TW201802829A - Transparent conductive film and touch panel - Google Patents

Transparent conductive film and touch panel Download PDF

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Publication number
TW201802829A
TW201802829A TW106119004A TW106119004A TW201802829A TW 201802829 A TW201802829 A TW 201802829A TW 106119004 A TW106119004 A TW 106119004A TW 106119004 A TW106119004 A TW 106119004A TW 201802829 A TW201802829 A TW 201802829A
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Taiwan
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transparent conductive
conductive film
film
transparent
resin layer
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TW106119004A
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Chinese (zh)
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TWI739847B (en
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松本圭祐
金谷実
梨木智剛
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日東電工股份有限公司
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Priority claimed from JP2016221744A external-priority patent/JP6796460B2/en
Priority claimed from JP2016248125A external-priority patent/JP6789801B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/685—Carboxylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds

Abstract

Provided are: a transparent conductive film which has excellent wet heat resistance; and a touch panel which is provided with this transparent conductive film. A transparent conductive film which sequentially comprises, on a transparent resin film, a cured resin layer and a transparent conductor film in this order. This transparent conductive film is configured such that: the cured resin layer has a thickness of 100 nm or less; the transparent conductor film is patterned; and the change ratio of the surface resistance of the transparent conductor film before and after 240 hours standing in an atmosphere at the temperature of 85 DEG C at the humidity of 85% is 1.5 or less.

Description

透明導電性膜及觸控面板Transparent conductive film and touch panel

本發明係關於一種透明導電性膜及觸控面板。The invention relates to a transparent conductive film and a touch panel.

近年來，於正迅速普及之觸控面板顯示裝置中使用有包含銦-錫複合氧化物(ITO)等透明導電層之透明電極。觸控面板所使用之附透明電極之導電體基本上使用玻璃或者塑膠膜作為基板，尤其是對於要求攜帶性之智慧型手機或平板，就薄度、重量之觀點而言，願意使用應用有塑膠膜之透明導電性膜。 面向上述觸控面板用途，例如揭示有如下透明導電性膜，其係於透明樹脂膜之一面經由至少1層硬化樹脂層而具有經圖案化之透明導電膜(專利文獻1)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2009-76432號公報In recent years, a transparent electrode including a transparent conductive layer such as indium-tin composite oxide (ITO) is used in a touch panel display device which is rapidly spreading. The conductive body with transparent electrodes used in touch panels basically uses glass or plastic film as the substrate, especially for smart phones or tablets that require portability. In terms of thinness and weight, they are willing to use plastics. Film is a transparent conductive film. For the aforementioned touch panel applications, for example, a transparent conductive film having a patterned transparent conductive film via at least one hardened resin layer on one side of the transparent resin film has been disclosed (Patent Document 1). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2009-76432

[發明所欲解決之問題] 於搭載於有時會放置於高溫高濕度下之智慧型手機或汽車導航系統等之觸控面板用途中，強烈期望即便於例如85℃85%RH之較先前更嚴酷之條件下，運行亦不會出現障礙之較高濕熱耐久性。然而，若對與上述技術相關之透明導電性膜進行於85℃85%RH氛圍下之耐濕熱試驗，則再次判明於經圖案化之透明導電膜產生裂痕，而電特性降低。 本發明之目的在於提供一種具有優異之耐濕熱性之透明導電性膜及具備該透明導電性膜之觸控面板。 [解決問題之技術手段] 本申請案發明者等人為了解決上述問題而進行了努力研究，結果獲得了如下見解：於將透明導電膜經圖案化之透明導電性膜放置於高溫高濕環境下之情形時，透明樹脂膜會因吸濕而膨脹，而透明導電膜無法追隨於該膨脹，從而透明導電膜會產生裂痕。本申請案發明者等人進一步進行了研究，結果發現：藉由採用下述構成而能夠達成上述目的，從而完成本發明。 即，本發明係關於一種透明導電性膜，其係於透明樹脂膜上依序具有硬化樹脂層、透明導電膜者，且 上述硬化樹脂層為將包含重量平均分子量為1500以上之環氧樹脂之樹脂組合物進行硬化而成之硬化物膜； 上述硬化樹脂層之厚度為150 nm以下； 上述硬化樹脂層之表面彈性模數為4 GPa以上且12 GPa以下。 該透明導電性膜由於使用包含重量平均分子量為1500以上之環氧樹脂之樹脂組合物而形成硬化樹脂層，且將該硬化樹脂層之表面彈性模數設為4 GPa以上且12 GPa以下，故而能夠形成結晶性較高且具有三維交聯結構之硬化物膜，而硬化樹脂層之膜強度變高。藉此，硬化樹脂層之耐水性及耐膨脹性能夠提昇，其結果為，能夠提昇將透明導電膜經圖案化時之透明導電性膜之耐濕熱性。若環氧樹脂之重量平均分子量未達1500、或硬化樹脂層之表面彈性模數未達4 GPa，則有硬化樹脂層之膜強度變得不充分，透明導電性膜之耐濕熱性降低之虞。再者，若硬化樹脂層之表面彈性模數超過12 GPa，則有硬化樹脂層之柔軟性降低，於將透明導電性膜彎折時產生白化或裂痕之虞。 較佳為將上述樹脂組合物與上述環氧樹脂之硬化促進劑之混合物於170℃下加熱時之凝膠化時間為50秒以下。關於凝膠化時間，一般而言，成為設為對象之組合物等之反應性、尤其是硬化反應性之指標，凝膠化時間越短，意味著硬化反應性越高。藉由將加入有硬化促進劑之樹脂組合物之凝膠化時間設為50秒以下，而能夠使樹脂組合物之硬化反應迅速且充分地進行，從而形成更牢固之硬化物膜。 較佳為上述硬化促進劑包含銻。含有銻之硬化促進劑由於反應性較高，故而能夠使樹脂組合物之硬化反應迅速且充分地進行，而能夠有效率地形成更牢固之硬化物膜。 較佳為上述環氧樹脂為橡膠改性環氧樹脂。藉此，能夠較佳地對硬化樹脂層賦予韌性或耐衝擊性。 較佳為上述硬化樹脂層於溫度85℃、濕度85%之氛圍下之飽和膨脹率為0.5%以下。藉由將硬化樹脂層之飽和膨脹率設為此種範圍，而透明導電性膜之耐濕熱性提高，從而能夠提高電特性之輸出之穩定性及確實性。 上述透明導電膜較佳為經圖案化，且於將上述透明導電膜於溫度85℃、濕度85%之氛圍下放置240小時之前後之表面電阻值之變化率為1.5以下。藉由將暴露於高溫高濕氛圍中之前後之表面電阻值之變化率設為上述範圍內，而即便於放置於苛刻環境下之情形時亦能夠發揮所期待之電特性，藉此能夠謀求於各種用途展開。 又，本發明係關於一種觸控面板，其包含上述透明導電性膜。該觸控面板由於使用有耐濕熱性較高之透明導電性膜，故而能夠發揮優異之耐久性及耐候性。[Problems to be Solved by the Invention] For touch panel applications mounted on smartphones, car navigation systems, and the like that are sometimes placed under high temperature and high humidity, it is strongly expected that, for example, a temperature of 85 ° C and 85% RH will be higher than before. Under severe conditions, high humidity and heat durability without obstacles during operation. However, if the transparent conductive film related to the above-mentioned technology is subjected to a humidity and heat resistance test under an atmosphere of 85 ° C and 85% RH, it is again confirmed that cracks are generated in the patterned transparent conductive film and the electrical characteristics are reduced. An object of the present invention is to provide a transparent conductive film having excellent moisture and heat resistance and a touch panel including the transparent conductive film. [Technical Means for Solving the Problem] The inventors of the present application conducted diligent research in order to solve the above problems, and as a result, they obtained the following insight: The patterned transparent conductive film was placed in a high temperature and high humidity environment. In this case, the transparent resin film swells due to moisture absorption, and the transparent conductive film cannot follow the expansion, and the transparent conductive film may be cracked. The inventors of the present application conducted further studies and found that the above-mentioned objects can be achieved by adopting the following constitutions, thereby completing the present invention. That is, the present invention relates to a transparent conductive film having a hardened resin layer and a transparent conductive film in this order on the transparent resin film, and the hardened resin layer includes an epoxy resin having a weight average molecular weight of 1500 or more. A cured product film obtained by curing the resin composition; the thickness of the cured resin layer is 150 nm or less; and the surface elastic modulus of the cured resin layer is 4 GPa or more and 12 GPa or less. This transparent conductive film uses a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more to form a hardened resin layer, and the surface elastic modulus of the hardened resin layer is 4 GPa or more and 12 GPa or less. A hardened film having a high crystallinity and a three-dimensional crosslinked structure can be formed, and the film strength of the hardened resin layer becomes higher. Thereby, the water resistance and swelling resistance of the hardened resin layer can be improved, and as a result, the moisture and heat resistance of the transparent conductive film when the transparent conductive film is patterned can be improved. If the weight average molecular weight of the epoxy resin is less than 1500, or the surface elastic modulus of the hardened resin layer is less than 4 GPa, the film strength of the hardened resin layer may be insufficient, and the moisture and heat resistance of the transparent conductive film may be reduced. . Furthermore, if the surface elastic modulus of the hardened resin layer exceeds 12 GPa, the softness of the hardened resin layer may decrease, and whitening or cracks may occur when the transparent conductive film is bent. The gelation time when the mixture of the resin composition and the hardening accelerator of the epoxy resin is heated at 170 ° C. is preferably 50 seconds or less. The gelation time is generally an indicator of the reactivity, particularly the hardening reactivity, of a composition or the like to be targeted, and a shorter gelation time means a higher hardening reactivity. By setting the gelation time of the resin composition to which a hardening accelerator is added to 50 seconds or less, the hardening reaction of the resin composition can be rapidly and sufficiently progressed to form a stronger hardened film. It is preferable that the said hardening accelerator contains antimony. Since the antimony-containing hardening accelerator has high reactivity, the hardening reaction of the resin composition can be performed quickly and sufficiently, and a harder hardened film can be formed efficiently. The epoxy resin is preferably a rubber-modified epoxy resin. This makes it possible to impart toughness or impact resistance to the cured resin layer. The saturation expansion ratio of the hardened resin layer under an atmosphere of a temperature of 85 ° C. and a humidity of 85% is preferably 0.5% or less. By setting the saturation expansion coefficient of the hardened resin layer to such a range, the moisture and heat resistance of the transparent conductive film is improved, so that the stability and reliability of the output of electrical characteristics can be improved. The transparent conductive film is preferably patterned, and the change rate of the surface resistance value of the transparent conductive film before and after being left in an atmosphere of 85 ° C. and 85% humidity for 240 hours is 1.5 or less. By setting the change rate of the surface resistance value before and after exposure to a high-temperature and high-humidity atmosphere to be within the above range, the expected electrical characteristics can be exhibited even when placed in a harsh environment. Various uses unfold. The present invention also relates to a touch panel including the transparent conductive film. Since this touch panel uses a transparent conductive film with high humidity and heat resistance, it can exhibit excellent durability and weather resistance.

