :疋：如電容式觸控面板般於玻璃上積層2 時，亦可維持+2.5以下之b*值之透明導電膜，且可容：膜成圖案狀電極部之透明導電膜。 v 本發明人等為了解決上述課題而進行努力研究，結發見藉由在透明臈基材之單面，依序形成耗化物層、透明低折射率層、透明導電層而使獲得之透明導電膜發揮期望之導電性’且於積層2片之情形、或進而於玻璃上積層2 片之If形時’亦維持較低之b*值，從而以至完成本發明。。即，本發明之透明導電膜之特徵在於：於透明臈基材之單面，依序形成有鈽氧化物層、折射率為1.4以上且未滿 1.7之透明低折射率層、透明導電層。上述透明低折射率層較佳為由矽氧化物構成之薄膜層，進而，該矽氧化物薄膜層較佳為藉由化學氣相蒸鍍法 (CVD法）而形成者。又’上述透明導電層較佳為由ITO構成之薄膜層。又’較佳為於上述透明膜基材與上述鈽氧化物層之間’存在聚醋系錨固塗層（anch〇r c〇at)。上述飾氧化物層之厚度較佳為5〜2〇〇 nm，上述透明低折射率層之厚度較佳為5〜200 nm，上述透明導電層之厚度較佳為1〇〜5〇〇 nm。 201244947 上述透明導雷腔^ 極部者。形成有引t ία/或圖案狀電配線及圖案狀電㈣之透明導電㈣積層體。透明黏著劑層貼合，而適於用作透明導電上述透明導電膜較佳為用於觸控面板，尤明導電積層體較佳為用於電容式觸控面板。迷透本發明之透明導電膜具有作為觸控面板之適當電特性，並且於重疊2片時，亦不易帶有黃色導感電覺膜 =膜=之透明導電膜尤其適合用於積層複數片透明導電膜而使用之電容式觸控面板。【實施方式】 .如圖1A所示，本發明之透明導電膜（5 )具有如下構成.於透明膜基材⑴上，至少依序積層㈣氧化物層（2)、透明低折射率層⑴、透明導電層（4)。透明膜基材⑴ 及3層（2〜4)係作為一片透明導電膜而具有全光線透過率為80%以上（較佳為85%以上）程度之透明性即可。再者，於本發明之透明導電膜中，所謂折射率係指相對於波長為550 nm之光的折射率，可藉由分光反射光譜測定來測定。又，各層之厚度係意味著物理性厚度，可藉由螢光X射線分析裝置而測定。本發明之透明導電膜中使用之透明膜基材（〇可使用聚對酞酸乙二酯膜、聚萘二甲酸乙二醇醋臈（—me naphthalate)、聚丙烯膜、丙烯酸膜、聚碳酸酯臈、氟膜等 201244947 透明塑膠骐，其中酸乙二酯膜。就耐熱性等方面而言較佳為聚對酞又，如圖4所示，亦可於上述透明塑膠膜（9)之單面或兩面’形成由樹脂構成之透明硬塗層（1〇)(圖4係表示於透明塑膠臈之兩面形成有硬塗層之例）。如上述，於單面或兩面形成有硬塗層者亦包含於本發明之透明膜基材⑴。藉由將硬塗層形成於透明塑膠膜表面，可隱藏原先存在於透明塑膠膜之劃痕，並且形成有硬塗層之透明膜基材表面之π動性或表面強度提高，故於後加工時，可防止於透明膜基材產生劃痕。尤其是，於將硬塗層形成於透明導電層側之透明塑膠膜表面時，除上述方面夕卜，進而亦可使本發明之透明導電膜的導電性穩定。用於硬塗層之樹脂較佳為使該硬塗層為鉛筆硬度2Η以上者，可使用三聚氰胺系樹脂、紫外線硬化型丙烯酸系樹脂、胺酯系樹脂等透明樹脂，且厚度較佳為丨〜7从爪。又’於形成硬塗層時’會有產生干涉條紋之情形，但於該情形時，較佳為於上述透明塑膠膜與硬塗層之間，設置由樹脂與尚折射率微粒子等構成之干涉防止層（厚度為 10〜50 nm左右，較佳為20〜30 nm左右）。作為上述樹脂，可使用例如丙烯酸系樹脂、聚酯系樹脂等，作為上述高折射率微粒子，可使用由例如氧化鈦、氧化鍅等構成之微粒子0 如上述，於透明塑膠膜與硬塗層之間具有干涉防止層者亦包含於本發明之透明膜基材中。 10 201244947 透明膜基材⑴之厚度較佳為10〜300从m，更佳為 5〇 260 " m，特佳為 50 " m〜2〇〇 " m » 右厚度薄於1〇以m，則尤其是用於觸控面板之情形時在以手指或筆等進行輸入時，塑膠膜之強度不充分，故使透明導電膜之變形過大而於透明導電層（4)上產生龜裂（crack )’其結果為表面電阻率變得不穩^，因此不佳。又會導致透明導電膜捲曲，其結果會使透明導電膜組裝至觸控面板等後作業中，作業性變差，因此不佳,、方面若厚度大於300 " m ,則產生如下問題：於用於電阻膜式觸控面板時，在利用手指或筆等進行輸入時’為了對透明導電膜施加負重而接觸相對之透明導電膜’必需施加所愛以I- + A本之負重的問題。又，透明導電膜之成本亦上升，故不佳。形成於本發明之透明導電膜的鈽氧化物層⑺係3層 (2〜4)中最接近透明膜基材（1)之層。鈽氧化物層⑺ 為透明高折射率層’其折射率為17以上且未滿25左右(更佳為2.0〜2.2)’且折射率高於鄰接之透明低折射率層㈠）。如上述’可認為藉由積層光之折射率不同的2層（2 而使透明性提高。尤盆β _ ^ 尤其疋，鈽氧化物層（2)與透明低折射率層（3)之折射率之差較伟主η。較佳為〇.2以上。進而，藉由使用 δ亥飾氧化物層，與使用右用有除鈽氧化物層外之透明高折射率之If形相比’重疊2片透明導雷眩聋且得到抑制。導電膜時d感覺之增強會錦氧化物層⑴之厚度較佳為5nm〜2〇〇nm。於厚度 201244947 小於5 rm時，無法充分發揮透明高折射率層之特性且透明低折射率層⑺之折射率之差會變小，而無法充分發揮透明南折射率層之作帛（藉由與透明低折射率層之併用而提高透明性）’故不佳。另一方面，若超過2〇〇nm，則因膜應力而容易產生龜裂，因此不佳。更佳之鈽氧化物層（2)之厚度為l〇nm〜5〇nm。再者，鈽氧化物（氧化鈽），其理論上之組成式係表示為Ce〇2,於本發明中，。與〇之元素比較佳亦為} : 2。然而’Ce與〇之元素比無需一定為1:2，而以與〇之元素比稍微變大或變小（具體而言，於組成式Ce〇x中，X處於1.6〜2.1之範圍内）亦包含於本發明之透明導電膜中使用之鈽氧化物。再者’本說明書中，代表上述。〇以16 各2.1 )而表記為Ce〇2。形成於本發明之透明導電膜的透明低折射率層（3 )係如下者，形成於鈽氧化物層（2)與透明導電層（4)之間，發揮提高本發明之透明導電膜的透明性作用。為了發揮上述作用，折射率較佳為14以上且未滿i 7 (更佳為1.4〜1.5) ’又，厚度較佳為5〜2〇〇 nm。於厚度小於5 nm時，無法充分發揮透明低折射率層之特性，且與鈽氧化物層（2 )之折射率之差會變小，而無法充刀發揮透明低折射率層之作用（藉由與透明高折射率層之併用而提高透明度），故不佳。另一方面，若超過200 nm，則因膜應力而容易產生龜因此不佳。更佳之透明低折射率層之厚度為nm〜5 〇 12 201244947 透明低折射率層α$ & 要為滿足上述折射率與厚度範圍之透明層，則無转3，丨ΡΡ糾 ”、特別限制，可使用矽氧化物（Si〇2 )薄膜層等無機氧化物薄膜居、岛7 膜層氟化鎂（MgF2)薄膜層等無機化合物薄膜層、由氟^斧谢氣糸樹月曰或聚矽氧系樹脂等樹脂構成之樹脂薄膜層等。尤其疋，就耐熱性、耐濕熱性之方面而言，較佳為將透明低折射率層（3 )設為矽氧化物薄膜層。再者1氧化物（氧切），其理論上之組成式係表示為Si〇2但Si與〇之元素比無需一定嚴格地為於滿足上述折射率之範圍使Si與。之元素比梢微變大或變小者 (具體而言’於組成式Si〇x中，X處於1.6〜2.1之範圍内者）亦I 3於本發明之透明導電膜中使用之矽氧化物。再者’本說明書中’代表上述Si〇x ( i…‘2 υ而表記為 Si02。再者，若將透明低折射率層（3 )設為由具有電氣絕緣物質（上述無機氧化物薄膜層、無機化合物薄膜層、樹月日溥膜層等）構成之層，則於形成圖案狀電極部時，必需蝕刻來去除之層只有透明導電層，故可削減蝕刻所需之時間及成本。即，本發明之透明導電膜，最接近透明膜基材（1)之層為具有電氣絕緣性之鈽氧化物層（2)，故若透明低折射率層（3 )亦由具有電氣絕緣性之物質構成，則需要圖案狀電極部之形成之層只有透明導電層（4)。然而，本發明使用之透明低折射率層並不限定於具有電氣絕緣性 13 201244947 ^，而只要處於滿士上述折射率之範圍，則亦可為聚。塞吩系、聚乙快系、聚苯胺系、聚吼略系等導電性聚向樹脂混入ΙΤ〇或氧化錫等透明導電性微粒子二二脂薄膜層。於透明低折射率層具有導電性之情形時护成圖案狀電極部時，亦需要蝕刻來去除該層。 y 形成於本發明之透明導電膜之透明導電層（4)係於透明導電膜的最表層之層，且係由透明物之薄膜構成’且發揮對本發明之透明導電膜賦予導電性之作用者。用於透明導電層（4)之透明導電性金屬氧化物薄獏，可使用氧化銦薄膜、氧化錫薄膜、氧化辞薄膜、氧化㈣膜、於氧化銦摻雜有氧化錫之薄膜（IT〇薄膜）等先前用作透明導電膜之透明導電層的導電性金屬氧化物薄膜。其中’特佳為導電性優異之ΙΤ〇薄膜。透月導電層（4 )係發揮決定本發明之透明導電膜具有之表面電阻率之大部分者’其表面電阻率大致較佳為$〜 1000 Ω/□，更佳為2〇〇 Ω/□以下。、彡月導電層（4)之厚度只要為具有上述表面電阻率程度之厚度即可，雖亦根據使用之金屬氧化物薄膜層之種類’但大致較佳為nm〜500 nm。若厚度小於10 nm’則發現表面電阻率有難以穩定之傾向，而無法穩定獲得所期望之導電性，因此不佳。另一方面，若厚度大於500 nm，則由於膜應力而會有於透明導電層⑷上產生龜裂且導電性變差之情形，因此 201244947 不佳。更佳之透明導電層（4)之厚度為15nm〜i〇〇nm。飾氧化物層（2)、透明低折射率層（3)、透明導電層 /4)之形成方法可使用先前公知之形成方法，可使用真空蒸鍍法、濺鍍蒸鍍法、電子束蒸鍍法、cvd法等蒸鍍法、或溶膠-凝膠法等塗佈法等。尤其是’於透明低折射率層（3)為碎氧化物層之情形時’利用CVD法形成’藉此於觸控面板中，可更減少電極部彼此重疊之部分之b *值。可認為其原因在於：利用CVD法形成石夕氧化物層時藉由石夕氧化物層側之飾氧化物層（2)氧化，而㈣氧化物層 (2)之氧化程度為妙氧化物層側會高於透明膜基材側，結果鈽氧化物層（2)之全光線透過率變高。為了將本發明之透明導電膜使用於電容式觸控面板，亦可形成引出配線。引出配線係、於圖ic表示為記號8 :細線二由金屬構成，⑨常僅設置於透明導電膜之外周部刀先刖如下情形為主流，即’引出配線係藉由將透明導電層圖案化I，印刷（網版印刷等）銀膏而形成，但最才木如下古、土 · 為了使邊框（存在於圖1 C左側之透明導電膜兩端之弓I出配線（8)束）之寬度變窄，將銅或者銅合金之薄膜形成於播、透月導電層上後，藉由蝕刻形成更微細之引出配線的方法。 iH * Sft , „ 户马藉由姓刻形成由銅構成之引出配線的方法，可列舉如下方法：藉由減鍵蒸鍵法，於透明導電層 15 201244947 之整面上積層銅層，於其上將抗蝕劑材料塗佈成引出配線之形狀，藉由蝕刻處理去除未塗佈有抗蝕劑材料之部分的銅層’於僅殘留塗佈有抗蝕劑材料之部分的銅層後，去除抗触劑材料’藉此於透明導電層上，形成由銅構成之引出配線的方法。通常’對引出配線要求0.4 Ω/□以下程度之表面電阻值。為了於銅之引出配線達成〇.4 β/□以下之表面電阻值’較佳為將銅厚度設為1 〇〇 nm以上0 又’為了將本發明之透明導電膜用於電容式觸控面板，亦可至少將透明導電層（4 )形成為電性連接於χ方向或Y方向之圖案狀電極部。又’為了不僅可用於觸控面板，而且亦可用於太陽電池或有機EL ( Electro Luminescence、電致發光）等透明電極用，而形成至少將透明導電層（4)設為電路狀之電路亦〇形成圖案狀電極部或電路之方法，可列舉利用有化學品或雷射之蝕刻、或利用水溶性樹脂層之方法。例如，II由钮刻形成圖案狀電極部之方法係於透明膜基材上之整面依序形成鈽氧化物層（2)、透明低折射率層⑴、及透明導電層（4)後，於透明導電層（4)上，將抗触劑材料塗佈成圖案狀電極部之形狀，藉由钱刻溶液 /氣化鐵水溶液、破酸水溶液、鹽酸、王水、草酸水溶液等溶液）進行處理，對未塗佈右怖有抗蝕劑材料之部分（成為 :極分）僅去除透明導電層（4)(即，殘留飾氧化物層⑺與透明低折射率層（3))，且對㈣有抗触劑 16 201244947 材料之部分（成為電極部之部分），殘留上述三層（2〜4 )。此後’可製造如下本發明之透明導電膜：#由去除抗姓劑材料而於透明臈基材之整面上，形成有鈽氧化物層（2)及透明低折射率層（3)，並於其上形成有由透明導電層（4) 構成之圖案狀電極部。再者，本發明之透明導電膜於透明臈基材上具有3層之方面’與專利文& 1及專利文獻2中記載之透明導電膜共通’但專利文獻丨及專利文獻2之實施例巾記載之透明導電膜係、於最接近膜基材之層（第—層）&含作為導電性物質之ITO,故僅蝕刻透明導電膜之最表層（第三層：導電層）會通過第一層而通電（參照圖5B)。因此，需要全部去除第一層至第三層（參照圖5C)，但去除至第一層會存在需要特殊之㈣技術且花費成本等之問冑。與此相對，本發月之透日月f電膜係、第一 & 具有$電性之飾氧化物構成，故無需藉由蝕刻去除整個層，能夠以短時間、低成本進仃利用I虫刻％圖案狀電極部之形成。尤其是’若由如叫之具有電氣絕緣性之物質構成第二層之透明低折射率層 j3、）’則僅蝕刻去除第三層之透明導電層（4)即可，故能 °以紐時間、低成本進行利用蝕刻的圖案狀電極部之形成。又，作為利用水溶性樹脂層來形成圖案狀電極部之方 ί榀：如可列舉如下方法：於透明膜基材之單面，除形成部外之部分（為非電極部之部分）形成水溶性樹脂、面依序形成鈽氧化物層（2 )、透明低折射率層 3)及透明導電層（4)後，浸潰至水中等而去除水溶性 201244947 樹脂層與該水溶性樹脂層上之上述三層（2〜4)，並且殘留未形成有水溶性樹脂層之部分（為電極部之部分）的上述 —層（2〜4)。藉由該方法’亦可製造於透明膜基材之單面， $成有飾氡化物層（2)、透明低折射率層⑴、及由透明導電層（4)構成之圖案狀電極部之本發明的透明導電膜。再者，本發明之透明導電膜中，不僅包含於透明膜基材之單面整面上，積層有上述三層（2〜4)之膜，而且亦包含如上述般形成有圖案狀電極部、或形成有引出配線。形成有引出配線及圖案狀電極部之本發明之透明導電膜係於2片重疊用作透明導電積層體時特佳。此種透明導電積層體係可藉由如下方式製造：上層之透明導電膜之非導電處理面（即’透明膜基材（1)側之面）、與下層之透明導電膜之導電處理面（即’透明導電層（4)側之面）以對向之方式積I，而藉由透明黏著劑層來貼合。用於透明點著劑層之透明黏著劑，可使用於該領域内用來貼合透明導電膜而使用之通常的透明黏著劑。例如為丙烯酸系黏著劑、聚醚系黏著劑等透明黏著劑。透明黏著劑層較佳為以成為介於2片透明導電膜之間均句之層的方式形成。為成為均句之層，較佳為使肖2片塑膠薄片間形成有均勾之透明黏著劑層之市售光學用高透明性黏著劑 (OCA，0pticaI Clear Adhesive )轉印薄片而向透明導電膜轉印該透明黏著劑層。作為本發明之觸控面板，層體之電容式觸控面板，此種特佳為利用上述透明導電積電容式觸控面板可藉由如下 18 201244947 方式構成：例如’ #|由上述透明黏著劑層貼合玻璃基板與上述透月導電積層體，連接上述引出配線與端子，經由可撓性印刷配線而與觸控面板控制驅動器（半導體等）連接。本發明之透明導電膜係不僅於2片重疊而作為透明導電積層體之情形時，可達成+2 5以下之b*值（下限並無尤其限疋，但通常為_3.〇左右），而且如實際之電容式觸控面板般設為於玻璃基板上配置有透明導電積層體之構成時，亦可達成+2.5以下之b*值（下限並無尤其限定，但通常為 -3.0左右）。再者，b*值係可利用色差計測定。如上述’於將本發明之透明導電膜用於電容式觸控面板時，需要藉由透明黏著劑層而與其他透明導電膜、或者玻璃基板貼合，但於如上述般與其他構件接著時，存在如下問題：若構成透明導電膜之透明膜基材/铈氧化物層/透明低折射率層/透明導電層之間的密合性（附著性）低，則會有變得易於產生剝離的問題。尤其疋，引出配線由銅構成之情形時，與透明黏著劑之接著性高，故其結果為透明導電膜會有力的接著於其他構件’而變得容易在透明導電膜内產生剝離（尤其是，透明膜基材與鈽氧化物層之間剝離）。為了解決該問題’需要提高透明膜基材與鈽氧化物層之間的密合性，但於本發明中，如圖4所示，可藉由在透明臈基材（1 )與鈽氧化物層（2 )之間設置聚酯系錨固塗層（11 )，而將全光線透過率及b*值維持於所期望之範圍内’並且提高透明膜基材與鈽氧化物層間之密合性。 201244947 於設置聚酯系錯固塗層之情形時，上述透明膜基材更佳為至少於形成有鈽氧化物層側之面具有硬塗層。換言之’更佳為於硬塗層上形成聚酯系錨固塗層。聚酯系錨固塗層係例如可利用會與羥基反應之硬化劑來使含有經基之聚醋系樹脂硬化而形成。上述含有經基之聚酯系樹脂可列舉聚酯多元醇，上述硬化劑可列舉聚異氛酸酯及/或聚異氰酸酯預聚物。推測為透明膜基材與鈽氧化物層之密合性係因水分而下降，但使上述聚酯多元醇、與上述聚異氰酸酯及/或聚異氰酸酯預聚物硬化而形成之聚酯系錨固塗層係耐水密合性優異，故可無經時變化而達成穩定之密合性。又，由於时熱性優異，故難以受到於形成聚酯系錯固塗層後進行之各成膜步驟（鈽氧化物層、透明低折射率層、透明導電層之形成步驟）中產生之熱影響（難以產生因熱引起之白化或龜裂等）。又作為較佳之聚異氰酸酯及/或聚異氰酸酯預聚物之例’可列舉IPDI系、XDI系、HDI系之聚異氛酸醋及/或聚異氰酸酯預聚物。II由使用該等’可形成難以黃化之聚酯系猫固塗層。此處，所謂IPDI系係指異佛爾酮二異氛酸醋 (is〇Ph〇rone diis〇cyanate)及其改質形態，所謂χΕ>ι系係才曰苯一甲基二異氰酸酯（xylene dHs〇 ηΜ 態，所謂腿系係指六亞甲基二異氛㈣ dnSOCyanate)及其改質形態。改質形態之例可列舉三羥甲基丙烷（TMP ’ trimethyi〇i pr〇pane )加成物體異氰尿酸 20 201244947 酉曰（isocyanurate )體、縮二脲體、脲基甲酸酯體等。聚醋系錯固塗層之厚度較佳為5〜1〇〇 nm。若厚度超過 1 〇〇 nm ’則存在無法將透明導電膜（或透明導電積層體、或者觸控面板）之b*值維持於所期望之範圍内之虞。另一方面，於小於5 nm時，無法充分提高透明膜基材與鈽氧化物層之密合性。又’本發明之透明導電膜亦可用於除電容式外之觸控面板’例如於設為電阻膜式觸控面板之情形時，可藉由如下方式構成.使點狀間隔物介於在形成於玻璃表面之透明導電層與本發明之透明導電膜之透明導電層對向者之間、或者使點狀間隔物介於以透明導電層面彼此對向之方式配置有2片本發明之透明導電膜者之間，且於端部形成引出配線。此時使用之透明導電膜可為形成有圖案狀電極部者’亦可為未形成有圖案狀電極部者。以下，使用實施例而更詳細地對本發明進行說明，但本發明並不限定於實施例。 [實施例1]透明導電膜（透明膜基材/Ce〇2層/Si〇2層 (CVD) /ITO層）之製造藉由反向塗佈法（reverse c〇at meth〇d),於厚度為125 "m之聚對酞酸乙二酯膜（透明塑膠膜）之兩面，形成由丙稀酸系樹脂構成厚度為2 ”之透明硬塗層，以製造兩面硬塗膜（透明膜基材）。接著，對原料藉由制Ce之真空蒸錄法，於上述兩面硬塗膜之單面，形成厚度為17nm之作為鈽氧化物層之Ce〇 21 201244947 薄膜層（透明高折射率層折射率：2ι)。茲i接者#使用'、甲基二石夕氧，於反應氣體中使用氧氣，化學吼相蒸銀法（CVD法）於原料形之叫相層（透明低折射率層折射率：^ 5)。接著，使用IT0而藉由賤鑛篸鑛法 ^ .Λ 於緞沄於原料形成厚度為3〇nmiITO薄膜層（透明導明導電膜。巾製块本發明之透再者’上述各層係形成於透明膜基之單面上的整面。膜基材（兩面硬塗膜) [實施例2]透明導電膜（透明膜基材心〇2層/si〇2層（濺鍍）/IT0層）之製造除使用Si，於製程翁贈φ蚀田与友孔體中使用氬軋，於反應氣體中使用氧氣’藉由義蒸鑛法來取代實施例丨之⑽法而於原料形成厚度為40⑽之叫薄膜層外，與實施例ι相同，製造於透明膜基材（兩面硬塗膜）之單面，依序形成有⑽ 層（透明高折射率層折射率：2.n、叫薄臈層（透明低折射率層折射率：15)、^層（透明導電層）之本發明的透明導電膜。再者，所s胃製程氣體係指用以製作濺鍍（喷濺原料）所用之電漿氣體，所謂反應氣體係指用以與經濺鍍之原料反應的氣體。 [比較例1]透明導電膜（透明膜基材/IT〇層/Si〇2層（濺鍍）/IT0層）之製造製造具有與專利文獻1揭示之透明導電膜相同構成之 22 201244947 透明導電膜（第一層為ITO層；^具體而言，對原料使用ITO 且藉由濺鍍蒸鍍法，在與實施例1相同地製造之兩面硬塗膜的單面’形成厚度為17 nm之ΙΤΟ薄膜層（透明高折射率層折射率：2· 1 )。接著’利用與實施例2相同之方法，形成厚度為40 nm 之Si〇2薄膜層（透明低折射率層折射率：1 ·5 )，接著，利用與實施例1相同之方法，形成厚度為 13 nm之ΙΤΟ薄膜層（透明導電層），以製造比較例1之透明導電膜。 [比較例2]透明導電膜（透明膜基材/SiOx層/Si02層（濺鑛）/ITO層）之製造除使用Si’於製程氣體令使用氬氣，於反應氣體中使用氧氣且藉由濺鍍蒸鍍法，於原料形成厚度為25 薄膜層（透明高折射率層折射率：175)來取代實施例2之Illumination, International Commission on Illumination) indicates the value of the position between yellow and blue in the L*a*b* color space. Negative values indicate a bluish color and a positive value indicates a yellowish color. In order to achieve this, the material used in the respective layers constituting the transparent conductive film 'substantially uses a colorless and transparent substance', but the light of a specific wavelength is still absorbed, so that there is a problem that it becomes yellow. The invention of Patent Document 2 provides a transparent conductive film suitable for a capacitive touch panel and is described in a transparent conductive film in which a transparent conductive layer is patterned, a pattern portion (electrode portion) and a pattern opening portion (non-electrode) The difference in the portion is suppressed, and a transparent conductive film having a good appearance can be obtained, so that it is particularly suitable for patterning a transparent conductive layer (patterned electrode) as in an electric valley type touch panel. The touch panel of the entire display portion. In the case of the transparent conductive film of Patent Document 2, the problem that the yellow feeling becomes strong when the two layers of the laminate are not removed is not eliminated. Further, the transparent conductive films disclosed in Patent Document 1 and Patent Document 2 are formed by forming three layers on a film substrate, but according to the constitution disclosed in the embodiment, the first layer (the closest one among the above three layers) The layer of the substrate and the third layer (the outermost layer) all contain ITO, so even if only the (10) layer of the third layer is removed by the etch, the patterned electrode portion is formed, and the first layer is provided via the yttrium-containing layer. Power up and other issues. Therefore, in order to prevent undesired energization, it is necessary to remove all of the first layer to the second layer, and there is a problem that requires special cooking techniques and the like." Patent Document 1: Japanese Patent No. 4 1 32 1 9 1 [Patent Document 2] 曰本特开20 10-23282号 7 201244947 [Explanation] Therefore, an object of the present invention is to provide a b* value that is not only in time but can maintain (1) or less, and that two