WO2015166850A1

WO2015166850A1 - Transparent electroconductive film

Info

Publication number: WO2015166850A1
Application number: PCT/JP2015/062181
Authority: WO
Inventors: 弘典高橋; 一成多田; 仁一粕谷; 健一郎平田
Original assignee: コニカミノルタ株式会社
Priority date: 2014-05-02
Filing date: 2015-04-22
Publication date: 2015-11-05
Also published as: JPWO2015166850A1; TWI554410B; TW201605641A

Abstract

　The present invention addresses the problem of providing a transparent electroconductive film having good electroconductivity, uniform transparency across the entire visible light region, and high durability. This transparent electroconductive film has at least a first high refractive index layer, a transparent electroconductive layer, and a second high refractive index layer on a transparent resin support body in the stated order, wherein the transparent electroconductive film is characterized in that the transparent electroconductive layer contains silver, the first high refractive index layer and/or the second high refractive index layer contains zinc sulfide, and the proportion of the number of sulfur atoms contained in the zinc sulfide is equal to or greater than 50 and less than 100 to 100 zinc atoms.

Description

Transparent conductive film

The present invention relates to a transparent conductive film, and more particularly to a transparent conductive film having good conductivity and transparency and having high durability.

In recent years, transparent conductive films have been used in various devices such as liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, touch panels, and solar cells.

As a material constituting such a transparent conductive film, metals such as gold, silver, platinum, copper, rhodium, palladium, aluminum, and chromium, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , and TiO _{2 are used.} , SnO ₂ , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.

In a display application, in a touch panel type display device or the like, a transparent conductive film made of a transparent conductive film or the like is disposed on an image display surface of a display element. Therefore, the transparent conductive film is required to have high light transmittance. In such various display devices, a transparent conductive film made of ITO having high light transmittance is often used.

In recent years, capacitive touch panel display devices have become widespread in product groups such as smartphones, and it has been required to further reduce the surface electrical resistance of transparent conductive films. However, the conventional ITO film has a problem that the surface electric resistance cannot be sufficiently lowered.

Thus, it has been studied to use a silver deposited film as a transparent conductive film (see, for example, Patent Document 1). Further, in order to increase the light transmittance of the transparent conductor, a silver deposited film is formed of a film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium / zinc oxide), ICO (indium / cerium oxide). ) And a-GIO (a film made of gallium, indium and oxygen containing amorphous oxide) or the like) (see, for example, Patent Documents 2 to 4). Further, it has been proposed to sandwich a vapor deposited silver film with a zinc sulfide film (see, for example, Non-Patent Documents 1 and 2).

As a problem in providing the above-described silver thin film as a transparent conductive film, there is a lack of reliability due to the reactivity of silver itself. For example, it is known that silver easily reacts and colors with sulfides in the atmosphere.

This coloring phenomenon is understood as a phenomenon in which a silver sulfide film is formed on the surface of bulk silver, but as described above, the transparent conductive material used in the form of a thin film obtained by vapor deposition of silver or the like. In the film, it becomes a significant and serious problem due to the characteristics of the thin film.

That is, a thin film obtained by vapor deposition or sputtering as compared with a bulk solid is characterized by an extremely small thickness (depth) and an extremely remarkable microporous property. Therefore, various components that invade silver such as sulfides in the atmosphere easily diffuse throughout the silver thin film, and the entire silver thin film is modified not only at the interface of the silver thin film structure. For this reason, all of the characteristics required as a constituent member of the transparent conductive film, such as conductivity, transparency, and wavelength uniformity of optical characteristics, are impaired.

When using a silver thin film as a transparent conductive layer, from the request to ensure light transmission, the film thickness used is limited to be thinner than that for mirror and surface decoration purposes. The influence of modification by atmospheric components is particularly great.

As described above, when silver is used in the form of a thin film, special attention must be paid to measures against deterioration due to atmospheric components, but the conventional methods represented by the above-mentioned literature mainly ensure high conductivity and transmittance. However, the measures to prevent the above-mentioned silver thin film modification that we focused on were not sufficient.

In addition, in the technology using a sulfur-containing material such as zinc sulfide as a material for sandwiching the silver thin film, the sulfur contained in the zinc sulfide causes silver to be sulfided in the process of forming the transparent conductive member. As well as becoming a problem, transparency was impaired.

On the other hand, information devices equipped with touch panels in recent years have been required to achieve higher image quality, operational accuracy, and response speed at the same time as demands for larger screens, lighter weights and thinners. Transparency is more important than ever, and it has become more widely used in consumer applications such as smartphones. As a result, it can withstand all temperature and humidity environments and atmospheric environments, and has the above conductivity and transparency. There is a strong demand to secure the product over a long period of use.

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-15623 A JP 2008-226581 A

The present invention has been made in view of the above problems and circumstances, and the solution is to provide a transparent conductive film having good conductivity and uniform transparency over the entire visible light range and having high durability. Is to provide.

In order to solve the above problems, the present inventor has at least a first high-refractive index layer, a transparent conductive layer, and a second high-refractive index layer in this order in the process of examining the cause of the above-described problem. Either one of the high refractive index layers contains zinc sulfide, and the ratio of the number of sulfur atoms contained in the zinc sulfide is less than the number of zinc atoms, that is, the transparent conductive layer of the transparent conductive film A high-refractive-index layer with a composition suitable for protecting the silver thin film from atmospheric components such as sulfides, and at the same time optimizing the light transmittance in the entire visible region of the transparent conductive member. It was found that the above-mentioned problems can be solved by providing the above, and the present work was started.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. On the transparent resin support, a transparent conductive film having at least a first high refractive index layer, a transparent conductive layer and a second high refractive index layer in this order,
The transparent conductive layer contains silver;
At least one of the first high refractive index layer or the second high refractive index layer is a layer containing zinc sulfide,
The ratio of the number of sulfur atoms contained in the zinc sulfide is 50 or more and less than 100 with respect to 100 zinc atoms.

2. 2. The transparent conductive film according to item 1, wherein the layer containing zinc sulfide is a first high refractive index layer.

3. The first item or the item having a first antisulfurization layer between the first high refractive index layer and the transparent conductive layer, wherein the first antisulfurization layer contains an oxide or a nitride. The transparent conductive film according to Item 2.

4. 4. The transparent conductive film according to claim 3, wherein the first sulfurization prevention layer contains zinc oxide or gallium oxide as the oxide.

5. The first high refractive index layer contains zinc sulfide and an oxide or nitride, and the content of the oxide or nitride is 5 to 30 volumes of the total volume of the first high refractive index layer. % In the range of%, The transparent conductive film as described in any one of 1st term | claim to 4th term | claim characterized by the above-mentioned.

6. The transparent conductive film according to any one of Items 1 to 5, wherein the first high refractive index layer contains zinc sulfide and silicon dioxide.

7. The second high refractive index layer is made of zinc sulfide, titanium dioxide, indium tin oxide, zinc oxide, niobium oxide, tin dioxide, indium zinc oxide, aluminum zinc oxide, gallium. Selected from zinc oxide, antimony / tin oxide, indium / cerium oxide, indium / gallium / zinc oxide, bismuth oxide, tungsten trioxide, indium oxide and amorphous oxide containing gallium / indium / oxygen Any one is contained, The transparent conductive film as described in any one of 1st term | claim to 6th term | claim characterized by the above-mentioned.

8. The transparent conductive film according to any one of items 1 to 7, wherein the second high refractive index layer contains zinc sulfide as the high refractive index material.

9. The transparent conductive film according to item 8, wherein the second high refractive index layer further contains silicon dioxide as the high refractive index material.

10. The said 2nd high refractive index layer contains a gallium zinc oxide as said high refractive index material, The transparent conductive film as described in any one of Claim 1-7 characterized by the above-mentioned.