針對本發明之實施形態，一面參照圖一面於以下進行說明。再者，不需要說明之部分係進行省略，又，存在為了便於說明而進行放大或縮小等而進行圖示之部分。 ＜第1實施形態＞ (透明導電性膜) 圖1係表示本實施形態之透明導電性膜之一例之剖視圖。圖1之透明導電性膜係於透明樹脂膜1之單面經由硬化樹脂層2而具有透明導電膜3。透明導電膜3係經圖案化。再者，於各圖中，透明導電膜3經圖案化之情況係藉由具有透明導電膜3之圖案部a及不具有透明導電膜3之非圖案部b而表示。又，於上述非圖案部b具有上述硬化樹脂層2。 (透明樹脂膜) 作為上述透明樹脂膜1，並無特別限制，可使用具有透明性之各種塑膠膜。例如，作為其材料，可列舉：聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、聚環烯烴系樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂等。其等之中，尤佳為聚酯系樹脂、聚碳酸酯系樹脂、聚烯烴系樹脂。 透明樹脂膜1之厚度並無特別限定，可為5 μm以上且200 μm以下之範圍內，亦可為20 μm以上且130 μm以下之範圍內，還可為40 μm以上且130 μm以下之範圍內。一般而言，透明樹脂膜1變得越厚，吸濕性變得越高而越容易膨脹，但藉由採用下述特定之硬化樹脂層，而即便為上述範圍之厚度之透明樹脂膜，亦能夠防止透明導電膜之裂痕而發揮所期待之電特性。 對於上述透明樹脂膜1，亦可預先對表面實施濺鍍、電暈放電、火焰、紫外線照射、電子束照射、化學處理、氧化等蝕刻處理或底塗處理，而使設置於其上之硬化樹脂層2對上述透明樹脂膜1之密接性提昇。又，亦可於設置硬化樹脂層2之前，視需要藉由溶劑洗淨或超音波洗淨等進行除塵、淨化。 (硬化樹脂層) 硬化樹脂層2為使包含重量平均分子量為1500以上之環氧樹脂(以下，為方便起見，亦稱為「高分子量環氧樹脂」)之樹脂組合物硬化而成之硬化物膜。高分子量環氧樹脂較佳為樹脂組合物之主成分。所謂主成分，係指樹脂組合物所包含之成分中含量最大之成分，其含量相對於樹脂組合物之合計量，較佳為20重量%以上，更佳為40重量%以上。 作為上述高分子量環氧樹脂，可廣泛地使用一般所使用者，可使用於分子中具有1個以上、較佳為2個以上之縮水甘油基、脂環式環氧基、脂肪族環氧基等環氧基之含環氧基化合物。具體而言，例如例示：表氯醇-雙酚A型環氧樹脂、表氯醇-雙酚F型環氧樹脂、四溴雙酚A之縮水甘油醚等阻燃型環氧樹脂、酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂、雙酚A環氧丙烷加成物之縮水甘油醚型環氧樹脂、對羥基苯甲酸-縮水甘油醚酯型環氧樹脂、III-胺基苯酚系環氧樹脂、二胺基二苯甲烷系環氧樹脂、各種脂環式環氧樹脂、如N,N-二縮水甘油基苯胺、N,N-二縮水甘油基-鄰甲苯胺、三縮水甘油基異氰尿酸酯、聚伸烷基二醇二縮水甘油醚、甘油等之多元醇之縮水甘油醚、乙內醯脲型環氧樹脂、具有環氧基之聚矽氧烷、如石油樹脂等之不飽和聚合物之環氧化物等環氧樹脂中重量平均分子量為1500以上之環氧樹脂。高分子量環氧樹脂可單獨使用，亦可併用2種以上。 其中，作為高分子量環氧樹脂，就所獲得之硬化物膜之強度或柔軟性、耐候性之方面而言，較佳為重量平均分子量為1500以上之氫化雙酚A型環氧樹脂或氫化雙酚F型環氧樹脂。 可與高分子量環氧樹脂一併使用上述所列舉之環氧樹脂中重量平均分子量未達1500之環氧樹脂(以下，為方便起見，亦稱為「低分子量環氧樹脂」)。作為低分子量環氧樹脂，較佳為脂環式環氧樹脂。作為脂環式環氧樹脂，可較佳地採用公知者，例如可列舉：3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、ε-己內酯改性3',4'-環氧環己基甲基3,4-環氧環己烷羧酸酯、1,2-環氧基-4-乙烯基環己烷、3,4-環氧環己烷-1-羧酸烯丙酯、重量平均分子量未達1500之氫化雙酚A型環氧樹脂等。低分子量環氧樹脂可單獨使用，亦可併用2種以上。 高分子量環氧樹脂之重量平均分子量只要為1500以上即可，較佳為1700以上，更佳為1800以上。再者，關於上述重量平均分子量之上限，就抑制所獲得之硬化樹脂層因過度之硬化而脆化之觀點而言，較佳為5000，更佳為2000。藉由將環氧樹脂之重量平均分子量設為上述範圍，能夠形成結晶性較高且具有優異之膜強度之硬化樹脂層。 再者，於本說明書中，重量平均分子量係藉由GPC(凝膠滲透層析儀，TOSOH製造之HLC-8320GPC)進行測定並藉由聚苯乙烯換算所算出之值。測定之條件係如下所示。管柱：SHODEXGPC KF-802.5/GPC KF-G；管柱尺寸：6.0 mm內徑×150 mm；溶劑：四氫呋喃(THF)；溶液濃度：0.05重量%；流量：1 mL/min；檢測器：示差折射計(RI)；管柱溫度：40℃；注入量：2 mL 高分子量環氧樹脂較佳為橡膠改性環氧樹脂。藉此，能夠較佳地對硬化樹脂層賦予韌性或耐衝擊性。作為用以將環氧樹脂改性之橡膠成分，並無特別限定，可列舉：丁二烯橡膠、丙烯腈丁二烯橡膠、苯乙烯丁二烯橡膠、丁基橡膠、腈橡膠、天然橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-丙烯橡膠、胺基甲酸酯橡膠、聚矽氧橡膠、氟橡膠、乙烯-乙酸乙烯酯橡膠、表氯醇橡膠等。其中，就韌性或耐化學品性之方面而言，較佳為丁二烯橡膠。橡膠改性環氧樹脂可單獨使用，亦可併用2種以上。 橡膠改性環氧樹脂之製備方法可採用先前公知之方法，例如可列舉：向橡膠成分之聚合物主鏈之末端導入羧基，使該羧基與環氧樹脂之環氧基於磷系觸媒或胺系觸媒等觸媒存在下進行反應之方法等。 上述樹脂組合物較佳為包含硬化促進劑。藉此，能夠使環氧樹脂之硬化反應迅速且充分地進行，而能夠形成膜強度較高之硬化物膜。作為硬化促進劑，並無特別限定，例如可列舉：辛酸、硬脂酸、乙醯基丙酮化物(acetylacetonate)、環烷酸、水楊酸等有機酸之鋅、銅、鐵、銻等有機金屬鹽；金屬螯合物等。其中，硬化促進劑較佳為包含銻。含銻硬化促進劑能夠使樹脂組合物之硬化反應迅速且充分地進行，而能夠有效率地形成更牢固之硬化物膜。再者，硬化促進劑可單獨使用，或將2種以上組合使用。 硬化促進劑之含量並無特別限定，相對於樹脂組合物中所包含之具有環氧基之化合物之總量(100重量份)，較佳為0.005～5重量份，更佳為0.01～4重量份，進而較佳為0.01～1重量份。若硬化促進劑之含量低於上述下限，則有硬化促進效果變得不充分之情形。另一方面，若硬化促進劑之含量超過上述上限，則有硬化物著色而色相變差之情形。 將上述樹脂組合物與上述環氧樹脂之硬化促進劑之混合物於170℃下加熱時之凝膠化時間較佳為50秒以下，更佳為20秒以下。藉由將加入有硬化促進劑之樹脂組合物之凝膠化時間設為50秒以下，而能夠使樹脂組合物之硬化反應迅速且充分地進行，而形成更牢固之硬化物膜。再者，關於上述凝膠化時間，雖較短者較佳，但就混合物之穩定性或操作性之觀點而言，較佳為10秒以上。 於樹脂組合物中，除環氧樹脂以外，亦可適當調配丙烯酸系樹脂、胺基甲酸酯樹脂、醯胺樹脂、聚矽氧樹脂等。進而於樹脂組合物中，亦可加入各種添加劑。作為添加劑，例如可使用調平劑、顏料、填充劑、分散劑、塑化劑、紫外線吸收劑、界面活性劑、抗氧化劑、搖變減黏劑等。 (硬化樹脂層之物性) 硬化樹脂層之表面彈性模數只要為4 GPa以上且12 GPa以下即可。進而，該表面彈性模數較佳為4.5 GPa以上，更佳為5 GPa以上。又，該表面彈性模數較佳為10 GPa以下，更佳為9 GPa以下。若硬化樹脂層之表面彈性模數未達上述下限，則有硬化樹脂層之膜強度變得不充分，而透明導電性膜之耐濕熱性降低之虞。另一方面，若硬化樹脂層之表面彈性模數超過上述上限，則有硬化樹脂層之柔軟性降低，而於將透明導電性膜彎折時產生白化或裂痕之虞。 較佳為硬化樹脂層於溫度85℃、濕度85%之氛圍下之飽和膨脹率為0.5%以下，更佳為0.4%以下。藉由將硬化樹脂層之飽和膨脹率設為此種範圍，透明導電性膜之耐濕熱性增高，而能夠提高電特性之輸出之穩定性及確實性。再者，上述飽和膨脹率越低越佳，就硬化樹脂層之柔軟性之方面而言，較佳為0.05%以上。飽和膨脹率可藉由如下方式求出：使用熱機械測定裝置(TMA)，將膜投入至溫度85℃、濕度85%之氛圍中，求出成為飽和狀態時之尺寸變化量。 硬化樹脂層2係設置於透明樹脂膜1與透明導電膜3之間者，且係不具有作為導電體層之功能者。即，硬化樹脂層2係以介電層之形式進行設置以於經圖案化之透明導電膜3之間能夠絕緣。因此，通常硬化樹脂層2之表面電阻為1×106 Ω/□以上，較佳為1×107 Ω/□以上，進而較佳為1×108 Ω/□以上。再者，硬化樹脂層2之表面電阻並無特別上限。一般而言，硬化樹脂層2之表面電阻之上限為作為測定極限之1×1013 Ω/□左右，但亦可超過1×1013 Ω/□。 硬化樹脂層2之厚度並無特別限制，就耐濕熱性、防止自上述透明樹脂膜1產生低聚物之效果、及光學特性之方面而言，為150 nm以下，較佳為20～100 nm左右，更佳為30～50 nm。再者，於設置2層以上之硬化樹脂層2之情形時，各層之厚度為20～60 nm左右，較佳為25～55 nm。 於本實施形態中，藉由具有經圖案化之透明導電膜3及硬化樹脂層2，而可獲得作為顯示元件之外觀良好者。就該觀點而言，硬化樹脂層2之折射率較佳為透明導電膜3之折射率與硬化樹脂層之折射率之差具有0.1以上。透明導電膜3之折射率與硬化樹脂層之折射率之差較佳為0.1以上且0.9以下，進而為0.1以上且0.6以下。再者，硬化樹脂層2之折射率較佳為通常1.3～2.5、進而1.38～2.3、進而1.4～2.3。 透明導電膜3如上所述，較佳為與硬化樹脂層2之折射率之差為0.1以上者。透明導電膜3之折射率通常為1.95～2.05左右。 硬化樹脂層之形成方法並無特別限定，但較佳為藉由塗覆而進行。首先，將調配有上述成分之樹脂組合物均勻地溶解、分散於溶劑中而製備塗覆溶液。作為溶劑，並無特別限定，例如可列舉：甲苯、二甲苯等芳香族系溶劑；甲基乙基酮、丙酮、甲基異丁基酮、環己酮等酮系溶劑；二乙醚、異丙醚、四氫呋喃、二㗁烷、乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚、苯甲醚、苯乙醚等醚系溶劑；乙酸乙酯、乙酸丁酯、乙酸異丙酯、乙二醇二乙酸酯等酯系溶劑；二甲基甲醯胺、二乙基甲醯胺、N-甲基吡咯啶酮等醯胺系溶劑；甲基溶纖素、乙基溶纖素、丁基溶纖素等溶纖素系溶劑；甲醇、乙醇、丙醇等醇系溶劑；二氯甲烷、氯仿等鹵素系溶劑等。可將該等溶劑單獨使用，又，亦可併用2種以上而使用。 塗覆溶液之固形物成分濃度較佳為0.5重量%～2.5重量%，更佳為1.0重量%～2.0重量%，尤佳為1.5重量%～1.9重量%。 硬化樹脂層可藉由將上述塗覆溶液塗佈於透明樹脂膜上並使之硬化而形成。再者，塗覆溶液可於透明樹脂膜1上直接進行塗覆，亦可於形成於透明樹脂膜1上之下塗層等之上進行塗覆。 塗覆溶液之塗佈方法可視塗覆溶液及塗裝步驟之情況而適時選擇，例如可藉由浸漬塗佈法、氣刀塗佈法、淋幕式塗佈法、滾筒塗佈法、線棒塗佈法、凹版塗佈法、模嘴塗佈法或擠壓塗佈法等進行塗佈。 最後，可藉由使所獲得之塗膜進行加熱硬化而形成硬化樹脂層。作為加熱方法，可採用利用熱風乾燥機、紅外線乾燥機、真空乾燥機、微波加熱乾燥機等之加熱。作為加熱溫度，例如為100～200℃，較佳為120～180℃。作為加熱時間，例如為0.5～10分鐘，較佳為1～5分鐘。 (透明導電膜) 作為上述透明導電膜3之構成材料，並無特別限定，可使用選自由銦、錫、鋅、鎵、銻、鈦、矽、鋯、鎂、鋁、金、銀、銅、鈀、鎢所組成之群中之至少1種金屬之金屬氧化物。於該金屬氧化物中，亦可視需要進而包含上述群中所示之金屬原子。例如可較佳地使用含有氧化錫之氧化銦、含有銻之氧化錫等。 透明導電膜3之厚度並無特別限制，為了製成具有其表面電阻為1×103 Ω/□以下之良好導電性之連續覆膜，較佳為設為厚度10 nm以上。若膜厚變得過厚，則會導致透明性之降低等，因此較佳為15～35 nm，更佳為20～30 nm之範圍內。若厚度未達15 nm，則表面電阻變高，且變得難以成為連續覆膜。又，若超過35 nm，則會導致透明性之降低等。 作為透明導電膜3之形成方法，並無特別限定，可採用先前公知之方法。具體而言，例如可例示真空蒸鍍法、濺鍍法、離子鍍敷法。又，亦可視所需之膜厚而採用適當之方法。再者，於形成透明導電膜3之後，可視需要於100～150℃之範圍內實施退火處理以進行結晶化。因此，透明樹脂膜1較佳為具有100℃以上、進而150℃以上之耐熱性。本實施形態中，透明導電膜3係進行蝕刻而圖案化。由於存在若將透明導電膜3進行結晶化則蝕刻變困難之情形，故而透明導電膜3之退火化處理較佳為於將透明導電膜3圖案化後而進行。進而，於對硬化樹脂層2進行蝕刻之情形時，較佳為於硬化樹脂層2之蝕刻之後進行透明導電膜3之退火化處理。 透明導電膜3亦可於硬化樹脂層2上進行圖案化。圖案化可針對各種態樣，視會應用透明導電性膜之用途而形成各種圖案。再者，藉由透明導電膜3之圖案化而會形成圖案部及非圖案部，但作為圖案部之形狀，例如可列舉條紋狀等。圖5係本實施形態之透明導電性膜之俯視圖，且係作為透明導電膜3而形成為條紋狀之情形之一例，且將透明導電膜3之圖案部a及非圖案部b形成為條紋狀。再者，於圖5中，圖案部a之寬度大於非圖案部b之寬度，但並不限於該範圍。 將經圖案化之透明導電膜於溫度85℃、濕度85%之氛圍下放置240小時之前後之透明導電膜之表面電阻值的變化率較佳為1.5以下，更佳為1.3以下。藉此，即便於將透明導電性膜放置於苛刻環境下之情形時，亦能夠發揮所期待之電特性，藉此能夠謀求於各種用途展開。 (其他構成) 於透明樹脂膜1之與形成有透明導電膜3之面相反側之面，亦可視需要設置硬塗層或易接著層、抗黏連層等。 (透明導電性膜之製造方法) 關於本實施形態之透明導電性膜之製造方法，只要為於透明樹脂膜之單面或兩面硬化樹脂層及透明導電膜具有上述構造者，則其製造方法並無特別限制。例如可藉由依據通常方法，製備於透明樹脂膜之單面或兩面，自透明樹脂膜之側經由至少1層硬化樹脂層而具有透明導電膜之透明導電性膜後，對上述透明導電膜進行蝕刻以進行圖案化而製造。於蝕刻時，藉由用以形成圖案之遮罩覆蓋透明導電膜，並藉由蝕刻液對透明導電膜進行蝕刻。 透明導電膜可較佳地使用含有氧化錫之氧化銦、含有銻之氧化錫，因此作為蝕刻液，可較佳地使用酸。作為酸，例如可列舉：氯化氫、溴化氫、硫酸、硝酸、磷酸等無機酸、乙酸等有機酸、及其等之混合物、以及其等之水溶液。 