pieces are used in two overlapping sheets. :疋: When a layer 2 is laminated on the glass like a capacitive touch panel, a transparent conductive film having a b* value of +2.5 or less can be maintained, and a transparent conductive film having a patterned electrode portion can be accommodated. The inventors of the present invention have made an effort to solve the above problems, and have found that transparent conductive layers are obtained by sequentially forming a consumable layer, a transparent low refractive index layer, and a transparent conductive layer on one side of a transparent tantalum substrate. The film exhibits a desired conductivity 'and a lower b* value when the two sheets are laminated, or further, when the two sheets are stacked on the glass, so that the present invention is completed. . That is, the transparent conductive film of the present invention is characterized in that a tantalum oxide layer, a transparent low refractive index layer having a refractive index of 1.4 or more and less than 1.7, and a transparent conductive layer are sequentially formed on one surface of the transparent tantalum substrate. The transparent low refractive index layer is preferably a thin film layer composed of tantalum oxide. Further, the tantalum oxide thin film layer is preferably formed by a chemical vapor deposition method (CVD method). Further, the transparent conductive layer is preferably a thin film layer made of ITO. Further, it is preferable that a polyester-based anchor coating layer is present between the transparent film substrate and the tantalum oxide layer. The thickness of the above-mentioned decorative oxide layer is preferably 5 to 2 Å, the thickness of the transparent low refractive index layer is preferably 5 to 200 nm, and the thickness of the transparent conductive layer is preferably 1 〇 to 5 〇〇 nm. 201244947 The above transparent guide mine cavity ^ pole part. A transparent conductive (four) laminated body having a conductive wiring and a patterned electrical wiring (4) is formed. The transparent adhesive layer is suitable for use as a transparent conductive. The transparent conductive film is preferably used for a touch panel, and the conductive laminated body is preferably used for a capacitive touch panel. The transparent conductive film of the present invention has appropriate electrical characteristics as a touch panel, and is not easily yellow with a conductive film when the two sheets are overlapped. The transparent conductive film is particularly suitable for laminating a plurality of transparent conductive films. Capacitive touch panel for film use. [Embodiment] As shown in Fig. 1A, the transparent conductive film (5) of the present invention has the following constitution. On the transparent film substrate (1), at least a layer (4) oxide layer (2) and a transparent low refractive index layer (1) are sequentially laminated. , transparent conductive layer (4). The transparent film substrate (1) and the three layers (2 to 4) may have a transparency of a total light transmittance of 80% or more (preferably 85% or more) as a single transparent conductive film. Further, in the transparent conductive film of the present invention, the refractive index means a refractive index with respect to light having a wavelength of 550 nm, which can be measured by spectroscopic reflection spectroscopy. Further, the thickness of each layer means a physical thickness and can be measured by a fluorescent X-ray analyzer. The transparent film substrate used in the transparent conductive film of the present invention (a polyethylene terephthalate film, a polyethylene naphthalate, a polypropylene film, an acrylic film, a polycarbonate) can be used. 201244947 transparent plastic enamel, such as ester oxime, fluorine film, etc., wherein the acid dianlate film is preferably a pair of yttrium in terms of heat resistance, etc., as shown in Fig. 4, or in the above transparent plastic film (9) One side or two sides 'forms a transparent hard coat layer (1 〇) made of a resin (Fig. 4 shows an example in which a hard coat layer is formed on both sides of a transparent plastic enamel). As described above, a hard coat is formed on one or both sides. The layer is also included in the transparent film substrate (1) of the present invention. By forming a hard coat layer on the surface of the transparent plastic film, the scratch film originally formed on the transparent plastic film can be hidden, and the transparent film substrate formed with the hard coat layer can be formed. The π-movement or surface strength of the surface is improved, so that scratches can be prevented from occurring on the transparent film substrate during post-processing. In particular, when the hard coat layer is formed on the surface of the transparent plastic film on the side of the transparent conductive layer, In addition, the transparency of the present invention can also be made The conductive film is preferably one having a pencil hardness of 2 Å or more, and a transparent resin such as a melamine resin, an ultraviolet curable acrylic resin or an amine ester resin can be used. Further, the thickness is preferably 丨7-7 from the claw. Further, when the hard coat layer is formed, there is a case where interference fringes are generated, but in this case, it is preferably disposed between the transparent plastic film and the hard coat layer. An interference preventing layer (having a thickness of about 10 to 50 nm, preferably about 20 to 30 nm) composed of a resin and a refractive index fine particle or the like. As the resin, for example, an acrylic resin or a polyester resin can be used as the resin. As the high refractive index fine particles, fine particles 0 composed of, for example, titanium oxide, cerium oxide or the like can be used. The interference preventing layer between the transparent plastic film and the hard coat layer is also included in the transparent film substrate of the present invention. 10 201244947 The thickness of the transparent film substrate (1) is preferably from 10 to 300 m, more preferably 5 〇 260 " m, particularly preferably 50 " m~2 〇〇" m » the right thickness is thinner than 1 〇 m, especially for In the case of a touch panel, when a finger or a pen is used for input, the strength of the plastic film is insufficient, so that the deformation of the transparent conductive film is excessively large and crack occurs on the transparent conductive layer (4). When the surface resistivity becomes unstable, it is not good, and the transparent conductive film is curled. As a result, the transparent conductive film is assembled into a touch panel or the like, and the workability is deteriorated, so that it is not preferable. If the thickness is greater than 300 " m , the following problems occur: When used for a resistive touch panel, it is necessary to contact a relatively transparent conductive film in order to apply a load to the transparent conductive film when inputting with a finger or a pen. Apply the problem of being loved by I- + A. Moreover, the cost of the transparent conductive film also rises, which is not preferable. The tantalum oxide layer (7) formed in the transparent conductive film of the present invention is the layer closest to the transparent film substrate (1) among the three layers (2 to 4). The tantalum oxide layer (7) is a transparent high refractive index layer having a refractive index of 17 or more and less than about 25 (more preferably 2.0 to 2.2) and having a refractive index higher than that of the adjacent transparent low refractive index layer (I). As described above, it can be considered that the transparency is improved by the two layers having different refractive indices of the laminated light (2), and the refraction of the yttrium oxide layer (2) and the transparent low refractive index layer (3) is improved. The difference between the rates is better than that of the main η. It is preferably 〇.2 or more. Further, by using the δ 亥氧化物 oxide layer, it is 'overlapping' with the transparent shape of the transparent high refractive index outside the yttrium oxide layer. Two transparent guides are stunned and suppressed. The thickness of the sensation of the conductive film is preferably 5 nm to 2 〇〇 nm. When the thickness is less than 5 rm at 201244947, the transparent high refractive index cannot be fully utilized. The characteristics of the rate layer and the difference in refractive index of the transparent low refractive index layer (7) become small, and the transparent south refractive index layer cannot be sufficiently exhibited (by improving the transparency by the use of the transparent low refractive index layer) On the other hand, when it exceeds 2 〇〇 nm, cracks are likely to occur due to film stress, which is not preferable. More preferably, the thickness of the ruthenium oxide layer (2) is from 10 nm to 5 〇 nm. , cerium oxide (cerium oxide), its theoretical composition is expressed as Ce 〇 2, in the present invention The better than the element of 〇 is also : : 2. However, the ratio of 'Ce to 〇 does not need to be 1:2, but slightly larger or smaller than the element of 〇 (specifically, in composition) In Ce〇x, X is in the range of 1.6 to 2.1) and is also included in the transparent conductive film of the present invention. Further, 'in the present specification, it means the above. 〇 is 16 each 2.1) and is expressed as Ce. 〇 2. The transparent low refractive index layer (3) formed on the transparent conductive film of the present invention is formed between the tantalum oxide layer (2) and the transparent conductive layer (4) to enhance the transparency of the transparent conductive film of the present invention. Sexual effect. In order to exert the above effects, the refractive index is preferably 14 or more and less than i 7 (more preferably 1.4 to 1.5). Further, the thickness is preferably 5 to 2 Å nm. When the thickness is less than 5 nm, the characteristics of the transparent low refractive index layer cannot be sufficiently exhibited, and the difference in refractive index from the tantalum oxide layer (2) becomes small, and the function of the transparent low refractive index layer cannot be performed by filling the knife. It is not preferable because it is used in combination with a transparent high refractive index layer to improve transparency). On the other hand, when it exceeds 200 nm, it is difficult to produce a turtle due to film stress, which is not preferable. The thickness of the transparent transparent low refractive index layer is nm~5 〇12 201244947 Transparent low refractive index layer α$ & To be transparent layer satisfying the above refractive index and thickness range, there is no rotation, no correction, no limitation An inorganic oxide film such as a ruthenium oxide (Si〇2) film layer, an inorganic compound film layer such as an island 7 film magnesium fluoride (MgF2) film layer, or a fluorinated axe A resin film layer made of a resin such as a decane resin, etc. In particular, the transparent low refractive index layer (3) is preferably a ruthenium oxide thin film layer in terms of heat resistance and moist heat resistance. 