11. A second antisulfurization layer is provided between the transparent conductive layer and the second high refractive index layer, and the second antisulfurization layer contains an oxide or a nitride. The transparent conductive film as described in any one of to the term.

12. The transparent conductive film according to item 11, wherein the second antisulfurization layer contains zinc oxide or gallium / zinc oxide as the oxide.

By the above means of the present invention, it is possible to provide a transparent conductive film having good conductivity and uniform transparency over the entire visible light region and having high durability.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

Generally, a thin film formed by a vacuum process exhibits a microporous property having a low density relative to a bulk solid. Sputtering can form a relatively bulky film among dry coating techniques, but still has a lower density than bulk solids. Therefore, it can be said that element diffusion is likely to occur.Therefore, even if a protective layer is provided for sealing the transparent conductive layer, there may be an upper limit on the film thickness that is practical in terms of adhesion and the like. The effect is presumed to be limited.

In light of such a scientific background, the present inventors made the following inferences while eagerly trying to find a practical and maximum means for suppressing the modification of the conductive layer, and concluded that the effects of the present invention were as follows. I came to find it.

That is, among the element species contained in the atmosphere, the sulfur component has the most adverse effect on the silver constituting the transparent conductive layer, and zinc sulfide (ZnS) is contained in the stoichiometric composition ratio (included in zinc sulfide). If the ratio of the number of sulfur atoms formed is in the vicinity of the conductive layer in a sulfur deficient state with respect to zinc element 1 as well as 1), when this is exposed to sulfur-containing components contained in the atmosphere, Transparent conductive film layer containing silver by incorporating sulfur (S) from the component and approaching the stoichiometric composition ratio without re-releasing from the strength of the covalent bond, acting as a sulfur trapping film Inhibiting the diffusion of sulfur components to the surface is a mechanism for manifesting the effects of the present invention.

Further, the refractive index of the layer containing zinc sulfide obtained in the present invention has a sufficiently high value. From this, by controlling the film thickness of the layer containing zinc sulfide appropriately, it is possible to remarkably reduce the decrease in transmission intensity due to the reflection of silver (Ag), and as a result, highly transparent and transparent with excellent visibility. A conductive film can be formed.

Schematic sectional view showing an example of the layer structure of the transparent conductive film of the present invention The schematic diagram which shows an example of the pattern which consists of a conduction | electrical_connection area | region and an insulation area | region of the transparent conductive film of this invention. The schematic diagram which shows an example of the electrode pattern which consists of a conduction | electrical_connection area | region and an insulation area | region of the transparent conductive film of this invention. Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography

The transparent conductive film of the present invention is a transparent conductive film having at least a first high refractive index layer, a transparent conductive layer, and a second high refractive index layer in this order on a transparent resin support, the transparent conductive film The layer contains silver, at least one of the first high refractive index layer or the second high refractive index layer is a layer containing zinc sulfide, and the ratio of the number of sulfur atoms contained in the zinc sulfide is It is characterized by being 50 or more and less than 100 with respect to 100 zinc atoms. This feature is a technical feature common to the inventions according to claims 1 to 12.

From the viewpoint of manifesting the effects of the present invention, it is preferable that the layer containing zinc sulfide is the first high refractive index layer because a high effect of preventing silver sulfidation of the transparent conductive layer can be obtained.

Further, the first high-refractive index layer and the transparent conductive layer have a first anti-sulfurization layer, and the first anti-sulfur layer contains an oxide or a nitride. As a result of removal of elemental elements in the trapping form of sulfur remaining in the chamber atmosphere, sulfur is not a problem when a transparent conductive layer containing silver is subsequently formed. A transparent conductive layer can be formed below, which is preferable.

The first antisulfurization layer contains zinc oxide or gallium oxide as the oxide, and the metal in zinc oxide or gallium oxide removes sulfur remaining slightly in the chamber atmosphere. As a result, when a transparent conductive layer containing silver is subsequently formed, the remaining of sulfur is not a problem, and it is possible to form a layer in a better atmosphere, which is preferable.

The first high refractive index layer contains zinc sulfide and an oxide or nitride, and the content of the oxide or nitride is 5 to 5% of the total volume of the first high refractive index layer. It is preferable that the content is within the range of 30% by volume because the internal structure of the first high refractive index layer approaches amorphous and the flexibility can be improved.

In addition, it is preferable that the first high refractive index layer contains zinc sulfide and silicon dioxide because the internal structure of the first high refractive index layer approaches an amorphous state and flexibility can be further improved.

In addition, the second high refractive index layer is made of zinc sulfide (ZnS), titanium dioxide (TiO ₂ ), indium tin oxide (ITO), zinc oxide (ZnO), niobium oxide (Nb ₂ ) as a high refractive index material. O ₅ ), tin dioxide (SnO ₂ ), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), antimony tin oxide (ATO), indium cerium Oxide (ICO), indium gallium zinc oxide (IGZO), bismuth oxide (Bi ₂ O ₃ ), tungsten trioxide (WO ₃ ), indium oxide (In ₂ O ₃ ), gallium indium, and oxygen Containing any one selected from amorphous oxides (a-GIO) can further reduce the surface resistance, It preferred because continuity is readily take as when subjected to grayed.

In addition, it is preferable that the second high refractive index layer contains zinc sulfide as the high refractive index material because it has a high effect of preventing silver sulfide of the transparent conductive layer.

In addition, since the second high refractive index layer further contains silicon dioxide as the high refractive index material, the internal structure of the second high refractive index layer approaches an amorphous state, and the flexibility can be further improved. preferable.

Further, it is preferable that the second high refractive index layer contains gallium / zinc oxide as the high refractive index material because it is suitable for patterning and at the same time a silver protective function can be obtained.

Moreover, it has a 2nd sulfurization prevention layer between the said transparent conductive layer and a 2nd high refractive index layer, and the said 2nd sulfide prevention layer contains an oxide or nitride, it is silver of a transparent conductive layer. This is preferable because it has an effect of preventing sulfidation.

In addition, it is preferable that the second antisulfurization layer contains zinc oxide or gallium / zinc oxide as the oxide because it has a high effect of preventing silver sulfide of the transparent conductive layer.

Hereinafter, constituent elements of the present invention, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.

≪Transparent conductive film≫
The transparent conductive film of the present invention is a transparent conductive film having at least a first high refractive index layer, a transparent conductive layer, and a second high refractive index layer in this order on a transparent resin support, the transparent conductive film The layer contains silver, at least one of the first high refractive index layer or the second high refractive index layer is a layer containing zinc sulfide, and the ratio of the number of sulfur atoms contained in the zinc sulfide is It is characterized by being 50 or more and less than 100 with respect to 100 zinc atoms.

FIG. 1 and FIG. 2 show one embodiment of the layer structure of the transparent conductive film of the present invention.

In FIG. 1, the transparent conductive film 100 of the present invention includes transparent resin support 1 / first high refractive index layer 2 / transparent conductive layer 3 / second high refractive index layer 4. In the transparent conductive film 100 of the present invention, either the first high refractive index layer 2 or the second high refractive index layer 4 is a layer containing zinc sulfide (ZnS). The ratio of the number of sulfur atoms contained is 50 or more and less than 100 with respect to 100 zinc atoms.

Further, it is preferable that at least one of the antisulfurization layers 5 a or 5 b is provided between the first high refractive index layer 2, the second high refractive index layer 4, and the transparent conductive layer 3. Moreover, these layers are layers formed from a thin film, and the sulfidation prevention layer preferably contains an oxide or a nitride.

In FIG. 1, one of the first high refractive index layer 2 and the second high refractive index layer 4 is a layer containing zinc sulfide, and the first high refractive index layer 2 or the second high refractive index layer. 4 and the transparent conductive layer 3 are preferably provided with an anti-sulfurization layer 5 (an

anti-sulfurization layer

5a or 5b containing zinc oxide).