又，可於本實施形態之透明導電性膜之單面，以於貼合有透明基體5之透明導電性膜之單面配置有上述經圖案化之透明導電膜3之方式經由透明之黏著劑層4而貼合透明基體5。圖4係於圖1之透明導電性膜之透明樹脂膜1(未設置透明導電膜3之面)經由透明之黏著劑層4貼合有透明基體5之構造的透明導電性膜。透明基體5亦可為藉由透明之黏著劑層貼合有至少2片透明之基體膜之複合構造。再者，上述透明導電膜3之圖案化亦可對設為該構造之透明導電性膜實施。 透明基體5之厚度通常較佳為90～300 μm，更佳為控制在100～250 μm。又，於藉由形成透明基體5之複數個基體膜而形成之情形時，各基體膜之厚度為10～200 μm，進而為20～150 μm，係以作為該等基體膜包含透明之黏著劑層在內之透明基體5的總厚度處於上述範圍之方式進行控制。作為基體膜，可列舉與上述透明樹脂膜1相同者。 透明導電性膜(例如，透明樹脂膜1)與透明基體5之貼合可預先將上述黏著劑層4設置於透明基體5側並對其貼合上述透明樹脂膜1，亦可反之，預先將上述黏著劑層4設置於透明樹脂膜1側並對其貼合透明基體5。關於後者之方法，由於可將透明樹脂膜1製成捲筒狀而連續地進行黏著劑層4之形成，故而於生產性之方面上進一步有利。又，亦可藉由利用黏著劑層將複數個基體膜依序貼合於透明樹脂膜1而積層透明基體5。再者，基體膜之積層所使用之透明之黏著劑層可使用與下述透明之黏著劑層4相同者。又，於透明導電性膜彼此之貼合時，亦可適當地選擇供積層黏著劑層4之透明導電性膜之積層面，而將透明導電性膜彼此進行貼合。 作為黏著劑層4，只要為具有透明性者，則可無特別限制地使用。具體而言，例如可適當地選擇將丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醯胺、聚乙烯醚、乙酸乙烯酯/氯乙烯共聚物、改性聚烯烴、環氧系、氟系、天然橡膠、合成橡膠等橡膠系等之聚合物作為基礎聚合物者而使用。特別是就光學透明性優異，且表現出適度之潤濕性、凝集性及接著性等黏著特性，並且耐候性或耐熱性等亦優異之方面而言，可較佳地使用丙烯酸系黏著劑。 根據作為黏著劑層4之構成材料之黏著劑之種類，有能夠藉由使用適當之黏著用底塗劑而使抓固力提昇者。因此，於使用此種黏著劑之情形時，較佳為使用黏著用底塗劑。 作為上述黏著用底塗劑，只要為能夠使黏著劑之抓固力提昇之層，則無特別限制。具體而言，例如可使用於同一分子內具有胺基、乙烯基、環氧基、巰基、氯基等反應性官能基及水解性之烷氧基矽烷基之矽烷系偶合劑、於同一分子內具有包含鈦之水解性之親水性基及有機官能性基之鈦酸酯系偶合劑、及於同一分子內具有包含鋁之水解性之親水性基及有機官能性基之鋁酸鹽系偶合劑等所謂偶合劑、環氧系樹脂、異氰酸酯系樹脂、胺基甲酸酯系樹脂、酯型胺基甲酸酯(ester urethane)系樹脂等具有有機反應性基之樹脂。就工業上容易操作之觀點而言，尤佳為含有矽烷系偶合劑之層。 又，可使上述黏著劑層4含有與基礎聚合物對應之交聯劑。又，於黏著劑層4中，亦可視需要例如調配包含天然物或合成物之樹脂類、玻璃纖維或玻璃珠、金屬粉或其他無機粉末等之填充劑、顏料、著色劑、抗氧化劑等適當之添加劑。又，亦可製成含有透明微粒子而賦予了光擴散性之黏著劑層4。 再者，於上述透明微粒子中，例如可使用1種或2種以上平均粒徑為0.5～20 μm之二氧化矽、氧化鈣、氧化鋁、二氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等導電性之無機系微粒子、或包含如聚甲基丙烯酸甲酯、聚胺基甲酸酯之適當聚合物之交聯或未交聯之有機系微粒子等適當者。 上述黏著劑層4通常係以使基礎聚合物或該組合物溶解或分散於溶劑中而得之固形物成分濃度為10～50重量%左右之黏著劑溶液的形式使用。作為上述溶劑，可適當地選擇甲苯或乙酸乙酯等有機溶劑或水等與黏著劑之種類對應者而使用。 又，若黏著劑層4之厚度未達1 μm，則無法期待其緩衝效果，因此存在如下傾向：變得難以使透明導電膜3之耐擦傷性或作為觸控面板用之手寫筆輸入耐久性及面壓耐久性提昇。另一方面，若使黏著劑層4之厚度過厚，則有損透明性、或者於黏著劑層4之形成或透明基體5之貼合作業性、進而成本之方面上亦難以獲得好結果。 經由此種黏著劑層4而貼合之透明基體5會對透明樹脂膜1賦予良好之機械強度，除手寫筆輸入耐久性及面壓耐久性以外，尤其是有助於防止捲曲等之產生。 於使用脫模膜S而轉印黏著劑層4之情形時，作為此種脫模膜S，例如較佳為使用於聚酯膜之至少會與黏著劑層4接著之面積層有移行防止層及/或脫模層之聚酯膜等。 上述脫模膜S之總厚較佳為30 μm以上，更佳為60～100 μm之範圍內。其目的在於：於形成黏著劑層4之後以捲筒狀態進行保管之情形時，抑制假定會因進入至捲筒間之異物等而產生之黏著劑層4之變形(凹痕)。 (觸控面板) 本實施形態之透明導電性膜例如可較佳地應用於光學方式、超音波方式、靜電電容方式、電阻膜方式等之觸控面板。尤其是適合於靜電電容方式之觸控面板。又，本實施形態之透明導電性膜例如可較佳地應用於電泳方式、扭轉球方式、熱敏可重寫(Thermal Rewritable)方式、光寫入液晶方式、高分子分散型液晶方式、賓主型液晶方式、調色劑顯示方式、變色(chromism)方式、電場析出方式等之軟性顯示元件。 ＜第2實施形態＞ 於第1實施形態中，形成有1層硬化樹脂層，相對於此，於本實施形態中設置有2層。圖2係硬化樹脂層2有2層之情形。於圖2中，自透明樹脂膜1之側依序設置有硬化樹脂層21、22。圖2係於非圖案部b具有硬化樹脂層21、22之情形。較第一層更上側之硬化樹脂層22可進行圖案化，亦可不進行圖案化。 除第1實施形態中之硬化樹脂層之形成材料以外，本實施形態中，可較佳地採用無機物。例如，作為無機物，可列舉：NaF(1.3)、Na3 AlF6 (1.35)、LiF(1.36)、MgF2 (1.38)、CaF2 (1.4)、BaF2 (1.3)、SiO2 (1.46)、LaF3 (1.55)、CeF3 (1.63)、Al2 O3 (1.63)等無機物[上述各材料之括弧內之數值係光之折射率]。該等之中，可較佳地使用SiO2 、MgF2 、A12 O3 等。尤其是SiO2 較佳。除上述以外，還可使用相對於氧化銦，包含氧化鈰10～40重量份左右、及氧化錫0～20重量份左右之複合氧化物。 由無機物所形成之硬化樹脂層能夠以真空蒸鍍法、濺鍍法、離子鍍敷法等乾式製程之形式形成、或者藉由濕式法(塗敷法)等形成。作為形成硬化樹脂層之無機物，如上所述，較佳為SiO2 。關於濕式法，可藉由塗佈矽溶膠等而形成SiO2 膜。 本實施形態中，作為硬化樹脂層21、22之形成材料，可將第1實施形態中之樹脂或上述無機物等適當組合而使用。 ＜其他實施形態＞ 圖2係例示硬化樹脂層2為2層之情形，硬化樹脂層2亦可為3層以上。於硬化樹脂層2為3層以上之情形時，亦於非圖案部b，自透明樹脂膜1側至少具有第一層硬化樹脂層21。較第一層更上側之硬化樹脂層可進行圖案化，亦可不進行圖案化。 圖3亦為表示本實施形態之透明導電性膜之一例之剖視圖。再者，圖3係以與圖1相同之構成進行說明，但於圖3中，當然亦能夠應用與圖2中所說明之構成相同之構成。圖3之透明導電性膜係於透明樹脂膜1之兩面經由硬化樹脂層2而具有經圖案化之透明導電膜3之情形。再者，圖3之透明導電性膜係於兩側具有經圖案化之透明導電膜3，但亦可僅單側進行圖案化。又，圖3之透明導電性膜係兩側之經圖案化之透明導電膜3之圖案部a與非圖案部b一致，但該等亦可不一致，於各種態樣中能夠於兩側適當地進行圖案化。於其他圖中亦相同。 [實施例] 以下，關於本發明，使用實施例詳細地進行說明，本發明只要不超出其主旨，則並不限定於以下之實施例。又，各例中，份、%均為重量基準。 《實施例1》 (硬化樹脂層之形成) 將以橡膠改性環氧樹脂(環氧樹脂骨架部分之重量平均分子量：2000)為主成分之ADEKA Filterra BUR-12A 10份、及作為銻系硬化促進劑之ADEKA Filterra BUR-12B 0.001份進行混合，對該混合物添加甲基異丁基酮90份而製備塗覆溶液。將混合物於170℃下加熱時之凝膠化時間為10秒。於包含厚度為50 μm之聚對苯二甲酸乙二酯膜(以下，稱為PET膜)之透明樹脂膜之一面塗佈上述塗覆溶液，使塗膜乾燥(於195℃下1分鐘)，藉此形成厚度為30 nm之硬化樹脂層。 關於混合物之凝膠化時間之測定，係將混合物量設為2 g，並將規定溫度設定為170℃，除此以外，依據「JIS C 6521 5.7 硬化時間」進行測定。即，將混合物2 g放置於已調節至170℃之加熱板上，開始時間計測。直接利用刮刀反覆進行密切圓(osculating circle)運動，對直至凝膠化為止之時間進行計時。於密切圓運動時，將混合物收容在直徑25 mm之範圍內，於混合物之黏度較低之期間不將刮刀上抬，黏度上升後，時時將刮刀自加熱板垂直地上抬約30 mm，反覆進行該上下運動直至絲狀者斷開。硬化時間係設為自將混合物放置於加熱板上時開始直至將刮刀上抬時絲狀者斷開時為止。再者，密切圓運動係設為1轉1秒左右之速度。測定係反覆進行3次，將其平均值設為硬化時間(凝膠化時間)。 (透明導電膜之形成) 繼而，於硬化樹脂層上，於包含氬氣98%及氧氣2%之0.4 Pa之氛圍中，藉由使用氧化銦90重量%、氧化錫10重量%之燒結體材料之反應性濺鍍法而形成厚度20 nm之ITO膜(光之折射率2.00)，從而獲得透明導電性膜。 (ITO膜之圖案化) 以圖案化為條紋狀之方式將透明膠帶貼合至上述ITO膜上後，將其浸漬於50℃、10重量%之鹽酸(氯化氫水溶液)中10分鐘，而進行ITO膜之蝕刻。所獲得之ITO膜之圖案寬度為6 mm，圖案間距為6 mm。其後，將透明膠帶去除，進行ITO膜之圖案化。 (ITO膜之結晶化) 進行ITO膜之蝕刻後，於140℃下進行90分鐘之加熱處理而使ITO膜結晶化，藉此製作ITO膜經圖案化之透明導電性膜。 《實施例2》 於硬化樹脂層之形成中，使用將以橡膠改性環氧樹脂(環氧樹脂骨架部分之重量平均分子量：2000)為主成分之ADEKA Filterra CRX-11 10份、及作為銻系硬化促進劑之ADEKA Filterra BUR-12B 0.001份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為32秒。 《實施例3》 於硬化樹脂層之形成中，使用將以橡膠改性環氧樹脂(環氧樹脂骨架部分之重量平均分子量：2000)為主成分之ADEKA Filterra CRX-10 10份、及作為銻系硬化促進劑之ADEKA Filterra BU-12B 0.001份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為28秒。 《比較例1》 於硬化樹脂層之形成中，使用將以丙烯酸改性環氧樹脂(環氧樹脂骨架部分之重量平均分子量：500)為主成分之ADEKA Filterra CRX-6 10份、及鋅系硬化促進劑(Adekastab)0.5份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為240秒。 《比較例2》 於硬化樹脂層之形成中，使用將以丙烯酸改性環氧樹脂(環氧樹脂骨架部分之重量平均分子量：500)為主成分之ADEKA Filterra CRX-5 10份、及鋅系硬化促進劑(Adekastab)0.5份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為99秒。 《比較例3》 於硬化樹脂層之形成中，使用將以未進行過改性處理之環氧樹脂(重量平均分子量：500)為主成分之ADEKA Filterra CRX-4 10份、及鋅系硬化促進劑(Adekastab)0.5份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為102秒。 《比較例4》 於硬化樹脂層之形成中，使用將以未進行過改性處理之環氧樹脂(重量平均分子量：500)為主成分之ADEKA Filterra CRX-3 10份、及鋅系硬化促進劑(Adekastab)0.5份進行混合而得之混合物，除此以外，以與實施例1相同之方式製作透明導電性膜。該混合物之凝膠化時間為67秒。 針對實施例及比較例之透明導電性膜(樣品)，進行下述評價。將結果示於表1或本文中。 (1)各層之厚度 關於透明樹脂膜等具有1 μm以上之厚度者，係利用Mitutoyo製造之微計測器(Micro Gauge)式厚度計進行測定。硬化樹脂層、ITO膜等之厚度係使用大塚電子(股)製造之Intensified Multichannel Photodetector即MCPD2000(商品名)，基於源自干涉光譜之波形而算出。 (2)硬化樹脂層之表面彈性模數 將透明導電性膜浸漬於50℃、10重量%之鹽酸(氯化氫水溶液)中10分鐘，將ITO膜去除並使硬化樹脂層露出。按照以下順序對該硬化樹脂層之表面彈性模數進行測定。使用Hysitron Inc.製造之Triboindenter裝置、使用壓頭：Berkovich(三角錐型)，並利用簡單壓入法於溫度25℃下以壓入量20 nm實施測定。 (3)耐濕熱特性 依據JIS K7194(1994年)，藉由四端子法對所獲得之結晶質之透明導電層之表面電阻值(Ω/□)進行測定，將其設為初期之表面電阻值R0。繼而，對在設定為85℃、85%RH之恆溫恆濕機(ESPEC公司製造，LHL-113)中放置了240小時之時之表面電阻值R240進行測定。根據其等求出R240/R0作為電阻變化率。將電阻變化率為1.5以下之情形評價為「○」，將超過1.5之情形評價為「×」。 (4)耐溶劑性 於25℃下將所製作之透明導電性膜浸漬於異丙醇中10分鐘，其後取出，利用純水洗淨，於乾燥後利用目視對硬化樹脂層之表面進行觀察。將外觀未產生變化之情形評價為「○」，將有粗化或變色等外觀之變化之情形評價為「×」。 (5)鹼耐久性 於50℃下將所製作之透明導電性膜浸漬於鹼性溶液(5 wt%)中5分鐘，其後取出，利用純水洗淨，於乾燥後利用目視對硬化樹脂層之表面進行觀察。將外觀未產生變化之情形評價為「○」，將有粗化或變色等外觀之變化之情形評價為「×」。 (6)低聚物有無滲出 於160℃下對所製作之透明導電性膜進行2小時加熱處理，利用目視對此時之低聚物自硬化樹脂層之滲出進行確認。按照以下基準進行評價。 ○：未確認到低聚物之滲出。 △：略微確認到低聚物之滲出。 ×：低聚物之滲出遍及廣範圍。 [表1]