1 oxide (oxygen cut), its theoretical composition is expressed as Si〇2, but the element ratio of Si to germanium does not necessarily have to be strictly in the range of the above refractive index, so that the element of Si and the element is slightly larger than the tip. Or smaller (specifically, 'in the composition formula Si〇x, X is in the range of 1.6 to 2.1) also I 3 is used in the transparent conductive film of the present invention. Further in this specification 'Represents the above Si〇x (i...'2 υ and the record is Si02. When the low refractive index layer (3) is made of a layer having an electrically insulating material (the above-described inorganic oxide thin film layer, inorganic compound thin film layer, or yoghurt film layer), it is necessary to etch the patterned electrode portion. The layer to be removed only has a transparent conductive layer, so that the time and cost required for etching can be reduced. That is, the transparent conductive film of the present invention, the layer closest to the transparent film substrate (1) is an electrically insulating tantalum oxide layer. (2) Therefore, if the transparent low refractive index layer (3) is also made of a material having electrical insulating properties, the layer requiring the formation of the patterned electrode portion has only the transparent conductive layer (4). However, the transparent low layer used in the present invention is low. The refractive index layer is not limited to having electrical insulating properties 13 201244947 ^, and may be polycondensed as long as it is in the range of the above refractive index of the full scale. The phenotype, the polyphenyl fast system, the polyaniline system, the poly fluorene system, etc. The conductive polycondensation resin is mixed with a transparent conductive fine particle 22D film layer such as tantalum or tin oxide. When the transparent low refractive index layer has conductivity, when the patterned electrode portion is protected, etching is also required to remove the conductive layer. y The transparent conductive layer (4) formed on the transparent conductive film of the present invention is layered on the outermost layer of the transparent conductive film, and is composed of a film of a transparent material and functions to impart conductivity to the transparent conductive film of the present invention. A transparent conductive metal oxide thin film for a transparent conductive layer (4), an indium oxide thin film, a tin oxide thin film, an oxidized thin film, an oxidized (tetra) film, or a film in which tin oxide is doped with tin oxide (IT) A conductive metal oxide film which has been used as a transparent conductive layer of a transparent conductive film, such as a ruthenium film. Among them, a ruthenium film which is excellent in conductivity is particularly preferable. The permeable layer (4) is a transparent conductive layer which determines the present invention. The majority of the surface resistivity of the film 'the surface resistivity is preferably about $1 to 1000 Ω/□, more preferably 2 〇〇Ω/□ or less. The thickness of the perovskiy conductive layer (4) may be a thickness having the above surface resistivity, and is preferably preferably from nm to 500 nm depending on the type of the metal oxide thin film layer used. If the thickness is less than 10 nm', it is found that the surface resistivity is difficult to stabilize, and the desired conductivity cannot be stably obtained, which is not preferable. On the other hand, when the thickness is more than 500 nm, cracks may occur in the transparent conductive layer (4) due to the film stress, and conductivity may deteriorate. Therefore, 201244947 is not preferable. More preferably, the transparent conductive layer (4) has a thickness of 15 nm to i 〇〇 nm. A method of forming the decorative oxide layer (2), the transparent low refractive index layer (3), and the transparent conductive layer / 4) may be a previously known forming method, and vacuum evaporation, sputtering vapor deposition, or electron beam evaporation may be used. A vapor deposition method such as a plating method or a cvd method, or a coating method such as a sol-gel method. In particular, when the transparent low refractive index layer (3) is a broken oxide layer, it is formed by a CVD method. Thereby, in the touch panel, the b* value of the portion where the electrode portions overlap each other can be further reduced. It is considered that the reason is that the formation of the shi shi oxide layer by the CVD method is oxidized by the decorative oxide layer (2) on the side of the shixi oxide layer, and the oxidization degree of the (iv) oxide layer (2) is a wonderful oxide layer. The side is higher than the side of the transparent film substrate, and as a result, the total light transmittance of the tantalum oxide layer (2) becomes high. In order to use the transparent conductive film of the present invention for a capacitive touch panel, lead wires may be formed. The wiring system is shown in Figure ic as symbol 8: the thin wire 2 is made of metal, and 9 is usually only provided on the outer periphery of the transparent conductive film. The following is the mainstream, that is, the 'lead wiring system is patterned by the transparent conductive layer. I, printing (screen printing, etc.) silver paste is formed, but the most wood is as follows: ancient, earth, in order to make the frame (the bundle of wires (8) present at both ends of the transparent conductive film on the left side of Figure 1 C) The method of forming a finer lead wire by etching after forming a thin film of copper or a copper alloy on a broadcast and a moon-transparent conductive layer. iH * Sft , „ The method of forming a lead wire made of copper by a surname is exemplified by a method in which a copper layer is laminated on the entire surface of the transparent conductive layer 15 201244947 by a key reduction method. The resist material is applied in the shape of the lead-out wiring, and the copper layer of the portion not coated with the resist material is removed by etching to remove only the copper layer of the portion coated with the resist material. The method of removing the anti-contact agent material to form a lead wiring made of copper on the transparent conductive layer. Generally, the surface resistance value of 0.4 Ω/□ or less is required for the lead-out wiring. 4 The surface resistance value below β / □ is preferably such that the copper thickness is set to 1 〇〇 nm or more and 0. In order to use the transparent conductive film of the present invention for a capacitive touch panel, at least a transparent conductive layer may be used ( 4) It is formed as a pattern electrode portion electrically connected to the χ direction or the Y direction. Further, it can be used not only for a touch panel but also for transparent electrodes such as solar cells or organic EL (electroluminescence). , A method of forming a pattern electrode portion or a circuit by forming a circuit in which at least the transparent conductive layer (4) is formed in a circuit shape, and a method using etching with a chemical or a laser or a method using a water-soluble resin layer can be exemplified. The method of forming the patterned electrode portion by the button is formed by sequentially forming the tantalum oxide layer (2), the transparent low refractive index layer (1), and the transparent conductive layer (4) on the entire surface of the transparent film substrate, and then transparent. On the conductive layer (4), the anti-contact agent material is applied into the shape of the patterned electrode portion, and is treated by a solution of a solution of a carbonized iron, an aqueous solution of an aqueous solution of acid, a solution of hydrochloric acid, a solution of aqua regia or an aqueous solution of oxalic acid, and the like. Only the transparent conductive layer (4) (ie, the residual decorative oxide layer (7) and the transparent low refractive index layer (3)) is removed for the portion of the uncoated resist material (being: the polar portion), and (4) There is a portion of the anti-contact agent 16 201244947 material (which becomes part of the electrode portion), and the above three layers (2 to 4) remain. Thereafter, the transparent conductive film of the present invention can be manufactured as follows: #: On the entire surface of the substrate, ruthenium oxide is formed. a layer (2) and a transparent low refractive index layer (3) having a patterned electrode portion formed of a transparent conductive layer (4) formed thereon. Further, the transparent conductive film of the present invention has a transparent conductive substrate The third layer is 'common with the transparent conductive film described in the patents & 1 and the patent document 2', but the transparent conductive film described in the patent document and the embodiment of the patent document 2 is the layer closest to the film substrate. (First layer) & ITO is contained as a conductive material, so that only the outermost layer (third layer: conductive layer) of the transparent conductive film is etched by the first layer (see FIG. 5B). Therefore, all removal is required. The first layer to the third layer (refer to FIG. 5C), but removal to the first layer may cause a problem that requires special (four) technology and cost. On the other hand, in the present month, the solar cell system and the first & have an electric oxide oxide structure, so that it is not necessary to remove the entire layer by etching, and it is possible to use I in a short time and at low cost. Insecting the formation of the % patterned electrode portion. In particular, if the transparent transparent refractive layer (3) of the second layer is formed by the material having the electrical insulating property, the transparent conductive layer (4) of the third layer can be etched and removed only. The formation of the patterned electrode portion by etching is performed at a low cost and time. Further, as a method of forming a pattern electrode portion by using a water-soluble resin layer, a method of forming a water-soluble solution on a single surface of a transparent film substrate except a portion other than the formation portion (part of the non-electrode portion) is exemplified. a resin, a surface of the tantalum oxide layer (2), a transparent low refractive index layer 3), and a transparent conductive layer (4), which are then impregnated into water or the like to remove the water-soluble 201244947 resin layer and the water-soluble resin layer. The above three layers (2 to 4) are left, and the above-mentioned layer (2 to 4) in which a portion of the water-soluble resin layer (which is a portion of the electrode portion) is not formed remains. By the method, it can also be fabricated on one side of a transparent film substrate, and has a decorative telluride layer (2), a transparent low refractive index layer (1), and a patterned electrode portion composed of a transparent conductive layer (4). The transparent conductive film of the present invention. Further, in the transparent conductive film of the present invention, not only the single-sided entire surface of the transparent film substrate but