The transparency and conductivity of the transparent conductive layer can be improved by the effect of the antisulfurization layer. When this transparent conductive layer and the high refractive index layer containing zinc sulfide are formed adjacent to each other, metal sulfide is likely to be generated, which may affect the light transmittance of the transparent conductive film.

When a high refractive index layer containing zinc sulfide is formed before and after a transparent conductive layer containing silver, this causes partial or total sulfidation of the transparent conductive layer containing silver for the following two reasons. The technical background, which is presumed to significantly reduce transparency and conductivity, and can solve this problem by providing an anti-sulfurization layer in the thickness range of 0.1 to 5 nm, is as follows. Can be explained.

First, when a high refractive index layer is provided on the support side of the transparent conductive layer, that is, when a layer containing silver is formed after forming a layer containing zinc sulfide, a layer containing zinc sulfide is formed. A layer containing silver is formed in a state where the sulfur component released in the film forming chamber remains slightly. As a result, sulfidation modification of the transparent conductive layer occurs at the time of forming the transparent conductive member. Needless to say, it is very difficult to solve this problem only with the exhaust performance of the apparatus and the cold trap function.

In response to this problem, if a layer containing zinc oxide or gallium oxide is formed immediately after forming a layer containing zinc sulfide, zinc or gallium in the zinc oxide traps sulfur remaining slightly in the chamber atmosphere. As a result of removal, when a silver-containing layer is subsequently formed, sulfur is not a problem, and film formation under a good atmosphere is possible, which is preferable.

Next, when the high refractive index layer containing zinc sulfide is formed after the transparent conductive layer containing silver is formed, the high concentration sulfur component directly touches the surface of the silver layer already existing on the support. Therefore, sulfidation modification of the transparent conductive layer also occurs at the time of forming the transparent conductive member.

In addition, when forming a transparent conductive member by sputtering, not only the exposure to the sulfur component of silver, but also the sulfur-containing component is incident with high incident energy, and the silver surface is slightly reverse-sputtered simultaneously with the sulfurization modification. However, the surface properties may be roughened. The transparent conductive layer using silver is provided with a very thin film thickness to increase the transparency, but when the surface properties deteriorate as described above, the conductive network is partially cut off, Not only is the conductivity lowered, but the cut-off portion has a rough island structure, plasmon absorption occurs due to this shape characteristic, and further scattering occurs in some cases, so that even transparency is lost.

In response to this problem, if a layer containing zinc oxide or gallium oxide is formed before providing zinc sulfide, it is possible to prevent both silver sulfide modification and reverse sputtering that occur when a layer containing zinc sulfide is subsequently formed. Yes, it is preferable.

In the transparent conductive film of the present invention, as shown in FIG. 1, the transparent conductive layer 3 may be laminated on the entire surface of the transparent resin support 1, and as shown in FIG. It may be patterned into a desired shape. In the transparent conductive film of the present invention, the region a where the transparent conductive layer 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, as shown in FIG. 2, the region b where the transparent conductive layer 3 is not included is an insulating region.

The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductive film 100. For example, when the transparent conductive film 100 is applied to an electrostatic touch panel, as shown in FIG. 3, the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. It is possible.

In addition, the transparent conductive film 100 of the present invention includes layers other than the transparent resin support 1, the first high refractive index layer 2, the transparent conductive layer 3, the second high refractive index layer 4, and the sulfurization prevention layer 5. May be included. For example, an underlayer that can be a growth nucleus when forming the transparent conductive layer 3 may be included between the transparent conductive layer and the first high refractive index layer 2 adjacent to the transparent conductive layer 3.

≪About layer structure of transparent conductive film≫
<1. Transparent resin support>
Examples of the transparent resin support 1 used for the transparent conductive film 100 include cellulose ester resins (for example, triacetylcellulose (Zerotac (manufactured by Konica Minolta)), diacetylcellulose, acetylpropionylcellulose, etc.), polycarbonate resins (for example, panlite, Multilon (both made by Teijin)), cycloolefin resin (for example, Zeonoa (made by Nippon Zeon), Arton (made by JSR), Apel (made by Mitsui Chemicals)), acrylic resin (for example, polymethyl methacrylate, acrylite ( (Mitsubishi Rayon Co., Ltd.) and Sumipex (Sumitomo Chemical Co., Ltd.)), and these resins are preferably 50% by mass or more of the transparent resin support. Two or more kinds of these resins may be used.

Of these resins, cellulose ester resins, cycloolefin resins and polycarbonate resins are preferred.

Other resins that may be mixed include polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate), polyether sulfone, ABS / AS resin, One or more resins selected from MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, and the like may be included.

Further, when the transparent resin support 1 used in the present invention is a cellulose ester, a lower fatty acid ester is preferable, and cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, or the like is preferable. Used. The cellulose ester used in the present invention preferably has an acyl group substitution degree of 2.85 to 3.00 because the degree of plane orientation can be kept lower, and particularly preferably 2.92 to 3.00.

The method for measuring the substitution degree of the acyl group can be measured in accordance with the provisions of ASTM-D817-96.

A cellulose ester having a polymerization degree of 250 to 400 is preferably used, and cellulose triacetate is particularly preferably used. The number average molecular weight Mn of the cellulose ester according to the present invention is preferably 70000 to 250,000, since it is excellent in mechanical strength and has an appropriate dope viscosity, and more preferably 80000 to 150,000. A cellulose ester having a ratio Mw / Mn to the weight average molecular weight Mw of 1.0 to 5.0 is preferably used.

When the transparent resin support contains at least one selected from a cellulose ester resin, a cycloolefin resin, and a polycarbonate resin, the in-plane retardation value Ro is 0 to 150 nm at a measurement wavelength of 589 nm of the transparent resin support. It can be adjusted within the range, that is, it is preferable because it can be obtained as a low retardation film frequently used in display applications, which is the main application form of the present invention.

The retardation value of the transparent resin support can be controlled by selection of the resin material, the draw ratio during film formation, and the like. Specifically, it can be controlled to an arbitrary value by appropriately selecting the stretching ratio in the longitudinal direction and the transverse direction, and the in-plane retardation value Ro and the thickness direction retardation value Rt are 23 ° C. · 55. In an environment of% RH, it can be measured by a phase difference measuring device “KOBRA-21ADH” (manufactured by Oji Scientific Instruments).

The transparent resin support 1 of the present invention preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more. And more preferably 85% or more. When the average light transmittance of the transparent resin support 1 is 70% or more, the light transmittance of the transparent conductive film 100 is likely to increase. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the transparent resin support 1 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent resin support 1. On the other hand, the average absorptance is measured by measuring the average reflectance of the transparent substrate 1 by making light incident from the same angle as the average transmittance.
Average absorptance = 100− (average transmittance + average reflectance) (%)
Calculate as Average transmittance and average reflectance are measured with a spectrophotometer.

In order to make the transmittance of the transparent resin support within the above range, the surface roughness Ra of the transparent resin support is preferably 3.5 nm or less on both surfaces of the transparent resin support, more preferably. Is 3.0 nm or less. When the surface roughness Ra of the transparent resin support is 3.5 nm or less on both surfaces of the transparent resin support, the haze value is reduced and a transparent resin support excellent in transparency can be obtained. Here, the surface roughness Ra refers to the arithmetic average roughness in JIS B0601: 2001.

The haze value of the transparent resin support 1 of the present invention is preferably 0.01 to 2.5 (%), more preferably 0.1 to 1.2 (%). The haze value of a transparent conductive film is suppressed as the haze value of a support body is 2.5 (%) or less.
The haze value of the transparent resin support is measured with a haze meter “model: NDH 2000” (manufactured by Nippon Denshoku Co., Ltd.).

The refractive index of light having a wavelength of 570 nm of the transparent resin support 1 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. It is. The refractive index of the transparent resin support is usually determined by the material of the support. The refractive index of the transparent resin support is measured with an ellipsometer at 23 ° C. and 55% RH.