Figure TW201802829AD00001
根據表1發現，實施例之透明導電性膜具有優異之耐濕熱性，且亦可耐受於高溫高濕條件下之使用。An embodiment of the present invention will be described below with reference to the drawings. It should be noted that parts that do not need to be described are omitted, and there are parts that are shown as enlarged or reduced for the convenience of explanation. <First Embodiment> (Transparent conductive film) Fig. 1 is a cross-sectional view showing an example of a transparent conductive film according to this embodiment. The transparent conductive film of FIG. 1 has a transparent conductive film 3 on one side of the transparent resin film 1 through a cured resin layer 2. The transparent conductive film 3 is patterned. In each figure, the case where the transparent conductive film 3 is patterned is represented by a pattern portion a having the transparent conductive film 3 and a non-pattern portion b having no transparent conductive film 3. The non-patterned portion b includes the hardened resin layer 2. (Transparent resin film) The transparent resin film 1 is not particularly limited, and various plastic films having transparency can be used. Examples of the material include polyester resins, acetate resins, polyether resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, Polycycloolefin resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide Department of resin and so on. Among these, polyester-based resins, polycarbonate-based resins, and polyolefin-based resins are particularly preferred. The thickness of the transparent resin film 1 is not particularly limited, and may be in a range of 5 μm or more and 200 μm or less, or in a range of 20 μm or more and 130 μm or less, or in a range of 40 μm or more and 130 μm or less. Inside. Generally, the thicker the transparent resin film 1 is, the higher the hygroscopicity becomes and the easier it is to swell. However, by using the specific hardened resin layer described below, even if the transparent resin film has a thickness in the above range, It is possible to prevent cracks in the transparent conductive film and exhibit desired electrical characteristics. For the transparent resin film 1 described above, the surface may be previously subjected to an etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical treatment, oxidation, or undercoating treatment, and a hardened resin provided thereon The adhesion of the layer 2 to the transparent resin film 1 is improved. In addition, before the hardening resin layer 2 is provided, if necessary, dust removal and purification may be performed by solvent washing, ultrasonic washing, or the like. (Hardened resin layer) The hardened resin layer 2 is obtained by hardening a resin composition containing an epoxy resin having a weight average molecular weight of 1,500 or more (hereinafter, also referred to as "high molecular weight epoxy resin" for convenience).物 膜。 The film. The high molecular weight epoxy resin is preferably a main component of the resin composition. The main component refers to the component having the largest content among the components contained in the resin composition, and the content thereof is preferably 20% by weight or more, more preferably 40% by weight or more with respect to the total amount of the resin composition. As the above-mentioned high molecular weight epoxy resin, it can be widely used by general users, and can be used in molecules having one or more glycidyl groups, alicyclic epoxy groups, and aliphatic epoxy groups. Isoepoxy-containing compounds. Specific examples include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A epoxy resin, epichlorohydrin-bisphenol F-type epoxy resin, glycidyl ether of tetrabromobisphenol A, and novolac Epoxy resin, phenol novolac epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, glycidyl ether epoxy resin of bisphenol A propylene oxide adduct, Hydroxybenzoic acid-glycidyl ether ester epoxy resin, III-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, various alicyclic epoxy resins, such as N, N-diglycidyl Aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerol, hydantoin The epoxy resins having a weight average molecular weight of 1500 or more are epoxy resins such as urea-type epoxy resins, polysiloxanes having epoxy groups, and epoxy resins of unsaturated polymers such as petroleum resins. The high molecular weight epoxy resin can be used alone or in combination of two or more. Among them, as the high molecular weight epoxy resin, in terms of strength, flexibility, and weather resistance of the obtained cured film, a hydrogenated bisphenol A type epoxy resin or a hydrogenated bisphenol having a weight average molecular weight of 1500 or more is preferable. Phenol F-type epoxy resin. Among the epoxy resins listed above, epoxy resins having a weight average molecular weight of less than 1500 (hereinafter, also referred to as "low molecular weight epoxy resin" for convenience) can be used together with the high molecular weight epoxy resin. The low molecular weight epoxy resin is preferably an alicyclic epoxy resin. As the alicyclic epoxy resin, a known one can be preferably used, and examples thereof include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone, and 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexyl Allyl alkane-1-carboxylate, hydrogenated bisphenol A epoxy resin with a weight average molecular weight of less than 1500, and the like. The low molecular weight epoxy resin can be used alone or in combination of two or more. The weight average molecular weight of the high molecular weight epoxy resin may be 1500 or more, preferably 1700 or more, and more preferably 1800 or more. The upper limit of the weight-average molecular weight is preferably 5,000, and more preferably 2,000 from the viewpoint of suppressing embrittlement of the obtained cured resin layer due to excessive hardening. By setting the weight average molecular weight of the epoxy resin to the above range, a hardened resin layer having high crystallinity and excellent film strength can be formed. In addition, in this specification, the weight average molecular weight is a value measured by GPC (gel permeation chromatography, HLC-8320GPC manufactured by TOSOH) and calculated by polystyrene conversion. The measurement conditions are shown below. Column: SHODEXGPC KF-802.5 / GPC KF-G; Column size: 6.0 mm ID × 150 mm; Solvent: Tetrahydrofuran (THF); Solution concentration: 0.05% by weight; Flow rate: 1 mL / min; Detector: Differential Refractometer (RI); column temperature: 40 ° C; injection volume: 2 mL High molecular weight epoxy resin is preferably rubber modified epoxy resin. This makes it possible to impart toughness or impact resistance to the cured resin layer. The rubber component for modifying the epoxy resin is not particularly limited, and examples thereof include butadiene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butyl rubber, nitrile rubber, natural rubber, Isoprene rubber, chloroprene rubber, ethylene-propylene rubber, urethane rubber, silicone rubber, fluorine rubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber, etc. Among them, a butadiene rubber is preferred in terms of toughness and chemical resistance. The rubber-modified epoxy resin may be used alone or in combination of two or more. The method for preparing the rubber-modified epoxy resin may adopt a conventionally known method. For example, a carboxyl group may be introduced into the end of the polymer main chain of the rubber component, and the epoxy of the carboxyl group and the epoxy resin is based on a phosphorus catalyst or an amine. It is a method for performing a reaction in the presence of a catalyst such as a catalyst. The resin composition preferably contains a hardening accelerator. Thereby, the hardening reaction of an epoxy resin can be performed quickly and sufficiently, and a hardened | cured material film with high film strength can be formed. The hardening accelerator is not particularly limited, and examples thereof include organic metals such as zinc, copper, iron, and antimony such as organic acids such as caprylic acid, stearic acid, acetylacetonate, naphthenic acid, and salicylic acid. Salts; metal chelates, etc. Among them, the hardening accelerator preferably contains antimony. The antimony-containing hardening accelerator enables the hardening reaction of the resin composition to proceed quickly and sufficiently, and can effectively form a stronger hardened film. Moreover, a hardening accelerator can be used individually or in combination of 2 or more types. The content of the hardening accelerator is not particularly limited, but is preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 4 parts by weight relative to the total amount (100 parts by weight) of the compound having an epoxy group contained in the resin composition. Parts, more preferably 0.01 to 1 part by weight. If the content of the hardening accelerator is lower than the lower limit described above, the hardening promoting effect may become insufficient. On the other hand, if the content of the hardening accelerator exceeds the above-mentioned upper limit, the cured product may be colored and the hue may be deteriorated. The gelation time when the mixture of the resin composition and the hardening accelerator of the epoxy resin is heated at 170 ° C. is preferably 50 seconds or less, and more preferably 20 seconds or less. By setting the gelation time of the resin composition to which a hardening accelerator is added to 50 seconds or less, the hardening reaction of the resin composition can be quickly and sufficiently progressed to form a stronger hardened film. The gelation time is preferably shorter, but it is preferably 10 seconds or more from the viewpoint of stability or operability of the mixture. In the resin composition, in addition to the epoxy resin, an acrylic resin, a urethane resin, a fluorene resin, a silicone resin, and the like may be appropriately blended. Further, various additives may be added to the resin composition. As the additive, for example, a leveling agent, a pigment, a filler, a dispersant, a plasticizer, an ultraviolet absorber, a surfactant, an antioxidant, a shake reducing agent, and the like can be used. (Physical properties of hardened resin layer) The surface elastic modulus of the hardened resin layer may be 4 GPa or more and 12 GPa or less. Furthermore, the surface elastic modulus is preferably 4.5 GPa or more, and more preferably 5 GPa or more. The surface elastic modulus is preferably 10 GPa or less, and more preferably 9 GPa or less. If the surface elastic modulus of the hardened resin layer does not reach the above-mentioned lower limit, the film strength of the hardened resin layer may become insufficient, and the moisture and heat resistance of the transparent conductive film may decrease. On the other hand, if the surface elastic modulus of the hardened resin layer exceeds the above-mentioned upper limit, the softness of the hardened resin layer may be reduced, and whitening or cracks may occur when the transparent conductive film is bent. The saturated expansion coefficient of the cured resin layer under an atmosphere of a temperature of 85 ° C. and a humidity of 85% is preferably 0.5% or less, and more preferably 0.4% or less. By setting the saturation expansion coefficient of the cured resin layer to be in such a range, the moisture and heat resistance of the transparent conductive film is increased, and the stability and reliability of the output of electrical characteristics can be improved. The lower the saturation expansion ratio, the better. In terms of the flexibility of the cured resin layer, it is preferably 0.05% or more. The saturation expansion coefficient can be obtained by using a thermomechanical measuring device (TMA) to put the film in an atmosphere having a temperature of 85 ° C and a humidity of 85%, and determine the amount of dimensional change when the film is saturated. The hardened resin layer 2 is provided between the transparent resin film 1 and the transparent conductive film 3, and does not have a function as a conductor layer. That is, the hardened resin layer 2 is provided as a dielectric layer so as to be able to be insulated between the patterned transparent conductive films 3. Therefore, the surface resistance of the hardened resin layer 2 is usually 1 × 10 6 Ω / □ or more, preferably 1 × 10 7 Ω / □ or more, and further preferably 1 × 10 8 Ω / □ or more. The surface resistance of the hardened resin layer 2 is not particularly limited. Generally the upper limit of the surface resistance, the cured resin layer 2 is used as the measurement limit of 1 × 10 13 Ω / □ or so, but also exceeds 1 × 10 13 Ω / □. The thickness of the hardened resin layer 2 is not particularly limited. In terms of moisture and heat resistance, the effect of preventing oligomers from the transparent resin film 1, and optical characteristics, the thickness is 150 nm or less, and preferably 20 to 100 nm. About 30 to 50 nm. When two or more hardened resin layers 2 are provided, the thickness of each layer is about 20 to 60 nm, and preferably 25 to 55 nm. In this embodiment, by having the patterned transparent conductive film 3 and the cured resin layer 2, a good appearance as a display element can be obtained. From this viewpoint, the refractive index of the cured resin layer 2 is preferably such that the difference between the refractive index of the transparent conductive film 3 and the refractive index of the cured resin layer is 0.1 or more. The difference between the refractive index of the transparent conductive film 3 and the refractive index of the cured resin layer is preferably 0.1 or more and 0.9 or less, and more preferably 0.1 or more and 0.6 or less. The refractive index of the cured resin layer 2 is preferably 1.3 to 2.5, further 1.38 to 2.3, and further 1.4 to 2.3. As described