also the above-mentioned three-layer (2 to 4) film is laminated, and the patterned electrode portion is formed as described above. Or lead wiring is formed. The transparent conductive film of the present invention in which the lead wiring and the pattern electrode portion are formed is particularly preferable when two sheets are used as a transparent conductive laminate. Such a transparent conductive laminated layer system can be manufactured by: a non-conductive treated surface of the upper transparent conductive film (ie, a surface on the side of the transparent film substrate (1)), and a conductive processed surface of the transparent conductive film of the lower layer (ie, The 'surface on the side of the transparent conductive layer (4)) is laminated in the opposite direction, and is bonded by a transparent adhesive layer. A transparent adhesive for a transparent dot-receiving layer can be used as a usual transparent adhesive for use in the field for bonding a transparent conductive film. For example, it is a transparent adhesive such as an acrylic adhesive or a polyether adhesive. The transparent adhesive layer is preferably formed in such a manner as to be a layer between the two transparent conductive films. In order to be a layer of a uniform sentence, it is preferable to form a commercially available optical high transparency adhesive (OCA, 0pticaI Clear Adhesive) transfer sheet having a transparent adhesive layer formed between the two plastic sheets of the shawl to be transparently conductive. The film transfers the transparent adhesive layer. As a touch panel of the present invention, a layered capacitive touch panel, such a transparent conductive capacitive touch panel can be formed by the following 18 201244947 method: for example, '#|from the above transparent adhesive The layer-bonding glass substrate and the vapor-permeable conductive laminate are connected to the lead wires and the terminals, and are connected to a touch panel control driver (semiconductor or the like) via the flexible printed wiring. The transparent conductive film of the present invention can achieve a b* value of +25 or less, not only when the two sheets are overlapped as a transparent conductive laminate, but the lower limit is not particularly limited, but is usually about _3. Further, when a transparent conductive laminated body is disposed on a glass substrate as in the case of an actual capacitive touch panel, a b* value of +2.5 or less can be achieved (the lower limit is not particularly limited, but is usually about -3.0). . Furthermore, the b* value can be measured using a color difference meter. As described above, when the transparent conductive film of the present invention is used for a capacitive touch panel, it is required to be bonded to another transparent conductive film or a glass substrate by a transparent adhesive layer, but when it is combined with other members as described above There is a problem that if the adhesion (adhesion) between the transparent film substrate/tantalum oxide layer/transparent low refractive index layer/transparent conductive layer constituting the transparent conductive film is low, peeling tends to occur. The problem. In particular, when the lead wire is made of copper, the adhesion to the transparent adhesive is high, and as a result, the transparent conductive film is strongly adhered to the other member', and it is easy to cause peeling in the transparent conductive film (especially , peeling between the transparent film substrate and the tantalum oxide layer). In order to solve this problem, it is necessary to improve the adhesion between the transparent film substrate and the tantalum oxide layer, but in the present invention, as shown in FIG. 4, the transparent tantalum substrate (1) and the tantalum oxide can be used. A polyester anchor coating (11) is provided between the layers (2) to maintain the total light transmittance and the b* value within a desired range' and to improve the adhesion between the transparent film substrate and the tantalum oxide layer. . In the case of providing a polyester-based staggered coating layer, the above-mentioned transparent film substrate preferably has a hard coat layer at least on the side on which the tantalum oxide layer layer is formed. In other words, it is more preferable to form a polyester anchor coating on the hard coat layer. The polyester anchor coating layer can be formed, for example, by curing a resin containing a base group by a curing agent which reacts with a hydroxyl group. The polyester-based resin containing a warp group may, for example, be a polyester polyol, and examples of the above-mentioned curing agent include a polyisocyanate and/or a polyisocyanate prepolymer. It is presumed that the adhesion between the transparent film substrate and the tantalum oxide layer is lowered by moisture, but the polyester polyol and the polyester is anchored with the polyisocyanate and/or the polyisocyanate prepolymer. Since the layer is excellent in water-resistant adhesion, stable adhesion can be achieved without change with time. Further, since it is excellent in heat resistance, it is difficult to be affected by heat generation in each film forming step (step of forming a tantalum oxide layer, a transparent low refractive index layer, and a transparent conductive layer) which is performed after forming a polyester-based offset coating layer. (It is difficult to produce whitening or cracking due to heat, etc.). Further, examples of the preferred polyisocyanate and/or polyisocyanate prepolymer include IPDI-based, XDI-based, HDI-based polyisophthalic acid vinegar and/or polyisocyanate prepolymer. II can form a polyester-based cat solid coating which is difficult to yellow by the use of these. Here, the term "IPDI" refers to isophorone diisocyanate (is〇Ph〇rone diis〇cyanate) and its modified form, and the so-called χΕ> ι system is benzene monomethyl diisocyanate (xylene dHs). 〇ηΜ state, the so-called leg system refers to hexamethylene diiso- ence (four) dnSOCyanate) and its modified form. Examples of the modified form include trimethylmethylpropane (TMP 'trimethyi〇i pr〇pane) addition object isocyanuric acid 20 201244947 is (isocyanurate) body, biuret body, allophanate body, and the like. The thickness of the vinegar-based staggered coating is preferably 5 to 1 〇〇 nm. If the thickness exceeds 1 〇〇 nm ', the b* value of the transparent conductive film (or the transparent conductive laminated body or the touch panel) cannot be maintained within a desired range. On the other hand, when it is less than 5 nm, the adhesion between the transparent film substrate and the ruthenium oxide layer cannot be sufficiently improved. Moreover, the transparent conductive film of the present invention can also be used for a touch panel other than a capacitive type. For example, when it is a resistive touch panel, it can be formed as follows. The dot spacer is formed in the formation. Two transparent conductive layers of the present invention are disposed between the transparent conductive layer on the surface of the glass and the transparent conductive layer of the transparent conductive film of the present invention, or the dot spacers are disposed opposite to each other with the transparent conductive layer facing each other. Lead wires are formed between the film and at the ends. The transparent conductive film used at this time may be a pattern electrode portion formed or a pattern electrode portion may not be formed. Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. [Example 1] Production of a transparent conductive film (transparent film substrate / Ce 2 layer / Si 2 layer (CVD) / ITO layer) by reverse coating method (reverse c〇at meth〇d) A two-sided hard coat layer (transparent film) is formed on the two sides of a polyethylene terephthalate film (transparent plastic film) having a thickness of 125 "m to form a transparent hard coat layer of 2" thick by an acrylic resin. Next, a CeC21 201244947 film layer (transparent high refractive index) having a thickness of 17 nm as a tantalum oxide layer was formed on the single side of the two-sided hard coat film by a vacuum evaporation method using Ce. Layer refractive index: 2 ι). I use #, use methyl oxalate, use oxygen in the reaction gas, chemical 吼 phase steaming method (CVD method) in the shape of the raw material called transparent phase The refractive index of the rate layer is: ^ 5). Next, a thickness of 3 〇 nmiITO film layer (transparent conductive film) is formed by using a yttrium ore yttrium method in the raw material using the IT0 (the transparent conductive film is formed. Further, the above layers are formed on the entire surface of one side of the transparent film substrate. Film substrate (two-sided hard coating film) [Example 2] Transparent The conductive film (transparent film substrate core layer 2 layer / si layer 2 layer (sputtering) / IT0 layer) is manufactured by using argon, in the process gas, in the process of the process. A single film made of a transparent film substrate (two-sided hard coat film) is used in the same manner as in Example ι except that the oxygen is used in place of the film layer by the method of the steaming method of the example (10) and the thickness of the raw material is 40 (10). The surface of the present invention is formed with (10) layers (transparent high refractive index layer refractive index: 2.n, called thin tantalum layer (transparent low refractive index layer refractive index: 15), ^ layer (transparent conductive layer) of the transparent conductive of the present invention Further, the s stomach process gas system refers to a plasma gas used for the sputtering (spraying material), and the so-called reaction gas system refers to a gas used for reacting with the sputtered material. [Comparative Example 1] The transparent conductive film (transparent film substrate/IT layer/Si2 layer (sputter)/IT0 layer) is manufactured and manufactured in the same manner as the transparent conductive film disclosed in Patent Document 1 201244947 Transparent conductive film (first layer) ITO layer; ^ Specifically, using ITO for the raw material and by sputtering evaporation method The single-sided hard coat film produced in the same manner as in Example 1 was formed into a thin film layer having a thickness of 17 nm (refractive high refractive index layer refractive index: 2.1). Then, the thickness was formed in the same manner as in Example 2. a 40 nm Si〇2 film layer (transparent low refractive index layer refractive index: 1.25), and then, in the same manner as in Example 1, a ruthenium film layer (transparent conductive layer) having a thickness of 13 nm was formed. The transparent conductive film of Comparative Example 1 was produced. [Comparative Example 2] Production of a transparent conductive film (transparent film substrate / SiOx layer / SiO 2 layer (sputtering) / ITO layer) In addition to using Si' in a process gas, argon gas was used. In the reaction gas, oxygen is used and a thin film layer (transparent high refractive index layer refractive index: 175) is formed in the raw material by sputtering evaporation method instead of the second embodiment.