The thickness of the transparent resin support 1 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the transparent resin support is 1 μm or more, the strength of the transparent resin support 1 is increased, and the first high refractive index layer 2 is difficult to be cracked or torn. On the other hand, if the thickness of the transparent resin support 1 is 20 mm or less, the flexibility of the transparent conductive film 100 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductive film 100 can be reduced. Moreover, the apparatus using the transparent conductive film 100 can also be reduced in weight.

<2. First High Refractive Index Layer>
The high refractive index layer in the present invention is a layer containing a high refractive index material and means a layer having a refractive index higher than that of the transparent resin support 1.

The first high refractive index layer 2 is a layer that adjusts the light transmission (optical admittance) of the conductive region a of the transparent conductive film, that is, the region where the transparent conductive layer 3 is formed, and at least the transparent conductive film 100. Formed in the conductive region a. The first high-refractive index layer 2 has a function of protecting the transparent conductive layer from moisture, sulfide, sulfur-containing components, etc. in the atmosphere, so that it is also formed in the insulating region b of the transparent conductive film 100. It is preferable that

In the present invention, at least one of the first high refractive index layer and the second high refractive index layer is a layer containing zinc sulfide, and the first high refractive index layer and the second high refractive index layer The first high refractive index layer 2 is preferably a layer containing zinc sulfide (ZnS). When zinc sulfide is contained in the first high refractive index layer 2, it becomes difficult for moisture to permeate from the transparent resin support 1 side, and corrosion of the transparent conductive layer 3 is suppressed. The first high refractive index layer 2 may contain other dielectric material or oxide semiconductor material together with zinc sulfide. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained together with zinc sulfide is preferably 0.1 to 1.1 higher than the refractive index of light having a wavelength of 570 nm of the transparent resin support 1. More preferably, it is larger by 4 to 1.0. On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably larger than 1.5, and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the first high refractive index layer 2. The refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material included in the first high refractive index layer 2 and the density of the material included in the first high refractive index layer 2. The refractive index is measured with an ellipsometer in an environment of 23 ° C. and 55% RH.

In the present invention, the first high refractive index layer is preferably a layer containing zinc sulfide, and the composition ratio at this time is 50 or more and less than 100 sulfur atoms with respect to 100 zinc atoms. . Preferably, the number of sulfur atoms is 83 or more and 90 or less with respect to 100 zinc atoms. Within this range, the anti-sulfuration effect of silver contained in the transparent conductive layer is excellent, so it has good conductivity and transparency, uniform light transmittance over the entire visible light range, and improved durability. The effect is obtained.

<Method for analyzing the number of sulfur atoms and the number of zinc atoms>
The number of sulfur atoms and the number of zinc atoms contained in the zinc sulfide contained in the first high refractive index layer can be analyzed using an ICP emission spectroscopic analyzer. Specifically, it can be analyzed by performing as follows.

For quantitative elemental analysis of zinc and sulfur, a reference sample in which a predetermined ZnS thin layer was formed as a single layer on BK7 glass was prepared, and ultra-high purity hydrogen peroxide (manufactured by Kanto Chemical Co., Ltd.) was used for these samples. For each element contained in a 20 ml solution obtained by sufficiently dissolving the ZnS layer using a solution and diluted with ultrapure water, an ICP emission spectroscopic analyzer “SPS3520UV” manufactured by Hitachi High-Tech Science Co., Ltd. is used. Perform matrix matching.

In the determination, a zinc standard solution for atomic absorption analysis 1000 mg / l (manufactured by Kanto Chemical Co., Inc.) is used as a reference for zinc, and a sulfur standard solution Sulfur 1000 mg / l (SPEX) is used for sulfur. The measurement wavelength is 213.924 nm for zinc and 180.734 nm for sulfur.

In the measurement, a solution sample obtained by performing the same treatment on clean BK7 glass is analyzed, and it is confirmed that the zinc and sulfur components as background noise that hinder the test are below the detection limit.

<Method for controlling sulfur content>
In the present invention, the ratio of the number of zinc atoms and the number of sulfur atoms contained in the first high refractive index layer can be controlled by co-evaporating or co-sputtering zinc sulfide and zinc and adjusting the respective conditions. it can.

In addition, a reactive sputtering method can be used to obtain a composition containing a large amount of sulfur, for example, zinc sulfide (ZnS) while blowing hydrogen sulfide (H ₂ S) gas diluted with Ar gas into a vacuum chamber. It is also possible to control by sputtering using as a target.

When layer formation is performed by a sputtering method, a sputtering target obtained mainly as a sintered body, which is adjusted to an appropriate elemental composition ratio in obtaining a desired composition in the formed layer, is prepared and used. It is simple and at the same time has excellent production process compatibility. Such sintered bodies having different elemental composition ratios can be obtained as commercial products.

About a 1st high refractive index layer, an oxide or nitride is preferable as a material used with the said zinc sulfide. The oxide is particularly preferably silicon dioxide (SiO ₂ ). Examples of the nitride include silicon nitride (Si ₃ N ₄ , SiN), aluminum nitride (AlN), titanium nitride (TiN), and the like.

As a method for controlling the composition of zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ), for example, sputtering using a zinc sulfide (ZnS) target containing silicon dioxide (SiO ₂ ) at an appropriate concentration, This can be performed by using a co-sputtering method using silicon (SiO ₂ ) and zinc sulfide (ZnS) targets simultaneously.

When silicon dioxide is contained in the high refractive index layer containing zinc sulfide (ZnS) at a concentration of 5 to 30 volume percent or less, the internal structure of the layer becomes close to amorphous and the flexibility can be improved.

Zinc sulfide (ZnS) is a material having a strong covalent bond, but when it is obtained in a state deviating from the stoichiometric composition ratio, the internal structure of the layer is considered to be crystalline with many grain boundaries. At this time, the properties of the obtained layer are hard and brittle, and in addition, the adhesion strength is inferior.

On the other hand, transparent conductive films are often unwound between roll-to-roll processes and handled while being repeatedly wound. Therefore, if the film is crystalline in this process, fine cracks originate from the grain boundaries. As a result, the sealing performance of the transparent conductive layer is impaired, so that flexibility is very preferable.

In addition, the flexible layer obtained by containing silicon dioxide also has excellent followability to the thermal expansion of the support made of resin, so it can also reduce the occurrence of fine cracks and is reliable under temperature stress Is still preferable.

The content needs to be adjusted to maintain the refractive index for adjusting the optical characteristics of the transparent conductive film and not to impair the above-described sulfur capturing function. From this viewpoint, it is preferable that silicon dioxide is contained at a concentration of 5 to 30 volume percent as described above.

The layer thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm. When the layer thickness of the first high refractive index layer 2 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductive film 100 is sufficiently adjusted by the first high refractive index layer 2. On the other hand, if the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease. The layer thickness of the first high refractive index layer 2 is measured by an ellipsometer “multi-incidence angle spectroscopic ellipsometer VASE (registered trademark)” (manufactured by JA Woollam).

The first high refractive index layer 2 is formed by a general vapor deposition method (also called a deposition method or a vapor deposition method) such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It can be a layer formed of From the standpoint that the refractive index (density) of the first high refractive index layer 2 is increased, the first high refractive index layer 2 is preferably a layer formed by an electron beam evaporation method or a sputtering method. In the case of the electron beam evaporation method, it is desirable to have assistance such as IAD (ion assist) in order to increase the density of the layer.

Further, when the first high refractive index layer 2 is a layer patterned in a desired shape, the patterning method is not particularly limited. The first high refractive index layer 2 may be, for example, a layer formed in a pattern by a vapor deposition method by placing a mask or the like having a desired pattern on the deposition surface. It may be a layer patterned by a method.