above, the transparent conductive film 3 is preferably one having a refractive index difference from the cured resin layer 2 of 0.1 or more. The refractive index of the transparent conductive film 3 is usually about 1.95 to 2.05. The method for forming the cured resin layer is not particularly limited, but it is preferably performed by coating. First, a resin composition prepared with the above components is uniformly dissolved and dispersed in a solvent to prepare a coating solution. The solvent is not particularly limited, and examples thereof include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether and isopropyl Ethers such as ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenyl ether Solvents; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone, etc. Amine-based solvents; lysin-based solvents such as methyl lysin, ethyl-cellolysin, and butyl lysin; alcohol-based solvents such as methanol, ethanol, and propanol; halogen-based solvents such as dichloromethane and chloroform. These solvents can be used alone or in combination of two or more. The solid content concentration of the coating solution is preferably 0.5% to 2.5% by weight, more preferably 1.0% to 2.0% by weight, and even more preferably 1.5% to 1.9% by weight. The hardened resin layer can be formed by applying the coating solution to a transparent resin film and curing it. In addition, the coating solution may be directly coated on the transparent resin film 1, or may be coated on the upper and lower coating layers formed on the transparent resin film 1. The coating method of the coating solution may be appropriately selected depending on the conditions of the coating solution and the coating step. For example, the coating method may be a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, or a wire rod Coating is performed by a coating method, a gravure coating method, a die coating method, an extrusion coating method, or the like. Finally, a hardened resin layer can be formed by heat-hardening the obtained coating film. As the heating method, heating using a hot air dryer, an infrared dryer, a vacuum dryer, a microwave heating dryer, or the like can be used. The heating temperature is, for example, 100 to 200 ° C, and preferably 120 to 180 ° C. The heating time is, for example, 0.5 to 10 minutes, and preferably 1 to 5 minutes. (Transparent conductive film) The constituent material of the transparent conductive film 3 is not particularly limited, and it can be selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, A metal oxide of at least one metal in the group consisting of palladium and tungsten. The metal oxide may further include a metal atom shown in the above group, if necessary. For example, indium oxide containing tin oxide, tin oxide containing antimony, and the like can be preferably used. The thickness of the transparent conductive film 3 is not particularly limited. In order to form a continuous film having a good electrical conductivity with a surface resistance of 1 × 10 3 Ω / □ or less, the thickness is preferably 10 nm or more. If the film thickness becomes too thick, it may result in a decrease in transparency, etc., so it is preferably in the range of 15 to 35 nm, and more preferably in the range of 20 to 30 nm. If the thickness is less than 15 nm, the surface resistance becomes high, and it becomes difficult to form a continuous film. Moreover, if it exceeds 35 nm, it will reduce transparency, etc. The method for forming the transparent conductive film 3 is not particularly limited, and a conventionally known method can be adopted. Specifically, for example, a vacuum evaporation method, a sputtering method, and an ion plating method can be exemplified. Also, an appropriate method may be adopted depending on the required film thickness. After the transparent conductive film 3 is formed, if necessary, an annealing treatment is performed in a range of 100 to 150 ° C. to perform crystallization. Therefore, the transparent resin film 1 preferably has heat resistance of 100 ° C. or higher, and further, 150 ° C. or higher. In this embodiment, the transparent conductive film 3 is patterned by etching. Since the etching becomes difficult if the transparent conductive film 3 is crystallized, the annealing treatment of the transparent conductive film 3 is preferably performed after patterning the transparent conductive film 3. Furthermore, when the hardened resin layer 2 is etched, it is preferable to perform the annealing treatment of the transparent conductive film 3 after the hardened resin layer 2 is etched. The transparent conductive film 3 may be patterned on the hardened resin layer 2. The patterning can be applied to various aspects, and various patterns can be formed depending on the application of the transparent conductive film. In addition, the patterned portion and the non-patterned portion are formed by patterning the transparent conductive film 3, but examples of the shape of the patterned portion include a stripe shape. FIG. 5 is a plan view of the transparent conductive film of this embodiment, and is an example of a case where the transparent conductive film 3 is formed in a stripe shape, and the pattern portion a and the non-patterned portion b of the transparent conductive film 3 are formed in a stripe shape. . Further, in FIG. 5, the width of the pattern portion a is larger than the width of the non-pattern portion b, but it is not limited to this range. The rate of change in the surface resistance of the transparent conductive film after the patterned transparent conductive film is left for 240 hours in an atmosphere with a temperature of 85 ° C. and a humidity of 85% is preferably 1.5 or less, and more preferably 1.3 or less. Thereby, even when the transparent conductive film is placed in a harsh environment, the expected electrical characteristics can be exhibited, thereby enabling development of various uses. (Other structure) A hard coat layer, an easy-adhesion layer, an anti-blocking layer, etc. may be provided on the surface of the transparent resin film 1 on the side opposite to the surface on which the transparent conductive film 3 is formed. (Manufacturing method of transparent conductive film) As for the manufacturing method of the transparent conductive film of this embodiment, as long as it has the above-mentioned structure on one or both sides of the transparent resin film and the transparent conductive film has the above-mentioned structure, the manufacturing method is not limited. No special restrictions. For example, the transparent conductive film can be prepared on one or both sides of a transparent resin film by a general method, and the transparent conductive film having a transparent conductive film through at least one hardened resin layer from the side of the transparent resin film can be prepared. It is manufactured by etching for patterning. During the etching, the transparent conductive film is covered by a mask for forming a pattern, and the transparent conductive film is etched by an etching solution. As the transparent conductive film, indium oxide containing tin oxide and tin oxide containing antimony can be preferably used, and an acid can be preferably used as the etching solution. Examples of the acid include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid; mixtures thereof; and aqueous solutions thereof. The transparent conductive film of this embodiment may be provided with a transparent adhesive in such a manner that the patterned transparent conductive film 3 is arranged on one side of the transparent conductive film to which the transparent substrate 5 is bonded. The layer 4 is bonded to the transparent substrate 5. 4 is a transparent conductive film having a structure in which a transparent substrate 5 is bonded to a transparent resin film 1 (the surface on which the transparent conductive film 3 is not provided) of the transparent conductive film of FIG. 1 through a transparent adhesive layer 4. The transparent substrate 5 may also have a composite structure in which at least two transparent substrate films are bonded via a transparent adhesive layer. The patterning of the transparent conductive film 3 described above can also be performed on a transparent conductive film having such a structure. The thickness of the transparent substrate 5 is generally preferably 90 to 300 μm, and more preferably controlled to 100 to 250 μm. In the case where a plurality of base films are formed by forming the transparent base 5, the thickness of each base film is 10 to 200 μm, and further 20 to 150 μm, as the base film contains a transparent adhesive. The total thickness of the transparent base 5 including the layers is controlled in such a manner as to be within the above range. As a base film, the same thing as the said transparent resin film 1 is mentioned. For bonding the transparent conductive film (for example, the transparent resin film 1) and the transparent substrate 5, the above-mentioned adhesive layer 4 may be provided on the transparent substrate 5 side in advance and the transparent resin film 1 may be bonded thereto, or vice versa. The above-mentioned adhesive layer 4 is provided on the transparent resin film 1 side, and the transparent substrate 5 is adhered thereto. In the latter method, since the transparent resin film 1 can be formed into a roll shape and the formation of the adhesive layer 4 can be continuously performed, it is further advantageous in terms of productivity. In addition, the transparent substrate 5 may be laminated by sequentially bonding a plurality of substrate films to the transparent resin film 1 using an adhesive layer. The transparent adhesive layer used for the build-up of the base film can be the same as the transparent adhesive layer 4 described below. When the transparent conductive films are bonded to each other, the transparent conductive films to which the adhesive layer 4 is to be laminated may be appropriately selected, and the transparent conductive films may be bonded to each other. The adhesive layer 4 can be used without particular limitation as long as it has transparency. Specifically, for example, an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyvinyl ether, a vinyl acetate / vinyl chloride copolymer, or a modified polymer can be appropriately selected. Polyolefin, epoxy-based, fluorine-based, natural rubber, synthetic rubber and other rubber-based polymers are used as the base polymer. In particular, an acrylic adhesive can be preferably used in terms of being excellent in optical transparency, exhibiting adhesive properties such as moderate wettability, cohesiveness, and adhesiveness, and also being excellent in weather resistance or heat resistance. Depending on the type of the adhesive used as a constituent material of the adhesive layer 4, there is a person who can improve the gripping force by using an appropriate adhesive primer. Therefore, when such an adhesive is used, it is preferable to use an adhesive primer. The above-mentioned adhesive primer is not particularly limited as long as it is a layer capable of improving the holding force of the adhesive. Specifically, for example, a silane-based coupling agent having reactive functional groups such as an amine group, a vinyl group, an epoxy group, a mercapto group, and a chloro group and a hydrolyzable alkoxysilyl group in the same molecule can be used in the same molecule. Titanate-based coupling agent having hydrolyzable hydrophilic group and organic functional group containing titanium, and aluminate-based coupling agent having hydrolyzable hydrophilic group and organic functional group containing aluminum in the same molecule Such resins as organic coupling groups such as so-called coupling agents, epoxy resins, isocyanate resins, urethane resins, and ester urethane resins. From the viewpoint of industrial ease of handling, a layer containing a silane-based coupling agent is particularly preferred. Moreover, the said adhesive layer 4 can be made to contain the crosslinking agent corresponding to a base polymer. Further, in the adhesive layer 4, if necessary, fillers, pigments, colorants, antioxidants, etc., such as resins containing natural or synthetic materials, glass fibers or glass beads, metal powders, or other inorganic powders, may be appropriately blended. Of additives. Moreover, the adhesive layer 4 containing transparent fine particles and providing light diffusibility can also be formed. Furthermore, in the transparent fine particles, for example, one or two or more kinds of silicon dioxide, calcium oxide, aluminum oxide, aluminum oxide, titanium dioxide, zirconia, tin oxide, indium oxide, and cadmium oxide having an average particle diameter of 0.5 to 20 μm can be used. It is appropriate to use conductive inorganic fine particles such as antimony oxide, or crosslinked or uncrosslinked organic fine particles containing a suitable polymer such as polymethyl methacrylate and polyurethane. The adhesive layer 4 is generally used in the form of an adhesive solution having a solid content concentration of about 10 to 50% by weight, obtained by dissolving or dispersing the base polymer or the composition in a solvent. As the solvent, an organic solvent such as toluene or ethyl acetate, or water and the like corresponding to the type of the adhesive can be appropriately selected and used. In addition, if the thickness of the adhesive layer 4 is less than 1 μm, the cushioning effect cannot be expected. Therefore, there is a tendency that it becomes difficult to make the scratch resistance of the transparent conductive film 3 or input durability as a stylus for a touch panel. And surface pressure durability is improved. On the other hand, if the thickness of the adhesive layer 4 is made too thick, it will be difficult to obtain good results in terms of loss of transparency, or