Ce〇2層外’利用與實施例2相同之方法獲得比較例2之透明導電膜。 [比較例3]透明導電膜（透明膜基材咖層/si〇2層（滅錢）MTO層）之製造除使用ZnS且藉由真空蒸鑛法，於原㈣% nn^ZnS薄膜層Q明高㈣率層折射率：Μ)來取代實施例2之Ce〇2層外，利用愈竇，、實施例2相同之方法獲得比較例3之透明導電膜。 L物性之測定] 對在實施例1及2、以及比_卜膜的表面電阻率、全光線透于透月導電千b值進行測定。表面電 23 201244947 阻率係使用—菱化學公司製造之LGresta Gp mCP T6〇〇來測定，全光線透過率係使用日本電色工業公司製造之Haze Meter NDH 2000來測定，b*值係使用日本電色工業公司製造之 SpeCtro Color Meter SQ2000 來測定。進而，為了調查形成於透明導電膜之各層間的密合性是否於實際使用上無問題，藉由以下之方法調查膠帶密合性。首先，於使透明膠帶（se丨丨〇tape )密合至透明導電層（ιτ〇層）上後，剝離透明膠帶來進行確認，將透明高折射率層、透明低折射率層、透明導電層中之任一層均未自透明導電膜剝離之情形評估為〇，將透明高折射率層、透明低折射率層、透明導電層中之任一層自透明導電膜剝離之情形評估X。又，於實際使用在實施例丨及2、以及比較例丨'3所得之透明導電膜纟製造透明導電積㈣、及觸控面板之情形時，為了掌握電極部彼此重疊部分之b*值與全光線透過率之值，製造電極部彼此於整面重疊之積層體（即，積層2 片未形成有圖案狀電極部之透明導電膜者）、及具有該積層體之面板’而對b*值與全光線透過率進行測定。首先，對於在實施例〗及2、以及比較例〗〜3所得之透明導電膜各者，藉由透明黏著劑層貼合2片透明導電膜而製造積層體。上述透明黏著劑層係藉由如下方式形成：使用2片塑膠薄片間形成有均勻之丙烯酸系透明黏著劑層之高透明性黏著劑轉印膠帶（住友3M公司製造製品編號： 8146-4)’轉印至一透明導電膜。再者，該積層體上層之透 24 201244947 明導電膜的非導電處理面（透明膜基材側之面）與下層之透明導電膜的導電處理面（ITO層側之面）以面對之方式貼合0 對於以此方式獲得之由2片透明導電膜構成之積層體’與上述相同地測定全光線透過率、b *值。又’形成具有如下構造之面板：於厚度為2 mm之無色透明之板狀玻璃上’積層上述積層體。玻璃與上述積層體係使用上述丙烯酸系透明黏著劑層而貼合。對於以此方式獲得的由上述積層體與玻璃構成之面板，與上述相同地測定全光線透過率、b *值。將測定結果示於表i。再者’上述積層體與面板除未形成有由透明導電層構成之圖案狀電極部外（透明導電層形成於整面），具有與圖 2B所示之透明導電積層體及圖3所示之觸控面板相同之構成。 25 201244947 < 综合評估04 ◎ 〇 X X X 面板η3 +1.59 +1.95 +3.10 +4.23 +4.30 積層體112 -0.89 oo 1 +2.70 +5.13 +1.80 透明導電膜111 -2.18 -2.92 +0.60 + 1.80 •3.49 全光線透過率（％) 面板η3 87.74 85.49 86.50 85.18 82.80 積層體112 86.19 82.87 82.10 82.60 82.40 透明導電膜ttl 89.25 85.34 88.10 86.38 86.90 膠帶密合性〇〇〇〇 X 表面電阻率（Ω/Π) 141.3 152.2 155.0 152.4 153.3 第三層透明導電層 1TO (30 nm) ITO (30 nm) ITO (13 nm ) ITO (30 nm) ITO (30 nm) Μ 浓透明低折射率層 Si02 (CVD)/(40 nm) Si02 (減鍵）/ ( 40 nm ) Si02 (滅鍵）/ ( 40 nm ) Si02 (¾^)/(50 nm) Si02 (激錄）/(45 nm) 第一層透明高折射率層 Ce02 (17 nm ) Ce02 (17 nm ) ITO (17 nm ) SiOx (25 nm) ZnS (36 nm) 透明膜基材 PET 05 (125 μτη) 實施例1 實施例2 比較例1 比較例2 比較例3 ^_!H^W ε7/<ν«5·^®1:杯嘀«>«€念：5¾ X礎钵·ΤΜΤι41·ϊτ«ί<筅 * (◎蜱啪绰妹^!?!^w^vee islr*) 〇％·ί5!%τΓ<·ί ς<Ν+^ίΓ«·^-Β·ν^ι4ί^··6-^« ,*3f«*®$.^s:BiHsniMl. T1/OS8 嫦«-頊韧诸·¥<!Μν^νΒ-〇砹恕<0俤给辁-ix-IPG ooz 砹铛进铖《<^栈实：寸讨 ^«wsi^€<l>s^li砌雜涅 ii-ffimf < 埋一,issi?ac3«i诨铝^«Mraiwsl铖蛴ff«f/s伊iss^/IF-isw : ε^ί 彻琏铖!*·®:Β^Μ:(Ν<<>«#Ί#砌«s^-ffias:<Ntf 1!»:埤侩«11跄诨^>璀《4£坩，雔噢«5"^3找噠«-^聆«1.^«画杯噠荦^:1找 201244947 如自表1可知，實施例1及2、以及比較例丨〜3之透明導電膜之b*值分別為+2.5以下。然而，於2片重疊而構成積層體之情形時，比較例i 及比較例2之透明導電膜之b*值超過+2 5。比較例3之透明導電膜可達成+2.5以下之b*值，但為膠帶密合性較差而不會耐於實際使用者。進而，於構成在玻璃上積層2片透明導電膜之面板之情形時，使用有比較例i〜3之透明導電膜之面板的b*值大幅超過+2.5而強烈地帶有黃色感覺。與此相對實施例1及貫施例2之本發明之透明導電膜無論於2片重疊而構成積層體之情形時，或是於在玻璃上積層2片透明導電膜而構成面板之情形時，均可維持值為+2.5以下，可實現所期望之無色透明性。又，透明導電膜於設為觸控面板之形態時，較佳為可達成85%以上之全光線透過率者，但使用有實施例】及實施例2之透明導電膜的面板均滿^該基準。與此相對，使用有比較们之透明導電膜的面板，其全光線透過率到 8 5%。又’若對藉由CVD法形成作為第2層（透明低折射率層）之Si〇2層的實施例i之透明導電膜、與藉由減錄蒸於法形成作為第2層（透明低折射率層）之si〇2層的實施： 2之透明導電臈進行比較，則如表！所示般觀察到如轉現象：於透明導電膜或積層體之情形時，實施例2之匕反* 值較小’但於面板之情形時，實施例！之b*值變小的反轉 27 201244947 見象又，全光線透過率於透明導雷中之杯一〜* 处乃導電膜、積層冑、及面板 ,月/·，均成為實施例1高於實施例2之結果。對此進行幾次追加試驗，_^ 概冑藉由CVD法而形成之Si02層與藉由濺鍍蒸鍍法而形成之Si0層 2僧進仃比較，但與上述實施例相同，藉由CVD ί#·來fib' a 法形成Sl〇2層於構成面板時，結果為全率高且b*值低。根據該等情形，可知藉由CVD法形成S1〇2層（透明低折射率層）之透明導電膜適於電容式觸控面板。十士不同Si〇2層形成方法對全光線透過率及值造成影響之原因進行研究，則可認為藉由CVD法形成Si〇2層，其Ce02層之Si〇2層側表面受到氧化而氧化程度會高於㈣蒸鍍法’其結果於㈤2氧化物層中產生氧化程度傾斜之 (Ce〇2層之氧化程度係Si〇2層側變得高於透明膜基材側）結果，該結果有助於全光線透過率及b*值之提高。 [利用蝕刻之圖案狀電極部之形成] 對於在實施例1及比較例丨製造之透明導電膜藉由蝕刻法形成電性連接於X或Y方向之圖案狀電極部。 [實施例3] 首先’在實施例1製造之本發明之透明導電膜（透明膜基材/Ce02層/Si02層（CVD) /ITO層）上，將抗蝕劑材料（關西塗料（Kansai Paint)公司製造ALESSSPR)塗佈成圖案狀電極部之形狀，使用2%鹽酸水溶液作為蝕刻液以 40°C進行70秒鐘之濕式蝕刻處理，對於未塗佈有抗蝕劑材料之部分，僅去除ITO層而殘留Ce〇2層/Si〇2層，對於塗 28 201244947 佈有抗蝕劑材料之部分，殘留Ce〇2層/Si〇2層/IT〇層。此後，製造如下之本發明之透明導電膜：藉由以2%氫氧化鈉水溶液去除抗蝕劑材料，而於透明膜基材之整面上形成有The transparent conductive film of Comparative Example 2 was obtained by the same method as in Example 2 except for the Ce 2 layer. [Comparative Example 3] Production of a transparent conductive film (transparent film substrate layer/si〇2 layer (killing money) MTO layer) except for using ZnS and by vacuum evaporation, in the original (tetra)% nn^ZnS film layer Q The transparent conductive film of Comparative Example 3 was obtained by the same method as in Example 2 except that the refractive index: Μ) was used instead of the Ce 〇 2 layer of Example 2. Measurement of L physical properties] The surface resistivities of the films of Examples 1 and 2, and the ratio of the total light permeation to the monthly conductivity of the b-thickness were measured. Surface Electricity 23 201244947 The resistivity was measured using the LGresta Gp mCP T6〇〇 manufactured by Ryo Chemical Co., Ltd., and the total light transmittance was measured using Haze Meter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the b* value was used by Nippon Electric Co., Ltd. The SpeCtro Color Meter SQ2000 manufactured by Seki Industrial Co., Ltd. was used for measurement. Further, in order to investigate whether or not the adhesion between the layers formed on the transparent conductive film was satisfactory in practical use, the tape adhesion was investigated by the following method. First, after the transparent tape (se丨丨〇tape) is adhered to the transparent conductive layer (the layer), the transparent tape is peeled off to confirm, and the transparent high refractive index layer, the transparent low refractive index layer, and the transparent conductive layer are formed. When any of the layers was not peeled off from the transparent conductive film, it was evaluated as 〇, and X of any of the transparent high refractive index layer, the transparent low refractive index layer, and the transparent conductive layer was peeled off from the transparent conductive film. Further, in the case where the transparent conductive film (four) and the touch panel are produced by using the transparent conductive film obtained in the examples 丨 and 2, and the comparative example 3 '3, in order to grasp the b* value of the overlapping portion of the electrode portions, The value of the total light transmittance is such that a laminated body in which the electrode portions overlap the entire surface (that is, a laminated transparent film in which the patterned electrode portion is not formed) and a panel having the laminated body are formed, and b* The value is measured with the total light transmittance. First, in each of the transparent conductive films obtained in Examples 2 and 2 and Comparative Examples 1-3, two laminated transparent conductive films were bonded together by a transparent adhesive layer to produce a laminate. The above transparent adhesive layer is formed by using a highly transparent adhesive transfer tape formed of a uniform acrylic transparent adhesive layer between two plastic sheets (Sumitomo 3M Co., Ltd. article number: 8146-4) Transfer to a transparent conductive film. Further, the non-conductive treated surface (the surface on the side of the transparent film substrate) of the conductive film of the upper layer of the laminated body and the conductive processed surface (the side of the side of the ITO layer) of the transparent conductive film of the lower layer are faced in a manner Bonding 0 The laminated body composed of two transparent conductive films obtained in this manner was measured for the total light transmittance and the b* value in the same manner as described above. Further, a panel having a structure in which the above laminated body was laminated on a colorless transparent plate glass having a thickness of 2 mm was formed. The glass and the above laminated layer are bonded together using the acrylic transparent adhesive layer. With respect to the panel composed of the laminate and the glass obtained in this manner, the total light transmittance and the b* value were measured in the same manner as described above. The measurement results are shown in Table i. Further, the laminated body and the panel are not formed with a patterned electrode portion made of a transparent conductive layer (the transparent conductive layer is formed on the entire surface), and have a transparent conductive laminated body as shown in FIG. 2B and FIG. The same composition of the touch panel. 25 201244947 < Comprehensive evaluation 04 ◎ 〇XXX panel η3 +1.59 +1.95 +3.10 +4.23 +4.30 laminate 112 -0.89 oo 1 +2.70 +5.13 +1.80 transparent conductive film 111 -2.18 -2.92 +0.60 + 1.80 •3.49 Light transmittance (%) Panel η3 87.74 85.49 86.50 85.18 82.80 Laminate 112 86.19 82.87 82.10 82.60 82.40 Transparent conductive film ttl 89.25 85.34 88.10 86.38 86.90 Tape adhesion 〇〇〇〇X Surface resistivity (Ω/Π) 141.3 152.2 155.0 152.4 153.3 Third transparent conductive layer 1TO (30 nm) ITO (30 nm) ITO (13 nm) ITO (30 nm) ITO (30 nm) 浓 Concentrated transparent low refractive index layer SiO 2 (CVD) / (40 nm) Si02 (minus) / ( 40 nm ) Si02 (off key) / ( 40 nm ) Si02 (3⁄4^) / (50 nm) Si02 (excited) / (45 nm) First transparent high refractive index layer Ce02 (17 Nm) Ce02 (17 nm) ITO (17 nm) SiOx (25 nm) ZnS (36 nm) Transparent film substrate PET 05 (125 μτη) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 ^_! H^W ε7/<ν«5·^®1: cup 嘀«>«€念:53⁄4 X基钵·ΤΜΤι41·ϊτ«ί<筅* (◎ sister ^!?!^w^ Vee islr*) 〇%·ί5!%τΓ<·ί ς<Ν+^ίΓ«·^-Β·ν^ι4ί^··6-^« ,*3f«*®$.^s:BiHsniMl. T1/OS8 嫦« -顼韧诸·¥<!Μν^νΒ-〇砹恕<0俤给辁-ix-IPG ooz 砹铛进铖&&;;实实实:寸讨^«wsi^€<l>s ^li杂杂涅ii-ffimf < buried one,issi?ac3«i诨aluminum^«Mraiwsl铖蛴ff«f/sIiss^/IF-isw : ε^ί 琏铖!*·®:Β ^Μ:(Ν<<>«#Ί#laying«s^-ffias:<Ntf 1!»:埤侩«11跄诨^>璀"4£坩,雔噢«5"^3 Looking for 哒«-^听«1.