<3. First sulfurization prevention layer>
Since the above-mentioned first high refractive index layer 2 contains zinc sulfide, an oxide or a nitride is contained between the first high refractive index layer 2 and the transparent conductive layer 3 as shown in FIG. The anti-sulfurization layer 5a preferably includes the anti-sulfuration layer 5a containing zinc oxide or gallium oxide. The first sulfurization preventing layer 5a has a function of preventing diffusion of sulfides and sulfur-containing components from the first high refractive index layer. Further, the first sulfidation preventing layer 5a may also be formed in the insulating region b of the transparent conductive film 100. In this case, the transparent conductive layer is made transparent from moisture, sulfide, sulfur-containing components, etc. in the atmosphere. Since it has a function of protecting the layer, it is preferably formed also in the insulating region b.

The first antisulfurization layer 5a is a layer that preferably contains zinc oxide or gallium oxide, and may be a layer that contains a metal oxide, a metal nitride, a metal fluoride, or the like. The first sulfidation preventing layer 5a may contain only one kind or two or more kinds. However, when the first high refractive index layer 2, the first sulfidation preventing layer 5a, and the transparent conductive layer 3 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. A compound is preferred. In the case where the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Examples of metal oxides include zinc oxide (ZnO) and gallium oxide (Ga ₂ O ₃ ), titanium dioxide (TiO ₂ ), indium tin oxide (ITO), niobium oxide (Nb ₂ O ₅ ), Zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), titanium pentoxide (Ti ₃ O ₅ ), titanium heptoxide (Ti ₄ O ₇ ), titanium trioxide (Ti ₂₎ O ₃ ), titanium oxide (TiO), tin dioxide (SnO ₂ ), lanthanum titanium oxide (La ₂ Ti ₂ O ₇ ), indium / zinc oxide (IZO), aluminum / zinc oxide (AZO), gallium / zinc oxide (GZO), antimony tin oxide (ATO), indium cerium oxide (ICO), bismuth oxide _(Bi _{2 O} 3), gallium Indium, and amorphous oxide composed of oxygen (a-GIO), germanium oxide _(GeO 2), silicon dioxide _(SiO 2), aluminum oxide _(Al _{2 O} 3), hafnium oxide _(HfO 2), silicon oxide ( SiO), magnesium oxide (MgO), yttrium oxide (Y ₂ O ₃ ), tungsten trioxide (WO ₃ ), and the like.

Examples of metal fluorides include lanthanum fluoride (LaF ₃ ), barium fluoride (BaF ₂ ), sodium aluminum fluoride (Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ ), aluminum fluoride (AlF ₃ ), Includes magnesium fluoride (MgF ₂ ), calcium fluoride (CaF ₂ ), barium fluoride (BaF ₂ ), cerium fluoride (CeF ₃ ), neodymium fluoride (NdF ₃ ), yttrium fluoride (YF ₃ ), etc. It is.

Examples of the metal nitride include silicon nitride (Si ₃ N ₄ , SiN), aluminum nitride (AlN), titanium nitride (TiN), and the like.

Among these, a layer containing zinc oxide or gallium oxide is preferable. When the first anti-sulfurization layer is a two-component layer such as zinc oxide and gallium oxide or zinc oxide and silicon nitride, the layer may be formed by sputtering using a target in which the respective materials are mixed in a desired ratio. it can. Moreover, a layer can be formed by using each target simultaneously and using a co-sputtering method.

Here, the layer thickness of the first sulfidation preventing layer 5a is preferably a layer thickness capable of protecting the surface of the first high refractive index layer 2 from an impact when forming the transparent conductive layer 3 described later. On the other hand, zinc oxide or gallium oxide that can be contained in the first high refractive index layer has a high affinity with the metal contained in the transparent conductive layer 3. Therefore, if the thickness of the first anti-sulfurization layer 5a is very thin and a part of the first high refractive index layer 2 is slightly exposed, a transparent metal film of the transparent conductive layer grows around the exposed part. However, the transparent conductive layer 3 tends to be dense. That is, the first sulfidation preventing layer 5a is preferably relatively thin, preferably 0.1 to 5.0 nm, and more preferably 0.5 to 2.0 nm.

The first antisulfurization layer 5a is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method or the like.

When the first antisulfurization layer 5a is a layer patterned into a desired shape, the patterning method is not particularly limited. The first sulfidation preventing layer 5a may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the deposition surface, and may be a known etching method. It may be a layer patterned by.

<4. Transparent conductive layer>
The transparent conductive layer 3 is a layer for conducting electricity in the transparent conductive film 100. As described above, the transparent conductive layer 3 may be formed on the entire surface of the transparent resin support 1, or may be patterned into a desired shape.

The transparent conductive layer 3 is a layer containing silver and may contain other metals. The metal used together with silver is not particularly limited as long as it is a metal having high transparent conductivity. For example, gold, copper, nickel, palladium, platinum, zinc, aluminum, manganese, germanium, bismuth, neodymium, and molybdenum are preferable.

Among these, gold, palladium, germanium, bismuth, copper, platinum, neodymium and niobium are preferable. The transparent conductive layer 3 may contain only one kind of these metals or two or more kinds. From the viewpoint of conductivity, the transparent conductive layer preferably contains an alloy containing 90 atm% or more of silver. When silver is contained at 90 atm% or more, excellent conductivity and high durability can be obtained.

Further, when at least one kind of the above highly conductive metal is contained within the above range, predetermined conductivity can be secured even if the thickness of the transparent conductive layer is reduced, and it is contained in the transparent conductive layer. The effect of preventing silver deterioration is obtained and the reliability is improved. For example, when silver and zinc are combined, the sulfidation resistance of the transparent metal layer is increased. When silver and gold are combined, salt resistance (NaCl) resistance increases. Furthermore, when silver and copper are combined, the oxidation resistance increases.

The layer thickness of the transparent conductive layer of the present invention is preferably in the range of 3 to 15 nm, more preferably in the range of 5 to 13 nm. The desired transparency and plasmon absorption rate can be ensured by this layer thickness.

The plasmon absorption rate of the transparent conductive layer 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less.

The transparent conductive layer 3 can be a layer formed by any forming method, but in order to change the average transmittance of the transparent conductive layer, it is formed on a layer formed by sputtering or an underlayer described later. It is preferable that it is a layer.

In the sputtering method, when the layer is formed, the material collides with the deposition target at high speed, so that a dense and smooth layer can be easily obtained, and the light transmittance of the transparent conductive layer 3 is likely to be increased. Moreover, when the transparent conductive layer 3 is a layer formed by sputtering, the transparent conductive layer 3 is hardly corroded even in an environment of high temperature and low humidity.

The type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like. The transparent conductive layer 3 is particularly preferably a layer formed by a counter sputtering method. When the transparent conductive layer 3 is a layer formed by the facing sputtering method, the transparent conductive layer 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent conductive layer 3 becomes lower and the light transmittance is likely to increase.

<5. Second anti-sulfur layer>
When the second high-refractive index layer to be described later is a zinc sulfide-containing layer, as shown in FIG. 1, zinc oxide, gallium / zinc oxide is interposed between the transparent conductive layer 3 and the second high-refractive index layer 4. Or it is preferable that the 2nd sulfide prevention layer 5b containing a gallium oxide is contained. The second sulfidation preventing layer 5b may be formed also in the insulating region b of the transparent conductive film 100, but from the viewpoint of making it difficult to visually recognize the pattern formed of the conductive region a and the insulating region b, only the conductive region a. It is preferable to be formed.

The second anti-sulfurization layer 5b is a layer containing zinc oxide, gallium / zinc oxide or gallium oxide, and may be a layer containing metal oxide, metal nitride, metal fluoride or the like. In addition to zinc oxide, only one of these may be contained in the second sulfurization prevention layer 5b, or two or more thereof may be contained. The metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2 described above. Among these, a layer containing zinc oxide is preferable.

When the second anti-sulfurization layer is a two-component layer such as zinc oxide and gallium oxide or zinc oxide and silicon nitride, the layer may be formed by sputtering using a target in which the respective materials are mixed in a desired ratio. it can. Moreover, a layer can be formed by using each target simultaneously and using a co-sputtering method.