the formation of the adhesive layer 4 or the adhesion of the transparent substrate 5 and further the cost. The transparent substrate 5 bonded through such an adhesive layer 4 imparts good mechanical strength to the transparent resin film 1, and in addition to stylus input durability and surface pressure durability, it is particularly helpful to prevent curling and the like. In the case of using the release film S to transfer the adhesive layer 4, as this release film S, for example, it is preferable to use a polyester film in which an area layer at least adjoining the adhesive layer 4 has a migration prevention layer And / or polyester film of release layer. The total thickness of the release film S is preferably 30 μm or more, and more preferably within a range of 60 to 100 μm. The purpose is to suppress the deformation (dent) of the adhesive layer 4 which is supposed to occur due to foreign matter or the like entering the rolls when the adhesive layer 4 is formed and stored in a roll state. (Touch Panel) The transparent conductive film of this embodiment can be preferably applied to touch panels such as an optical method, an ultrasonic method, an electrostatic capacitance method, and a resistive film method. Especially suitable for the touch panel of electrostatic capacitance method. In addition, the transparent conductive film of this embodiment can be preferably applied to, for example, an electrophoretic method, a twisted ball method, a thermal rewritable method, a light writing liquid crystal method, a polymer dispersed liquid crystal method, and a guest-host type. Flexible display elements such as a liquid crystal method, a toner display method, a chromism method, and an electric field precipitation method. <Second Embodiment> In the first embodiment, one hardened resin layer is formed, while in this embodiment, two layers are provided. FIG. 2 shows a case where the hardened resin layer 2 has two layers. In FIG. 2, hardened resin layers 21 and 22 are sequentially provided from the transparent resin film 1 side. FIG. 2 shows a case where the non-patterned portion b has the hardened resin layers 21 and 22. The hardened resin layer 22 above the first layer may or may not be patterned. In addition to the material for forming the hardened resin layer in the first embodiment, in this embodiment, an inorganic substance can be preferably used. Examples of the inorganic substance include NaF (1.3), Na 3 AlF 6 (1.35), LiF (1.36), MgF 2 (1.38), CaF 2 (1.4), BaF 2 (1.3), SiO 2 (1.46), Inorganic substances such as LaF 3 (1.55), CeF 3 (1.63), Al 2 O 3 (1.63) [The values in parentheses of the above materials are the refractive index of light]. Among these, SiO 2 , MgF 2 , A1 2 O 3 and the like can be preferably used. Especially, SiO 2 is preferable. In addition to the above, a composite oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide with respect to indium oxide can also be used. The hardened resin layer made of an inorganic substance can be formed by a dry process such as a vacuum evaporation method, a sputtering method, an ion plating method, or the wet method (coating method). As the inorganic substance forming the hardened resin layer, as described above, SiO 2 is preferred. As for the wet method, a SiO 2 film can be formed by applying a silica sol or the like. In this embodiment, as a material for forming the hardened resin layers 21 and 22, the resin in the first embodiment, the above-mentioned inorganic substances, and the like can be appropriately combined and used. <Other Embodiments> FIG. 2 illustrates a case where the cured resin layer 2 is two layers, and the cured resin layer 2 may be three or more layers. When the hardened resin layer 2 is three or more layers, at least the first hardened resin layer 21 is provided on the non-patterned portion b from the transparent resin film 1 side. The hardened resin layer above the first layer may or may not be patterned. FIG. 3 is also a cross-sectional view showing an example of a transparent conductive film according to this embodiment. Note that FIG. 3 is described with the same configuration as FIG. 1. Of course, in FIG. 3, the same configuration as that illustrated in FIG. 2 can be applied. The transparent conductive film of FIG. 3 is a case where the transparent resin film 1 has a patterned transparent conductive film 3 on both sides thereof via a cured resin layer 2. Furthermore, the transparent conductive film of FIG. 3 has the patterned transparent conductive film 3 on both sides, but it may be patterned on only one side. In addition, the transparent conductive film in FIG. 3 has the pattern portion a and the non-pattern portion b of the patterned transparent conductive film 3 on both sides, but these may also be inconsistent. Be patterned. The same is true in the other figures. [Examples] Hereinafter, the present invention will be described in detail using examples. The present invention is not limited to the following examples as long as it does not exceed the gist thereof. In each case, parts and% are based on weight. «Example 1» (Formation of a hardened resin layer) 10 parts of ADEKA Filterra BUR-12A containing rubber-modified epoxy resin (weight average molecular weight of the epoxy resin skeleton portion as the main component) and antimony-based hardening 0.001 parts of ADEKA Filterra BUR-12B as an accelerator was mixed, and 90 parts of methyl isobutyl ketone was added to the mixture to prepare a coating solution. The gelation time when the mixture was heated at 170 ° C was 10 seconds. Apply the coating solution to one side of a transparent resin film containing a polyethylene terephthalate film (hereinafter referred to as a PET film) with a thickness of 50 μm, and dry the coating film (at 195 ° C for 1 minute). Thereby, a hardened resin layer having a thickness of 30 nm was formed. The measurement of the gelation time of the mixture was performed in accordance with "JIS C 6521 5.7 Hardening Time" in addition to setting the amount of the mixture to 2 g and setting the predetermined temperature to 170 ° C. That is, 2 g of the mixture was placed on a hot plate adjusted to 170 ° C, and the time measurement was started. The osculating circle motion was directly repeated with a spatula, and the time until gelation was timed. During close circular motion, the mixture is contained within a range of 25 mm in diameter, and the scraper is not lifted during the low viscosity of the mixture. After the viscosity increases, the scraper is sometimes lifted vertically from the heating plate by about 30 mm, repeatedly. This up-and-down motion is performed until the filament is broken. The hardening time is set from when the mixture is placed on a hot plate to when the filament is broken when the spatula is raised. The close circular motion is set at a speed of about 1 revolution and 1 second. The measurement system was repeated three times, and the average value was set as the curing time (gelation time). (Formation of Transparent Conductive Film) Next, on a hardened resin layer, in an atmosphere containing 0.4 Pa of 98% of argon and 2% of oxygen, 90% by weight of indium oxide and 10% by weight of sintered body were used. An ITO film (refractive index of light of 2.00) having a thickness of 20 nm was formed by a reactive sputtering method, thereby obtaining a transparent conductive film. (Patternization of ITO film) After the transparent tape is pasted on the ITO film in a stripe pattern, it is immersed in 10% by weight hydrochloric acid (aqueous hydrogen chloride solution) at 50 ° C for 10 minutes to perform ITO. Etching of the film. The pattern width of the obtained ITO film was 6 mm, and the pattern pitch was 6 mm. Thereafter, the scotch tape is removed, and the ITO film is patterned. (Crystalization of ITO film) After the ITO film is etched, it is heat-treated at 140 ° C. for 90 minutes to crystallize the ITO film, thereby producing a patterned transparent conductive film. «Example 2» In the formation of the hardened resin layer, 10 parts of ADEKA Filterra CRX-11, which contains a rubber-modified epoxy resin (weight average molecular weight of the epoxy resin skeleton portion: 2000) as the main component, and antimony were used. A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.001 parts of ADEKA Filterra BUR-12B, which is a hardening accelerator, was mixed. The gelation time of the mixture was 32 seconds. «Example 3» In the formation of the hardened resin layer, 10 parts of ADEKA Filterra CRX-10 containing rubber-modified epoxy resin (weight average molecular weight of the epoxy resin skeleton portion: 2000) as a main component, and antimony were used. A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.001 parts of ADEKA Filterra BU-12B, a hardening accelerator, was mixed. The gelation time of this mixture was 28 seconds. [Comparative Example 1] In the formation of the cured resin layer, 10 parts of ADEKA Filterra CRX-6, which contains acrylic modified epoxy resin (weight average molecular weight of the epoxy resin skeleton portion: 500) as a main component, and zinc-based A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.5 parts of a hardening accelerator (Adekastab) was mixed. The gelation time of the mixture was 240 seconds. [Comparative Example 2] In the formation of the cured resin layer, 10 parts of ADEKA Filterra CRX-5, which contains acrylic modified epoxy resin (weight average molecular weight of the epoxy resin skeleton portion: 500) as a main component, and zinc-based A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.5 parts of a hardening accelerator (Adekastab) was mixed. The gelation time of the mixture was 99 seconds. [Comparative Example 3] In the formation of the cured resin layer, 10 parts of ADEKA Filterra CRX-4, which contains epoxy resin (weight average molecular weight: 500) as the main component without modification treatment, and zinc-based hardening promotion, were used. A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.5 parts of an agent (Adekastab) was mixed. The gelation time of the mixture was 102 seconds. [Comparative Example 4] For the formation of the cured resin layer, 10 parts of ADEKA Filterra CRX-3, which contains epoxy resin (weight average molecular weight: 500) as the main component without modification treatment, and zinc-based hardening promotion, were used. A transparent conductive film was produced in the same manner as in Example 1 except that a mixture of 0.5 parts of an agent (Adekastab) was mixed. The gelation time of the mixture was 67 seconds. The transparent conductive films (samples) of the examples and comparative examples were evaluated as follows. The results are shown in Table 1 or herein. (1) Thickness of each layer For those having a thickness of 1 μm or more, such as a transparent resin film, the thickness is measured using a Micro Gauge type thickness meter manufactured by Mitutoyo. The thickness of the hardened resin layer, ITO film, etc. is calculated based on the waveform derived from the interference spectrum using MCPD2000 (trade name), an Intensified Multichannel Photodetector manufactured by Otsuka Electronics Co., Ltd. (2) Surface elastic modulus of the hardened resin layer The transparent conductive film was immersed in 50 ° C, 10% by weight hydrochloric acid (aqueous hydrogen chloride solution) for 10 minutes, the ITO film was removed, and the hardened resin layer was exposed. The surface elastic modulus of the cured resin layer was measured in the following order. The measurement was performed using a Triboindenter device manufactured by Hysitron Inc., using an indenter: Berkovich (triangular cone type), and a simple indentation method at a temperature of 25 ° C. with an indentation amount of 20 nm. (3) Moisture and heat resistance According to JIS K7194 (1994), the surface resistance value (Ω / □) of the obtained crystalline transparent conductive layer was measured by a four-terminal method, and this was set as the initial surface resistance value. R0. Next, the surface resistance value R240 when it was left for 240 hours in a constant temperature and humidity machine (ESPEC Corporation, LHL-113) set at 85 ° C and 85% RH was measured. From these, R240 / R0 was obtained as the resistance change rate. A case where the resistance change rate was 1.5 or less was evaluated as “○”, and a case where the resistance change rate was more than 1.5 was evaluated as “×”. (4) Solvent resistance The transparent conductive film produced was immersed in isopropyl alcohol at 25 ° C for 10 minutes, and then taken out, washed with pure water, and after drying, the surface of the hardened resin layer was observed visually. . A case where the appearance was not changed was evaluated as "○", and a case where the appearance was changed such as roughening or discoloration was evaluated as "x". (5) Alkali durability The transparent conductive film produced was immersed in an alkaline solution (5 wt%) at 50 ° C for 5 minutes, and then taken out, washed with pure water, and dried. The surface of the layer was observed. A case where the appearance was not changed was evaluated as "○", and a case where the appearance was changed such as roughening or discoloration was evaluated as "x". (6) Presence or absence of oligomer: The transparent conductive film produced was heated at 160 ° C for 2 hours, and the bleed out of the oligomer self-curing resin layer at this time was visually confirmed. Evaluation was performed according to the following criteria. ○: No bleeding of oligomer was observed. △: Slight exudation of oligomer was confirmed. X: Exudation of oligomers over a wide range. [Table 1]
Figure TW201802829AD00001
 According to Table 1, it was found that the transparent conductive film of the example has excellent moisture and heat resistance, and can also withstand use under high temperature and high humidity conditions.