^«画杯哒荦:1 looking for 201244947 As can be seen from Table 1, the b* values of the transparent conductive films of Examples 1 and 2 and Comparative Example 丨3 are respectively +2.5. the following. However, in the case where two sheets were stacked to form a laminate, the b* value of the transparent conductive films of Comparative Example i and Comparative Example 2 exceeded +25. The transparent conductive film of Comparative Example 3 can achieve a b* value of +2.5 or less, but the adhesiveness of the tape is poor and it is not resistant to actual users. Further, in the case of constituting a panel in which two transparent conductive films were laminated on glass, the panel using the transparent conductive films of Comparative Examples i to 3 had a large b* value exceeding +2.5 and strongly exhibited a yellow sensation. In contrast, in the case where the transparent conductive film of the present invention of the first embodiment and the second embodiment is formed by laminating two sheets, or when two transparent conductive films are laminated on the glass to form a panel, The value can be maintained below +2.5 to achieve the desired colorless transparency. Further, when the transparent conductive film is in the form of a touch panel, it is preferable to achieve a total light transmittance of 85% or more, but the panels using the transparent conductive films of the examples and the second embodiment are all full. Benchmark. On the other hand, a panel having a transparent conductive film of comparison has a total light transmittance of 85%. Further, the transparent conductive film of Example i in which the Si 2 layer as the second layer (transparent low refractive index layer) is formed by the CVD method and the second layer (transparent low) are formed by subtractive evaporation. The implementation of the Si〇2 layer of the refractive index layer: 2 The transparent conductive 臈 is compared, as shown in the table! As shown, the phenomenon of rotation is observed: in the case of a transparent conductive film or a laminate, the inverse value of Example 2 is small', but in the case of a panel, the embodiment! The b* value becomes smaller and reversed. 27 201244947 See also, the total light transmittance is in the cup 1~* of the transparent guide mine, the conductive film, the laminated layer, and the panel, the month/·, both become the height of the embodiment 1. The result of Example 2. Several additional tests were carried out on this, and the SiO 2 layer formed by the CVD method was compared with the SiO 2 layer formed by the sputtering vapor deposition method, but the same as in the above embodiment, by CVD. ί#·来fib' a method to form the S1〇2 layer to form the panel, the result is high full rate and low b* value. From these circumstances, it is understood that a transparent conductive film in which an S1 2 layer (transparent low refractive index layer) is formed by a CVD method is suitable for a capacitive touch panel. It is considered that the Si〇2 layer is formed by the CVD method, and the Si〇2 layer side surface of the Ce02 layer is oxidized and oxidized by the reason that the Si 〇 2 layer formation method affects the total light transmittance and the value. The degree is higher than (4) the vapor deposition method. As a result, the degree of oxidation in the (5) 2 oxide layer is inclined (the degree of oxidation of the Ce〇2 layer is higher than the side of the transparent film substrate). Helps increase the total light transmittance and b* value. [Formation of Patterned Electrode Portion by Etching] The transparent conductive film produced in Example 1 and Comparative Example was formed into a pattern electrode portion electrically connected to the X or Y direction by an etching method. [Example 3] First, a resist material (Kansai Paint) was applied to the transparent conductive film (transparent film substrate/Ce02 layer/SiO 2 layer (CVD) / ITO layer) of the present invention produced in Example 1. The company manufactured ALESSSPR) was applied in the shape of a patterned electrode portion, and a wet etching treatment was performed at 40 ° C for 70 seconds using a 2% hydrochloric acid aqueous solution as an etching solution, and only the portion to which the resist material was not applied was used. The ITO layer was removed to leave a layer of Ce 〇 2 layer/Si 〇 2 layer, and for the portion of the coating material of 2012 2012947, which was coated with a resist material, a Ce 〇 2 layer/Si 〇 2 layer/IT 〇 layer remained. Thereafter, the following transparent conductive film of the present invention was produced by forming a resist material on a whole surface of a transparent film substrate by removing the resist material with a 2% aqueous sodium hydroxide solution;

Ce〇2層/Si〇2層，且於其上形成有電性連接於χ方向之由 ITO層構成之圓案狀電極部。再者’除圖案狀電極部外之部分係由Ce〇2層/Si〇2層構成之非電極部。實施例1之透明導電膜中，Ce〇2層、Si〇2層均為絕緣性，故可僅藉由蝕刻去除作為第三層（最表層）之IT〇層，而獲得具有所期望之特性的形成有圖案狀電極部的透明導電臈。進而，與上述相同，亦製造形成有電性連接於γ方向之圖案狀電極部的本發明之透明導電膜。 [比較例4] 除使用於比較例1製造之透明導電膜（透明膜基材/ιτ〇層/Si〇2層/ΙΤΟ層）來取代於實施例i中所製造之本發明之透明導電膜外，與實施例3相同地製造形成有電性連接於χ 方向之由ITO層/S丨〇2層/1丁〇層構成之圖案狀電極部的比較例4之透明導電膜。再者，除圖案狀電極部外之部分係未殘留有IT〇層 /Si〇2層/ΙΤ〇層中之任—者之非電極部（參照圖5C)。進而，與上述相同’亦製造形成有電性連接於Υ方向之圖案狀電極部之比較例4的透明導電膜。再者，對比較例1中製造之透明導電膜進行姓刻時， 29 201244947 僅蚀刻去除作為第三層（最表層）之…，結果產生通過第-層之ΓΓΟ層而通電之問題(參照圖5B之部分放大圖中之箭頭）。因此，為了獲得具有所期望之特性的形成有圖案狀電極部的透明導電冑’需要蝕刻去除全部之層。然而，第二層之Si02層難以第二層為了去除至第一層為止，需要使用Μ蝕刻去除，故沐_料特殊蚀刻法，與僅藉由_去除第三層之㈣相比，本與時間。文尺夕之成根據上述結果，證短時間且低成本進行利點。明本發明之透料電膜具有能夠以用蝕刻之圖案狀電極部的形成等優 [透明導電積層體之製造] [實施例4] 藉由使用上述高透明性黏著劑轉印膠帶而轉印形成之透明黏著劑層，使實施例3製造之形成有電性連接於X方向之圖案狀電極部的本發明之透明導電膜、與形成有電性連接於Y方向之圖案狀電極部的本發明之透明導電膜貼合，藉此製造本發明之透明導電積層體（參照圖2)。雖然形成於各透明導電膜之電極部彼此係以儘可能不重疊之方式積層，但透明導電積層體之構造上，會使電極部彼此猶微重疊之部分產生。再者’如圖2B所示，該透明導電積層體’上層之透明導電膜之非導電處理面（透明膜基材⑴ 側之面）與下層之透明導電膜之導電處理面（㈣層⑷ 側之面）係以面對之方式貼合。 201244947 [比較例5] 除使用比較例4中製造之形成有圖案狀電極部之透明導電膜來取代實施你"中製造的形成有圖案狀電極部的本發明之透明導電膜外，與實施例4相同地製造比較例5之透明導電積層體。利用目測對實施例4中製造之本發明之透明導電積層體、與比較例5中製造之透明導電積層體進行比較，結果可明確地確認比較例5中製造之透明導電積層體，其電極部彼此重疊之部分帶有黃色感覺。另一方面，實施例4中製造的本發明之透明導電積層體中，幾乎不會由目測感覺到電極部彼此重疊部分之黃色感覺，且完全不察覺其存在。 [電容式觸控面板之製造] [實施例5 ] 藉由使用上述高透明性黏著劑轉印膠帶而轉印形成之透明黏著劑層，使上述厚度為2 mm之無色透明之板狀玻璃、與本發明之透明導電積層體之透明導電層面（導電處理面）貼合，並且連接引出配線與端子，經由可撓性印刷配線而連接觸控面板控制驅動器’以製造本發明之電容式觸控面板。上述透明導電積層體除於各透明導電膜上形成有引出配線外，具有與實施例4中製造之透明導電積層體相同之構成。上述引出配線係由Ag或Cu形成。於形成由Ag構成之引出配線時’在進行與實施例3相 31 201244947 同之處理而製造形成有由IT0層構成之圖案狀電極部的透明導電膜後，使用Ag膏且藉由網版印刷法形成。於形成由Cu構成之引出配線時，藉由濺鍍蒸鍍法於 ιτο層之整面，積層厚度為120 nm之Cu層，並於其上將抗蝕劑材料（關西塗料公司製造ALESSSPR)塗佈成引出配線之形狀，使用5〇/〇氣化銅水溶液作為Cu用蝕刻液以4〇艺進行60秒鐘之濕式蝕刻處理，藉此僅去除未塗佈有抗蝕劑材料之部分之Cu層，對於塗佈有抗蝕劑材料之部分，殘留 Cu層。此後，藉由利用2%氮氧化納水溶液去除抗姓劑材料，而於ITO層上製作由Cu構成之引出配線。於形成引出配線後，進行與實施例3相同之處理，從而製造形成有由 ITO層構成之圖案狀電極部之透明導電膜。 [比較例6] 除使用比較例之透明導電積層體（除形成有上述引出配線外’具有與比較例5中製造之透明導電積層體相同之構成）來取代本發明之透明導電積層體外，與實施例5相同地製造比較例6之電容式觸控面板。以目測對實施例5中製造的本發明之電容式觸控面板、與比較例6中製造的電容式觸控面板進行比較，結果可明確地確認出比較例6中製造之電容式觸控面板，電極部彼此重疊之部分帶有黃色感覺。另一方面’實施例5中製造之本發明之電容式觸控面板’幾乎不會由目測感覺到電極部彼此重疊部分之黃色感覺’且完全不察覺其存在。 32 201244947 [關於透明膜基材/Ce02層之密合性之研究] 於製造電容式觸控面板時’當引出配線由Ag構成之情形時’未於透明導電膜觀察到於實際使用上成為問題之層間剝離（於透明膜基材/Ce〇2層/透明低折射率層/透明導電層中之任一者之間產生剝離）’但當引出配線由Cu構成之情形時’觀察到於透明膜基材與Ce〇2層之間，變得容易產生剝離之傾向。可認為其原因在於，由Cu構成之引出配線與透明黏著劑之接著性高於由Ag構成之引出配線，故透明導電膜之表面與其他構件（其他透明導電膜或者玻璃）牢固地接著，其結果，變得易於在透明導電膜中最低密合性 (附著性）之透明膜基材與Ce〇2層之間產生剝離。為了提高透明膜基材與Ce〇2層之密合性，首先研究藉由電暈放電、離子束照射、電漿處理而對透明膜基材表面進行改質（導入羥基），但無論使用哪種表面加工法之情形時，與未進行表面加工之情形相比，結果均會使透明膜基材與Ce〇2層之密合性下降。根據如下情形可認為因水分而使透明膜基材與Ce02層之密合性下降：因羥基導入反而會使透明膜基材與GO〗層之密合性變差的情形；及若對透明導電膜進行加熱處理 (140 c、10分鐘），則觀察到密合性提高之傾向。接著，研究於透明膜基材上設置錨固塗層而提高透明膜基材與Ce〇2層之密合性。將結果示於表2 ^ .實施例6-1及實施例6_2中使用之透明膜基材係如下者.藉由反向塗佈法’於厚度為125 Mm之聚對酞酸乙二 33 201244947 酯膜之兩面，形成由丙烯酸系樹脂構成之厚度為2 /zm的透明硬塗層。此後，藉由凹版法（gravure method )而僅於實施例6-2之透明膜基材形成厚度為20 nm之聚酯系錨固塗層（僅單面）。實施例6-3及實施例6-4中使用之透明膜基材係如下者：藉由反向塗佈法，於厚度為125 /zm之聚對酞酸乙二酯膜之兩面，形成由胺基甲酸乙酯系樹脂構成之厚度為2 "m的透明硬塗層。此後，藉由凹版法而僅於實施例6〜4 之透明膜基材形成厚度為20 nm之聚酯系|苗固塗層（僅單面）。再者’上述聚酯系猫固塗層係藉由如下方式形成：使A Ce 2 layer/Si 2 layer is formed thereon, and a round electrode portion composed of an ITO layer electrically connected to the χ direction is formed thereon. Further, the portion other than the patterned electrode portion is a non-electrode portion composed of a Ce 2 layer/Si 2 layer. In the transparent conductive film of the first embodiment, the Ce〇2 layer and the Si〇2 layer are both insulative, so that the IT layer as the third layer (the outermost layer) can be removed only by etching, and the desired characteristics can be obtained. A transparent conductive crucible having a patterned electrode portion is formed. Further, in the same manner as described above, the transparent conductive film of the present invention in which the pattern electrode portion electrically connected to the γ direction is formed is also produced. [Comparative Example 4] The transparent conductive film of the present invention produced in Example i was used instead of the transparent conductive film (transparent film substrate / 〇〇〇 layer / Si 〇 2 layer / ΙΤΟ layer) manufactured in Comparative Example 1. Further, in the same manner as in Example 3, a transparent conductive film of Comparative Example 4 in which a pattern electrode portion made of an ITO layer/S丨〇2 layer/1 butyl layer was electrically connected to the χ direction was produced. Further, in the portion other than the pattern electrode portion, the non-electrode portion of any of the IT layer/Si 2 layer/layer is not left (see Fig. 5C). Further, in the same manner as described above, the transparent conductive film of Comparative Example 4 in which the pattern electrode portion electrically connected to the Υ direction was formed was also produced. Further, when the transparent conductive film produced in Comparative Example 1 was subjected to a surname, 29 201244947 only etched and removed as the third layer (the outermost layer), and as a result, a problem of energization by the first layer of the germanium layer was generated (refer to the figure). The arrow in the enlarged part of 5B). Therefore, it is necessary to etch away all of the layers in order to obtain a transparent conductive ruthenium having patterned electrode portions having desired characteristics. However, it is difficult for the SiO 2 layer of the second layer