On the other hand, the thickness of the second antisulfurization layer 5b is preferably a thickness capable of protecting the surface of the transparent conductive layer 3 from damage during the formation of the second high refractive index layer 4 described later. On the other hand, the metal contained in the transparent conductive layer 3 and the ZnS contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfurization layer 5b is very thin and a part of the transparent conductive layer 3 is slightly exposed, the transparent conductive layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. Adhesion with 4 tends to increase. Therefore, the specific layer thickness of the second sulfidation preventing layer 5b is preferably 0.1 to 5.0 nm, and more preferably 0.5 to 2.0 nm. The layer thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.

The second antisulfurization layer 5b may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.

When the second antisulfurization layer 5b is a layer patterned into a desired shape, the patterning method is not particularly limited. The second antisulfurization layer 5b may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the deposition surface, and may be a known etching method. It may be a layer patterned by.

<6. Second High Refractive Index Layer>
The second high refractive index layer 4 is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductive film 100, that is, the region where the transparent conductive layer 3 is formed. The conductive film 100 is formed in the conduction region a. The second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductive film 100, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a. Preferably it is formed. Since the second high refractive index layer 4 makes it difficult for water molecules and sulfide molecules to pass through from the atmosphere side, it has an effect of suppressing the corrosion of the transparent conductive layer 3.

The second high refractive index layer 4 is a layer containing a high refractive index material, and is a layer having a refractive index higher than the refractive index of the transparent resin support 1 described above, and one of the first high refractive index layers. The layer is a layer containing zinc sulfide (ZnS). The second high refractive index layer 4 may include zinc sulfide or other dielectric material or oxide semiconductor material. The refractive index of light having a wavelength of 570 nm of zinc sulfide or other dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 higher than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1. More preferably, it is larger by 1.0.

On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material contained in the second high refractive index layer 4 is preferably larger than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductive film 100 is sufficiently adjusted by the second high refractive index layer 4. The refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material included in the second high refractive index layer 4 and the density of the material included in the second high refractive index layer 4.

The dielectric material or oxide semiconductor material contained in the second high refractive index layer 4 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. Examples of metal oxides include silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), ITO (indium tin oxide), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), titanium pentoxide (Ti ₃ O ₅ ), titanium heptoxide (Ti ₄ O ₇ ), titanium trioxide (Ti ₂ O ₃ ), Titanium oxide (TiO), tin dioxide (SnO ₂ ), lanthanum titanium oxide (La ₂ Ti ₂ O ₇ ), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide ( GZO), antimony tin oxide (ATO), indium cerium oxide (ICO), indium gallium zinc oxide (IGZO) Bismuth oxide _(Bi _{2 O} 3), gallium oxide _(Ga _{2 O} 3), germanium oxide _(GeO 2), three tungsten oxide _(WO 3), hafnium oxide _(HfO 2), amorphous of gallium-indium and oxygen Oxides (a-GIO) and the like are included. The second high refractive index layer 4 may include only one kind of the metal oxide or two or more kinds.

In the present invention, among the above metal oxides, indium / zinc oxide (ITO), indium / zinc oxide (IZO), gallium / zinc oxide (GZO), indium / gallium / zinc oxide (IGZO) Is preferred. These materials are suitable for patterning, and at the same time, can provide a protective function for silver, and by using these wide gap semiconductors, the surface resistance value of the transparent conductive film is lowered, and current can be easily taken out. There is an effect to become.

Furthermore, in the present invention, zinc sulfide (ZnS) is particularly preferable as the dielectric material or oxide semiconductor material contained in the second high refractive index layer 4. When zinc sulfide (ZnS) is contained in the second high refractive index layer 4, water molecules and sulfide molecules are hardly transmitted from the transparent resin support 1 side, and corrosion of the transparent conductive layer 3 is suppressed.

The second high refractive index layer may contain only zinc sulfide (ZnS). The composition ratio at this time is 50 or more and less than 100 sulfur atoms with respect to 100 zinc atoms. Preferably, the number of sulfur atoms is 83 or more and 90 or less with respect to 100 zinc atoms.

The second high refractive index layer 4 may contain other materials together with zinc sulfide (ZnS). Materials included with zinc sulfide (ZnS), said dielectric material or metal may be an oxide semiconductor material oxide or silicon dioxide (SiO ₂₎ and the like, particularly preferably silicon dioxide (SiO _2). When silicon dioxide (SiO ₂ ) is contained together with zinc sulfide (ZnS), the second high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced. The composition ratio at this time is the same as that of zinc sulfide (ZnS) alone, and the composition ratio is preferably 50 or more and less than 100 sulfur atoms with respect to 100 zinc atoms. More preferably, the number of sulfur atoms is 83 or more and 90 or less with respect to 100 zinc atoms.

When the second high refractive index layer 4 contains other materials together with zinc sulfide (ZnS), the amount of zinc sulfide (ZnS) is 0.1 to 95 with respect to the total volume of the second high refractive index layer 4. The volume is preferably 50%, more preferably 50 to 90% by volume, and still more preferably 60 to 85% by volume. When the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases. On the other hand, when many components other than ZnS are contained, the amorphous nature of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.

As a method for controlling the composition of zinc sulfide and silicon dioxide (SiO ₂ ) within the above range, for example, a sputtering method using a zinc sulfide (ZnS) target containing silicon dioxide (SiO ₂ ) at an appropriate concentration, This can be performed by utilizing a co-sputtering method using silicon dioxide (SiO ₂ ) and zinc sulfide (ZnS) targets simultaneously.

When silicon dioxide (SiO ₂ ) is contained in the above range together with zinc sulfide, the second high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductive film is likely to be enhanced.

When the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases. On the other hand, when the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.

The layer thickness of the second high refractive index layer 4 is preferably 15 to 150 nm, and more preferably 20 to 80 nm. When the layer thickness of the second high refractive index layer 4 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. On the other hand, if the layer thickness of the second high refractive index layer 4 is 150 nm or less, the light transmittance of the region including the second high refractive index layer 4 is unlikely to decrease. The layer thickness of the second high refractive index layer 4 is measured with an ellipsometer.

The formation method of the second high refractive index layer 4 is not particularly limited, and is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It can be. From the viewpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a film formed by a sputtering method.

Further, when the second high refractive index layer 4 is a layer patterned into a desired shape, the patterning method is not particularly limited. The second high refractive index layer 4 may be, for example, a layer formed in a pattern by a vapor deposition method by disposing a mask having a desired pattern on the deposition surface. Moreover, the layer patterned by the well-known etching method may be sufficient.

<7. Hard coat layer>
A hard coat layer is provided on at least one surface of the transparent resin support, preferably on the transparent conductive layer side, for the purpose of preventing scratches on the surface of the transparent resin support during the production of the transparent conductive film. It is preferable.

By providing a hard coat layer on at least one surface of the transparent resin support, the film can be wound, conveyed, and unwound in the production process of the transparent conductive film of the present invention from the time of forming the transparent resin support. It has the effect of preventing the occurrence of scratches due to surface pressure and friction between the film surfaces.

The hard coat layer is provided by applying and drying an ultraviolet curable acrylate resin and then curing with an ultraviolet light source.

The layer thickness of the hard coat layer is preferably in the range of 0.2 to 5.0 μm, and if the layer thickness of the hard coat layer is in the above range, a sufficient scratch resistance effect can be obtained. Scratches can be prevented and sufficient transparency can be obtained when a transparent conductive film is formed.

The hard coat layer can be produced by laminating a SiO ₂ thin film by a CVD method, a sputtering method, a vapor deposition method or the like with a layer thickness of 100 nm or less in addition to the application.