1‧‧‧透明樹脂膜
2‧‧‧硬化樹脂層
3‧‧‧透明導電膜
4‧‧‧黏著劑層
5‧‧‧透明基體
6‧‧‧硬塗層
21‧‧‧硬化樹脂層
22‧‧‧硬化樹脂層
a‧‧‧圖案部
b‧‧‧非圖案部1‧‧‧ transparent resin film
2‧‧‧hardened resin layer
3‧‧‧ transparent conductive film
4‧‧‧ Adhesive layer
5‧‧‧ transparent substrate
6‧‧‧hard coating
21‧‧‧hardened resin layer
22‧‧‧hardened resin layer
a‧‧‧Pattern Department
b‧‧‧ non-patterned department

圖1係表示本發明之一實施形態之透明導電性膜之剖視圖。 圖2係表示本發明之一實施形態之透明導電性膜之剖視圖。 圖3係表示本發明之一實施形態之透明導電性膜之剖視圖。 圖4係表示本發明之一實施形態之透明導電性膜之剖視圖。 圖5係表示本發明之透明導電性膜之圖案之一例的俯視圖。FIG. 1 is a cross-sectional view showing a transparent conductive film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a transparent conductive film according to an embodiment of the present invention. 3 is a cross-sectional view showing a transparent conductive film according to an embodiment of the present invention. 4 is a cross-sectional view showing a transparent conductive film according to an embodiment of the present invention. FIG. 5 is a plan view showing an example of a pattern of the transparent conductive film of the present invention.