to be removed by the ruthenium etching in order to be removed to the first layer. Therefore, the special etching method is the same as the removal of the third layer by _. time. According to the above results, it is proved that the profit is short-term and low-cost. The dielectric film of the present invention has excellent pattern formation of an electrode portion which can be patterned by etching [manufacture of a transparent conductive laminate] [Example 4] Transfer by using the above-mentioned highly transparent adhesive transfer tape The transparent adhesive layer formed in the third embodiment is formed by forming the transparent conductive film of the present invention electrically connected to the patterned electrode portion in the X direction and the pattern electrode portion formed to be electrically connected to the Y direction. The transparent conductive film of the invention is bonded to thereby produce the transparent conductive laminate of the present invention (see Fig. 2). The electrode portions formed in the respective transparent conductive films are laminated in such a manner as not to overlap each other as much as possible, but the structure of the transparent conductive laminated body is caused to partially overlap the electrode portions. Further, as shown in FIG. 2B, the non-conductive treatment surface (the surface on the side of the transparent film substrate (1)) of the transparent conductive film of the upper layer of the transparent conductive laminate body and the conductive treatment surface of the transparent conductive film of the lower layer ((4) layer (4) side) The face is attached in a face-to-face manner. 201244947 [Comparative Example 5] Except that the transparent conductive film of the present invention having the patterned electrode portion manufactured in Comparative Example 4 was used instead of the transparent conductive film of the present invention formed with the pattern electrode portion manufactured in "You" The transparent conductive laminate of Comparative Example 5 was produced in the same manner as in Example 4. When the transparent conductive laminate of the present invention produced in Example 4 was visually observed and compared with the transparent conductive laminate produced in Comparative Example 5, the transparent conductive laminate produced in Comparative Example 5 and the electrode portion thereof were clearly confirmed. The parts that overlap each other have a yellow feel. On the other hand, in the transparent electroconductive laminate of the present invention produced in Example 4, the yellow feeling of the portions where the electrode portions overlap each other was hardly visually perceived, and the existence thereof was not observed at all. [Manufacturing of Capacitive Touch Panel] [Example 5] The transparent adhesive layer formed by transfer using the above-mentioned highly transparent adhesive transfer tape was used to make the above-mentioned colorless transparent plate glass having a thickness of 2 mm, Bonding to the transparent conductive layer (conductive processing surface) of the transparent conductive laminated body of the present invention, and connecting the lead wiring and the terminal, and connecting the touch panel control driver via the flexible printed wiring to manufacture the capacitive touch of the present invention panel. The transparent conductive laminated body has the same configuration as that of the transparent conductive laminated body produced in the fourth embodiment except that the lead wires are formed on the respective transparent conductive films. The above-mentioned lead wiring is formed of Ag or Cu. When the lead wiring made of Ag is formed, the transparent conductive film in which the patterned electrode portion formed of the IT0 layer is formed is processed in the same manner as in the third embodiment 31 201244947, and then Ag paste is used and screen printing is performed. The law is formed. When a lead wiring made of Cu is formed, a Cu layer having a thickness of 120 nm is laminated on the entire surface of the layer by sputtering deposition, and a resist material (ALESSSPR manufactured by Kansai Paint Co., Ltd.) is coated thereon. The shape of the lead-out wiring was used, and a 5 〇/〇 vaporized copper aqueous solution was used as a etching solution for Cu for 60 seconds of wet etching treatment, thereby removing only a portion not coated with the resist material. The Cu layer remains on the portion coated with the resist material, and the Cu layer remains. Thereafter, the anti-surname material was removed by using a 2% aqueous solution of nitrogen oxide, and a lead wiring made of Cu was formed on the ITO layer. After the lead wiring was formed, the same treatment as in Example 3 was carried out to produce a transparent conductive film in which a pattern electrode portion made of an ITO layer was formed. [Comparative Example 6] In place of the transparent conductive laminate of the present invention, in place of the transparent conductive laminate of the comparative example (having the same configuration as the transparent conductive laminate produced in Comparative Example 5 except for the above-described lead-out wiring), The capacitive touch panel of Comparative Example 6 was produced in the same manner as in Example 5. The capacitive touch panel of the present invention manufactured in the fifth embodiment was visually compared with the capacitive touch panel manufactured in Comparative Example 6. As a result, the capacitive touch panel manufactured in Comparative Example 6 was clearly confirmed. The portion where the electrode portions overlap each other has a yellow sensation. On the other hand, the capacitive touch panel of the present invention manufactured in the embodiment 5 hardly visually perceived the yellow feeling of the portions where the electrode portions overlap each other and was completely unaware of its existence. 32 201244947 [Research on the adhesion of the transparent film substrate/Ce02 layer] When manufacturing the capacitive touch panel, 'When the lead wiring is made of Ag', it is not a problem in the actual use of the transparent conductive film. Inter-layer peeling (peeling occurs between any of the transparent film substrate/Ce〇2 layer/transparent low-refractive-index layer/transparent conductive layer)' but when the lead wiring is composed of Cu, 'observed in transparency Between the film substrate and the Ce〇2 layer, peeling tends to occur. This is considered to be because the adhesion between the lead wiring made of Cu and the transparent adhesive is higher than that of the lead line made of Ag, so that the surface of the transparent conductive film is firmly adhered to other members (other transparent conductive film or glass). As a result, peeling occurs between the transparent film substrate and the Ce〇2 layer which are likely to have the lowest adhesion (adhesion) in the transparent conductive film. In order to improve the adhesion between the transparent film substrate and the Ce〇2 layer, first, the surface of the transparent film substrate is modified (introduced into a hydroxyl group) by corona discharge, ion beam irradiation, or plasma treatment, but no matter which one is used. In the case of the surface processing method, as compared with the case where the surface processing is not performed, the adhesion between the transparent film substrate and the Ce 2 layer is lowered as a result. It is considered that the adhesion between the transparent film substrate and the CeO layer due to moisture is lowered as follows: the adhesion between the transparent film substrate and the GO layer is deteriorated due to the introduction of the hydroxyl group; and if the adhesion is transparent, When the film was subjected to heat treatment (140 c, 10 minutes), the adhesion was observed to be improved. Next, it was investigated to provide an anchor coating on the transparent film substrate to improve the adhesion between the transparent film substrate and the Ce 2 layer. The results are shown in Table 2 ^. The transparent film substrates used in Examples 6-1 and 6-2 are as follows. By reverse coating method, the poly-p-benzoic acid B 33 having a thickness of 125 Mm 201244947 On both sides of the ester film, a transparent hard coat layer made of an acrylic resin and having a thickness of 2 /zm was formed. Thereafter, a polyester-based anchor coating layer (only one side) having a thickness of 20 nm was formed only on the transparent film substrate of Example 6-2 by a gravure method. The transparent film substrate used in Example 6-3 and Example 6-4 was as follows: by the reverse coating method, on both sides of a polyethylene terephthalate film having a thickness of 125 /zm, The urethane-based resin is a transparent hard coat layer having a thickness of 2 " m. Thereafter, a polyester-based seed coat layer (only one side) having a thickness of 20 nm was formed only on the transparent film substrates of Examples 6 to 4 by the gravure method. Further, the above polyester-based cat solid coating is formed by:

用東洋油墨（Toyoink)股份有限公司之VMANCHORP331S (於溶劑中，以1 : 1之重量比包含聚酯多元醇與硝化纖維素）作為主劑，使用三井化學股份有限公司之Using the VMANCHORP331S of Toyoink Co., Ltd. (containing polyester polyol and nitrocellulose in a solvent ratio of 1:1 by weight), Mitsui Chemicals Co., Ltd. was used as a main agent.

對於實施例6-1〜6-4 4之各透明膜基材，利用與實施例For each of the transparent film substrates of Examples 6-1 to 6-4, use and examples

以形成本發明之透明導電膜。To form the transparent conductive film of the present invention.