<8. Anti-blocking layer>
A blocking prevention layer having a 10-point average roughness Rz of 50 nm or less is provided on the surface of the transparent conductive film of the present invention opposite to the surface provided with the transparent conductive layer of the transparent resin support. preferable. The anti-blocking layer is used to prevent sticking between films when winding and handling the film. This is done by providing an arbitrary roughness on the surface of the film and filling this gap with air. It is possible to prevent sticking between films during unwinding and winding operations.

10-point average roughness Rz means Rz defined in JIS B0601: 1994.

The anti-blocking layer can be provided by applying a coating liquid in which fine particles are mixed with a resin such as an acrylate resin. In addition to inorganic fine particles such as silica, resin fine particles can be used as the fine particles. The average particle diameter of the fine particles is preferably within the range of 10 to 300 nm.

In the transparent conductive film of the present invention, each thin film layer of a high refractive index layer, an antisulfurization layer and a transparent conductive layer provided on a transparent resin support is formed by a sputtering method or a vapor deposition method. Is preferred. When each thin film layer provided on the transparent resin support is formed by a sputtering method or a vapor deposition method, productivity is improved and an effect suitable for mass production is obtained. However, the value obtained by the present invention is not impaired even if it is based on any other thin layer manufacturing method such as chemical vapor deposition (CVD).

≪Patterning of transparent conductive layer≫
For example, in order to produce a capacitive touch panel using the transparent conductive film of the present invention, as shown in FIG. 3, the transparent conductive layer is divided into a plurality of conductive regions a and a line-shaped insulating region that divides the conductive regions a. It is preferable to pattern it into a predetermined shape including b.

Examples of the deterioration factor of the transparent conductive layer containing silver include moisture and sulfide contained in the atmosphere. These are taken into the transparent resin support and the hard coat layer, and pass through the hard coat layer to reach the transparent conductive layer. Therefore, the transparent resin support and the hard coat layer alone do not provide sufficient silver protective function for the transparent conductive layer. Therefore, if there is a first high refractive index layer, preferably a first antisulfurization layer, the antisulfurization layer is included. From the viewpoint of preventing the deterioration of the transparent conductive layer, it is preferable to leave it on the transparent resin support without being patterned.

As a method of patterning the transparent conductive layer, a known method can be used. Specifically, such a patterning method can be performed as follows.

(Patterning process)
Hereinafter, a method for forming an electrode pattern by photolithography will be described.

The photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping. The transparent conductive layer is processed into a desired pattern as shown in FIG.

In the present invention, a conventionally known general photolithography method can be used as appropriate. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used.

After development, a resist pattern is formed by stopping development with a rinse solution such as water and washing. Next, the formed resist pattern is pretreated or post-baked as necessary, and then is etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a silver thin film electrode Remove.

After etching, the remaining resist is removed to obtain a transparent electrode having the desired pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.

Next, an electrode pattern forming method applicable to the present invention will be described with reference to FIG.

FIG. 4 is a process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by a photolithography method.

As a first step, as shown in FIG. 4A, on the transparent resin support 1, the first high refractive index layer 2, the first antisulfurization layer 5a, the transparent conductive layer 3, the second antisulfurization layer 5b, the second high A transparent conductive film 100 in which the refractive index layer 4 is laminated in this order is produced.

Next, in the resist film forming step shown in FIG. 4B, a resist film 6 composed of a photosensitive resin composition or the like is uniformly coated on the transparent conductive film 100. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used.

As a coating method, it is applied on the transparent conductive film 100 by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, oven, etc. It can be pre-baked with a heating device. Pre-baking can be performed, for example, using a hot plate or the like in the range of 50 ° C. or higher and 150 ° C. or lower for 30 seconds to 30 minutes.

Next, in the exposure process shown in FIG. 4C), an exposure machine such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner, or the like is used through a mask 7 made with a predetermined electrode pattern to obtain 10 to 4000 J / mm. The resist film 6A to be removed in the next step is irradiated with light of about m ² (wavelength 365 nm exposure amount conversion). The exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

Next, in the developing step shown in FIG. 4D, the exposed transparent conductive film is immersed in a developing solution to dissolve the resist film 6A in the region irradiated with light.

As the developing method, it is preferable to immerse in the developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include aqueous solutions containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed in the range of 50 ° C. to 150 ° C.

Thereafter, “PURE ETCH 100” manufactured by Hayashi Pure Chemical Industries, Ltd. is used as an etchant to remove the second high refractive index layer and the second antisulfurization layer. (Fig. 4E)
Next, “SEA-5” manufactured by Kanto Chemical Co., Inc. is carried out in a short time etching in order to dissolve only the transparent conductive layer and the first antisulfuration layer. (Fig. 4F)
Finally, as shown in FIG. 4G, the resist film 6 is removed by immersing it in a resist film remover, for example, “N-300” manufactured by Nagase ChemteX Corporation, leaving the first high refractive index layer 2. A transparent conductive film having an electrode pattern can be produced.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

≪Preparation of transparent conductive film≫
For the production of the transparent conductive film, the following transparent resin support and conductive material were used.

(Transparent resin support material)
Here, d is the thickness of the support, Ro is the in-plane retardation, and Rt is the retardation in the thickness direction. Ro and Rt are values at a measurement wavelength of 589 nm and are representative values.

1. TPS1: “Zero Tack” manufactured by Konica Minolta Co., Ltd.
d = 50 μm Ro = 0 nm Rt = 0 nm
2. TPS2: “Konica Minolta Tac” manufactured by Konica Minolta, Inc.
Thickness 50 μm Ro = 5 nm Rt = 30 nm
3. PET: Toyobo polyethylene terephthalate film “Cosmo Shine A4300” thickness 50 μm Ro = 5000 nm Rt = 10000 nm
4). PC: Kaneka polycarbonate film “Elmec R40 # 435 film” thickness 40 μm Ro = 435 nm Rt = 600 nm
5. TPS3: ZEON cycloolefin film “ZEONOR Z14 (50 μm)” thickness 50 μm Ro = 1.5 nm Rt = 10 nm
6). TPS4: “VA-TAC” manufactured by Konica Minolta Co., Ltd., thickness 80 μm Ro = 50 nm Rt = 130 nm
(Conductive material)
7). APC: Furuya Metal "Ag alloy" (containing Pd and Cu)
8). APC-TR: “Ag alloy” made of Furuya Metal (containing Pd and Cu)
9. APC-SR: Furuya Metal's “Ag alloy” (containing Pd and Cu)
The above three grade alloys have different compositions.

10. GB-100: “Ag alloy” manufactured by Kobelco Research Institute, Ag (99.0 atm%) / Bi (1.0 atm%)
11. GBR-15: “Ag alloy” manufactured by Kobelco Research Institute, Ag (98.35 atm%) / Bi (0.35 atm%) / Ge (0.3 atm%) / Au (1.0 atm%)
12 Ag: Silver (Purity 99.9% or more)
13. Cu: Copper (purity 99.9% or more)
14 Au: Gold (Purity 99.9% or more)
The following materials were used for the high refractive index layer and the sulfidation prevention layer.
15. ITO: indium tin oxide 16. SiN: silicon nitride n = 2.02 (n represents a refractive index)
17. Nb ₂ O ₅ : Niobium pentoxide n = 2.31
18. ZnO: zinc oxide n = 1.95
19. IZO: indium / zinc oxide 20. 20. GZO: gallium / zinc oxide IGZO: indium gallium zinc oxide 22. TiN: titanium nitride 23. Ga ₂ O ₃ : Gallium oxide 24. Bi ₂ O ₃ : Bismuth oxide 25. ZnS: Sintered body in which the composition of Zn and S is adjusted 26. ZnS—SiO ₂ : a mixture in which the composition of ZnS and SiO ₂ is adjusted 27. ZnO—Ga ₂ O ₃ : a mixture in which the composition of ZnO and Ga ₂ O ₃ is adjusted 28. ZnO—SiN: a mixture in which the composition of ZnO and SiN is adjusted 29. Ga ₂ O ₃ —SiN: mixture in which the composition of Ga ₂ O ₃ and SiN is adjusted 30. ZnS—ZnO: a mixture in which the composition of ZnS and ZnO is adjusted 31. ZnS—SiN: mixture in which the composition of ZnS and SiN is adjusted 32. ZnS—TiN: a mixture in which the composition of ZnS and TiN is adjusted 33. ZnS—Bi ₂ O ₃ : A mixture in which the composition of ZnS and Bi ₂ O ₃ is adjusted. In addition, the ZnS of 26, 30 to 33 is the same as 25, using a sintered body in which the composition of Zn and S is adjusted. A mixture was obtained.