1‧‧‧透明樹脂膜 1‧‧‧ transparent resin film

2‧‧‧硬化樹脂層 2‧‧‧hardened resin layer

3‧‧‧透明導電膜 3‧‧‧ transparent conductive film

a‧‧‧圖案部 a‧‧‧Pattern Department

b‧‧‧非圖案部 b‧‧‧ non-patterned department

Claims (7)

一種透明導電性膜，其係於透明樹脂膜上依序具有硬化樹脂層、透明導電膜者，且 上述硬化樹脂層為將包含重量平均分子量為1500以上之環氧樹脂之樹脂組合物進行硬化而成之硬化物膜； 上述硬化樹脂層之厚度為150 nm以下； 上述硬化樹脂層之表面彈性模數為4 GPa以上且12 GPa以下。A transparent conductive film is a transparent resin film having a cured resin layer and a transparent conductive film in this order. The cured resin layer is a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more. The thickness of the cured resin layer is 150 nm or less; and the surface elastic modulus of the cured resin layer is 4 GPa or more and 12 GPa or less. 如請求項1之透明導電性膜，其中將上述樹脂組合物與上述環氧樹脂之硬化促進劑之混合物於170℃下加熱時之凝膠化時間為50秒以下。The transparent conductive film according to claim 1, wherein the gelation time when the mixture of the resin composition and the hardening accelerator of the epoxy resin is heated at 170 ° C is 50 seconds or less. 如請求項2之透明導電性膜，其中上述硬化促進劑包含銻。The transparent conductive film according to claim 2, wherein the hardening accelerator contains antimony. 如請求項1至3中任一項之透明導電性膜，其中上述環氧樹脂為橡膠改性環氧樹脂。The transparent conductive film according to any one of claims 1 to 3, wherein the epoxy resin is a rubber-modified epoxy resin. 如請求項1至3中任一項之透明導電性膜，其中上述硬化樹脂層於溫度85℃、濕度85%之氛圍下之飽和膨脹率為0.5%以下。The transparent conductive film according to any one of claims 1 to 3, wherein a saturation expansion coefficient of the hardened resin layer under an atmosphere of a temperature of 85 ° C and a humidity of 85% is 0.5% or less. 如請求項1至3中任一項之透明導電性膜，其中上述透明導電膜經圖案化，且 於將上述透明導電膜於溫度85℃、濕度85%之氛圍下放置240小時之前後之表面電阻值之變化率為1.5以下。The transparent conductive film according to any one of claims 1 to 3, wherein the transparent conductive film is patterned, and the surface of the transparent conductive film before and after being left for 240 hours in an atmosphere having a temperature of 85 ° C and a humidity of 85% The rate of change of the resistance value is 1.5 or less. 一種觸控面板，其包含如請求項1至6中任一項之透明導電性膜。A touch panel includes the transparent conductive film according to any one of claims 1 to 6.
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CN109313962A (en) 2019-02-05
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CN109313963B (en) 2022-10-25
TWI739847B (en) 2021-09-21

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