龜裂之產生而無法耐於實際使用者設為χ，，將因白將其他設為 34 201244947 進而’利用與苐測定表® f 頁第4段相同之方法，對各透明膜叙表面電阻率、膠帶密合性、全光線透過率、6值。月膜法：Γ2與第24頁第1段及第24頁第2段相同之方體二成之? 板’從而測定全光線透過率、b*值。進而’為了研究形成膜内之^Cu構成之引出配線時透明導電联η夂層間剝離的程度，膜ΙΤΟ層側之整面n 泰鑛法而於各透明導電積層厚度為120 nm之Cu層，且获ώ 依據JIS Κ5 600 <5 τοα 且藉由玄幻“ (〇24〇9)之橫切法（⑽s cut)，對密合性"(附著性）進行評估。再者，mK觸叫系)以;; 方格進行試驗，但於本試驗中，、為了更洋細地研究密合性’ 0方格進行試驗，將Cu層、IT〇層、Si〇2層、⑽ 層均未剝離之部位於⑽個中為9Q個以上評估為◎ 2 個以上評估為Q，將30個以上評估為△，將小於3〇個呼估為X。評估為〇以上係於實際使用上無㈣之等級。將結果示於表2。 35 201244947 橫切密合性tt5 〇 ◎ 〇 ◎ 面板114 +1.59 +1.61 +1.45 +2.20 積層趙* -0.89 •0.83 s 1 -0.94 透明導電膜α2 -2.18 00 On 1 -2.21 +0.50 全光線透過率（％) I 面板tt4 87.74 87.47 88.10 87.96 積層體n3 86.19 86.33 86.33 86.51 透明導電膜112 89.25 88.50 88.94 87.34 膠帶密合性αι 〇〇〇〇表面電阻率（Ω/Π) 141.3 150.3 146.2 155.3 外觀〇〇〇〇三層之構成〇^〇E ◦ i⑺夂一二i ^ = ¢, 〇 ξ .> c (i| r〇 ' v J C J V J 帐 w 蛛猫固塗層聚酯系聚酯系透明膜基材硬塗層丙烯酸系 2 βϊΏ 胺基甲酸乙酯系 2 /^m 透明塑膠膜 PET 125 //m 實施例 6-1 實施例 6-2 實施例 6-3 實施例 6-4 ^$iJtli^^il?-®«-«<(uluofsl^ttJ(®t:)®isn3^^Tfof-Il?-^:s^ 埠《w^染vf<Dslr砌？ts^-efr«i-sl.^B:a^x(N硃铌甸噢箔欢罾》璀1.跄5:帘/琏_蚧5:帘/诨隹¾:寸《 ♦琏一一掛 s^=c(N<os^_ 雜 s«f-fflff: ε 找 GE毋侩®^fi(t-s??w^«w17^ ,钼_無 W {:找噠班.啭敢«1,^« 困杯嗜染<:3找 _ 鉬$i-H-«/vgfe·验s^tusTf oll^-ffil# : 1 找 201244947 如表2所示，於設置有聚醋系施例0-2及6_4 )，盥去机苗士增疋It形時（實及6 3U" 與未5又置有錨固塗層之情形（實施例6-】 L之Λ,橫切密合性提高。又，透明導電膜、積層體、 =ΓΓ均為85%以上，均為+2.5以下。产形時：1有由環氧系樹脂構成之錯固塗層之 =過Γ設置有錯固塗層之情形相比，不僅可發現全 =:率，值惡化之傾向，而且亦可發現膠帶密合性、橫切密合性惡化之傾向。 [產業上之可利用性] :發明之透明導電膜即便於2片重叠而使用之情形 Β片透::：有黃色感覺，故於如電容式觸控面板般積層2 導電膜而使用之情形時，亦可鮮明地視認顯示畫面，從而非常有用。又，利用I虫刻之圖案狀電極部的形成較為容易，故能夠以低成本、短時間形成圖案狀電極部。【圖式簡單說明】圖1係示意性地表示本發明之透明導電膜之—例，八係透明導電膜之剖面圖’Β係、形成有圖案狀電㈣之透明導電膜的剖面圖’C係具有電性連接力χ方向之圖案狀電極部之透明導電膜（左側）、與電性連接於γ方向之圖案狀電極部之透明導電膜（右側）的俯視圖。圖2係示意性地表示藉由透明黏著劑層來貼合二片圓丄之透明導電膜而構成之本發明之透明導電積層體，A係俯視 37 201244947 圖，B係A中之線B-B剖面圖，（：係由a中圓c包圍之部分放大圖® 圖3係表示藉由透明黏著劑層來貼合圖2之透明導電積層體與玻璃而構成之本發明之觸控面板（其中引出配線並未圖示）。If cracks are generated and cannot be set to 实际 by the actual user, the others will be set to 34 201244947, and then the surface resistivity of each transparent film will be described by the same method as the fourth step of the 苐measurement table. , tape adhesion, total light transmittance, 6 values. Moon film method: Γ2 is the same as the second panel on page 24 and the second paragraph on page 24, and the plate is used to measure the total light transmittance and b* value. Further, in order to study the degree of peeling of the transparent conductive η 夂 layer when forming the wiring formed by the Cu in the film, the entire surface of the film ΙΤΟ layer side is a Cu layer having a thickness of 120 nm for each transparent conductive layer. And obtained 密 according to JIS Κ 5 600 < 5 τοα and by the illusion "(〇24〇9) cross-cutting method ((10) s cut), the adhesion " (adhesion) is evaluated. The test was carried out in square; but in this test, in order to study the adhesion '0 squares more carefully, the Cu layer, the IT layer, the Si〇2 layer, and the (10) layer were not tested. The number of stripping parts in the (10) is 9Q or more. The evaluation is ◎ 2 or more evaluations are Q, 30 or more are evaluated as △, and less than 3 呼 are estimated as X. The evaluation is 〇 or more in actual use. The results are shown in Table 2. 35 201244947 Transverse Adhesion tt5 〇◎ 〇 ◎ Panel 114 +1.59 +1.61 +1.45 +2.20 Laminated Zhao* -0.89 •0.83 s 1 -0.94 Transparent Conductive Film α2 -2.18 00 On 1 -2.21 +0.50 Total light transmittance (%) I Panel tt4 87.74 87.47 88.10 87.96 Laminate n3 86.19 86.33 86 .33 86.51 Transparent Conductive Film 112 89.25 88.50 88.94 87.34 Tape Adhesion αι 〇〇〇〇 Surface Resistivity (Ω/Π) 141.3 150.3 146.2 155.3 Appearance 〇〇〇〇 Three-layer Composition 〇^〇E ◦ i(7)夂一二i ^ = ¢, 〇ξ .> c (i| r〇' v JCJVJ 帐 w spider cat solid coating polyester polyester transparent film substrate hard coat acrylic 2 β ϊΏ urethane 2 /^m Transparent plastic film PET 125 //m Example 6-1 Example 6-2 Example 6-3 Example 6-4 ^$iJtli^^il?-®«-«<(uluofsl^ttJ( ®t:)®isn3^^Tfof-Il?-^:s^ 埠"w^染vf<Dslr ??ts^-efr«i-sl.^B:a^x(N Zhu Judian 噢 foil罾》璀1.跄5: Curtain/琏_蚧5: Curtain/诨隹3⁄4: Inch ♦ 琏琏 s s^=c(N<os^_ Miscellaneous s«f-fflff: ε Find GE毋侩®^fi(ts??w^«w17^, molybdenum_ no W {: find 哒班.啭敢«1,^« 困杯染染<:3 find _ molybdenum $iH-«/vgfe·test s ^tusTf oll^-ffil# : 1 Looking for 201244947 As shown in Table 2, in the setting of the vinegar system examples 0-2 and 6_4), when the machine Miao Shizeng increased its shape (real and 6 3U" and not 5 with anchor coating Examples of Λ L] 6- embodiment, transverse to improve the adhesion. Further, the transparent conductive film, the laminate, and =ΓΓ are both 85% or more, and both are +2.5 or less. When the shape is formed: 1 There is a mis-solid coating made of epoxy resin = Compared with the case where the erroneous coating is provided, it is possible to find not only the full =: rate, but also the tendency to deteriorate the value, and the tape can also be found. Adhesion and cross-cut adhesion tend to deteriorate. [Industrial Applicability]: The transparent conductive film of the invention is used when the two sheets are overlapped. The film is transparent::: It has a yellow sensation, so it is used in a conductive film like a capacitive touch panel. It is also very useful to clearly visualize the display. Further, since it is easy to form the pattern electrode portion by the I insect, the pattern electrode portion can be formed at a low cost and for a short time. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a transparent conductive film of the present invention, a cross-sectional view of an eight-layer transparent conductive film, and a transparent conductive film formed with a patterned electric (four). A plan view of a transparent conductive film (left side) having a pattern electrode portion electrically connected to the direction of the electrical direction and a transparent conductive film (right side) electrically connected to the pattern electrode portion in the γ direction. Fig. 2 is a view schematically showing a transparent conductive laminated body of the present invention which is formed by laminating two transparent conductive films of a circular enamel by a transparent adhesive layer, and a line A is a plan view of Fig. 37 201244947, a line BB of the B line A. Fig. 3 shows a partially enlarged view of a circle c surrounded by a. Fig. 3 shows a touch panel of the present invention which is formed by laminating the transparent conductive laminate of Fig. 2 and a glass by a transparent adhesive layer. Wiring is not shown).

圖4係示意性地表示本發明之透明導電膜之另一例，A 係透明導電膜之剖面圖，B係由A中圓B包圍之部分放大圖。圖5係示意性地表示先前技術之透明導電膜（於第〆層與第三層含有導電性物質之透明導電膜），A係表示該透明導電膜之刮面圖。B係藉由蝕刻僅局部去除第三層（最表層）之圖、與由圓包圍之部分放大圖，放大圖中之箭頭表示電之流動。C係表示藉由蝕刻局部去除所有第—層至第彡層而形成圖案狀電極部之狀態。【主要元件符號說明】 1 ' 1' 透明膜基材 2 鈽氧化物層 2' 包含導電物質之透明高折射率層 3、 3'透明低折射率層 4、 4' 透明導電層 4P、4’P由透明導電層構成之圖案狀電極部 4Px 由透明導電層構成之電性連接於案狀電極部 X方向之圖 38 201244947 4Py 由透明導電層構成之電性連接於Y方向之圖案狀電極部 5、5' 透明導電膜 6 透明黏著劑層 7 玻璃 8 引出配線 9 透明塑膠膜 10 硬塗層 11 聚酯系錨固塗層 C 圓〇上下重疊之部分 39Fig. 4 is a cross-sectional view schematically showing another example of the transparent conductive film of the present invention, the A-type transparent conductive film, and B is a partially enlarged view surrounded by a circle B in A. Fig. 5 is a view schematically showing a transparent conductive film of the prior art (a transparent conductive film containing a conductive material in the second and third layers), and A is a plan view showing the transparent conductive film. B is a partial view of the third layer (the most superficial layer) by etching, and a partially enlarged view surrounded by a circle. The arrows in the enlarged view indicate the flow of electricity. C shows a state in which the patterned electrode portions are formed by locally removing all of the first layer to the second layer by etching. [Description of main component symbols] 1 '1' Transparent film substrate 2 钸Oxide layer 2' Transparent high refractive index layer containing conductive material 3, 3' Transparent low refractive index layer 4, 4' Transparent conductive layer 4P, 4' The patterned electrode portion 4Px composed of a transparent conductive layer is electrically connected to the case electrode portion X in the form of a transparent conductive layer. FIG. 38 201244947 4Py A patterned electrode portion electrically connected to the Y direction by a transparent conductive layer 5, 5' transparent conductive film 6 transparent adhesive layer 7 glass 8 lead wiring 9 transparent plastic film 10 hard coating 11 polyester anchor coating C round upper and lower overlapping part 39

Claims

201244947 VII. Patent application scope: 1. A transparent conductive film is formed on one side of a transparent film substrate, sequentially forming a tantalum oxide layer, a refractive index of 丨·4 or more and less than 7 transparent low refractive index Layer, transparent conductive layer. 2. The transparent conductive film of claim 1, wherein the transparent low refractive index layer is a thin film layer composed of tantalum oxide. 3. The transparent conductive film of claim 2 or 2, wherein a polyester-based anchor coating layer is present between the transparent film substrate and the tantalum oxide layer. 4. Patent Application No. 2 or 3 In the transparent conductive film, the thin film layer composed of the tantalum oxide is formed by a chemical vapor deposition method (cv D method). 5. The transparent conductive film according to any one of claims 4 to 4, wherein the transparent conductive layer is a thin film layer composed of ITO. 6. The transparent conductive film according to any one of claims 5 to 5, wherein the thickness of the tantalum oxide layer is 5 to 200 nm, and the thickness of the transparent low refractive index layer is 5 to 20 nm. The transparent conductive layer has a thickness of 1 〇 to 5 〇〇 nm 〇 7. The transparent conductive film according to any one of the items of the fourth aspect of the invention, which has a lead-out wiring and/or a patterned electrode portion. 8. A transparent conductive laminate which is formed by laminating a transparent conductive film layer of any one of the application of the lead wire and the patterned electrode portion, and is formed by laminating a transparent adhesive layer . A touch panel comprising a transparent conductive film according to any one of claims 7-1. 201244947 1 〇· A capacitive touch panel is a transparent conductive laminate with patent application No. 8. Eight, the pattern: (such as the next page) 41