<Preparation of transparent conductive film 1>
(First high refractive index layer)
As a transparent resin support, “Zero tack” (TPS1) (Ro = 0 nm, Rt = 0 nm, d = 50 μm) manufactured by Konica Minolta Co., Ltd. cut into 100 mm square was used. The first high refractive index layer was formed by sputtering using a magnetron sputtering apparatus manufactured by Osaka Vacuum.

A ZnS target with an adjusted composition is placed on the cathode, and the target-side power is 150 W so that the overall formation rate is 3.0 Å / sec (0.3 nm / sec) at Ar 20 sccm, sputtering pressure 0.2 Pa, and room temperature. A first high refractive index layer having a layer thickness of 40.0 nm was formed. RF power was supplied to the cathode.
The distance between the target and the substrate was 90 mm. According to the composition analysis test described later, the composition ratio of Zn and S at this time was 83 with respect to 100 Zn atoms.

(First sulfurization prevention layer)
Next, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, power on the target side is 150 W, and ZnO is formed to a layer thickness of 1.0 nm at a formation rate of 1.1 Å / sec (0.11 nm / sec). Thus, RF sputtering was performed.

(Transparent conductive layer)
Subsequently, silver is sputtered on the first antisulfurization layer by using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., with Ar 20 sccm, sputtering pressure 0.5 Pa, room temperature, and a formation rate of 14 Å / sec (1.4 nm / sec). Then, a transparent conductive layer having a layer thickness of 7.5 nm was formed.

(Second anti-sulfur layer)
Subsequently, RF sputtering was performed with ArO 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, ZnO with a formation rate of 1.1 ｓｅｃ / sec (0.11 nm / sec) and a layer thickness of 1.0 nm. .

(Second high refractive index layer)
Subsequently, ZnS was sputtered by the same method as that for the first high refractive index layer to form a second high refractive index layer having a layer thickness of 40.0 nm, and the transparent conductive film 1 was produced. At this time, the composition ratio of Zn and S was 83 with respect to 100 Zn atoms.

<Preparation of transparent conductive films 2 to 36 and 101 to 107>
The transparent conductive films 2 to 36 of the present invention and the transparent conductive film 101 of the comparative example were used in the same manner as the transparent conductive film 1 except that the configurations shown in Tables 1 and 2 were used. To 107 were produced.

Here, adjustment of each elemental composition ratio of zinc and sulfur in the first high refractive index layer and the second term refractive index layer is performed by adjusting the element composition ratio of the desired ratio in the formed layer. This was done by sputtering using the body as a target. Moreover, also about formation of the layer containing two types of materials in each other layer, it sputters using the mixture prepared beforehand as a target so that each material may become the ratio indicated in Table 1 and Table 2 as a target. To form a layer.

(Composition ratio analysis of the number of zinc and sulfur atoms)
For quantitative elemental analysis of zinc and sulfur, a reference sample in which a predetermined ZnS thin layer was formed as a single layer on BK7 glass was prepared, and ultra-high purity hydrogen peroxide (manufactured by Kanto Chemical Co., Ltd.) was used for these samples. For each element contained in a 20 ml solution obtained by sufficiently dissolving the ZnS layer using a solution and diluting with ultrapure water, a matrix using an ICP emission spectroscopic analyzer “SPS3520UV” manufactured by Hitachi High-Tech Science Co., Ltd. is used. Matching was done.

In the determination, zinc reference solution for atomic absorption analysis 1000 mg / l (manufactured by Kanto Chemical Co., Inc.) was used for zinc as a reference, and sulfur standard solution Sulfur 1000 mg / l (SPEX) was used for sulfur. The measurement wavelength is 213.924 nm for zinc and 180.734 nm for sulfur. A solution sample obtained by performing the same treatment on clean BK7 glass was analyzed, and it was confirmed that the zinc and sulfur components as background noise that hinder the test were below the detection limit.

≪Evaluation of transparent conductive film≫
With respect to the transparent conductive films 1 to 36 of the present invention produced as described above and the transparent conductive films 101 to 107 of the comparative example, the following three types of evaluation were tested before and after the reliability acceleration test described later.

<1. Conductivity evaluation (surface resistance)>
The conductivity of the transparent conductive film was evaluated using a low resistivity meter “Loresta-EP” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

(Evaluation criteria)
◎: Less than 8 Ω / □ ○: 8 Ω / □ or more and less than 10 Ω / □ △: 10 Ω / □ or more and less than 15 Ω / □ ×: 15 Ω / □ or more

<2. Transparency evaluation>
The initial transparency of the transparent conductive film was measured by measuring the average transmittance at a measurement wavelength of 400 to 800 nm using a spectrophotometer “U4100” (manufactured by Hitachi High-Tech).
Assuming that this measurement is applied to a transmissive capacitive touch panel, in order to reflect the actual system, a transparent conductive film comprising a support, a high refractive index layer, an antisulfurization layer and a transparent conductive layer is used. The evaluation was performed by pasting on a glass substrate with immersion oil “type A (n = 1.515)” (manufactured by Nikon Corporation) used in the oil immersion optical system and measuring the total transmittance.

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductive film on the transparent resin support side. On the other hand, the average absorptivity is measured by measuring the average reflectance of the transparent conductive film by making light incident from the same angle as the average transmittance.
Average absorptance = 100− (average transmittance + average reflectance) (%)
Calculated as Average transmittance and average reflectance were measured with a spectrophotometer.

(Evaluation criteria)
◎: Average transmittance is 92% or more ○: Average transmittance is 90% or more and less than 92% △: Average transmittance is 85% or more and less than 90% ×: Average transmittance is less than 85%

<3. Appearance evaluation>
The appearance of the transparent conductive film was evaluated by using a research stereo microscope “SZX10” (manufactured by Olympus) and observing a 30 mm square in the center of the sample (transparent conductive film) at a magnification of 60 times.
With this observation method, the number of occurrences of typical appearance defects such as film cracking and film floating within the observation range was counted and evaluated according to the following criteria.

(Evaluation criteria)
◎: Appearance defect of 4 points or less exists ○: Appearance defect of 5 to 10 points exists Δ: Appearance defect of 11 to 20 points exists ×: Appearance defect of 21 points or more exists

<4. Reliability Acceleration Test>
In the reliability acceleration test (durability test), a small environmental tester “SH-222” (manufactured by ESPEC CORP.) Was used and left in an environment of 80 ° C. and 85% RH for 168 hours. The above-described conductivity evaluation, transparency evaluation, and appearance evaluation were performed before and after this reliability acceleration test.

The initial evaluation and the evaluation after the reliability acceleration test were performed according to the same evaluation criteria as the above-described conductivity evaluation, transparency evaluation, and appearance evaluation.
The above evaluation results are shown in Table 3.

From the above results, it can be seen that the transparent conductive films 1 to 36 of the present invention can provide a transparent conductive film having good conductivity and uniform transparency over the entire visible light range and having high durability.

On the other hand, the transparent conductive films 101 to 107 produced as comparative examples for the effects of the present invention tended to be inferior in initial performance in various characteristics as compared with the present invention.

In addition, the transparent conductive films 101 to 107 of the comparative example were evaluated to be the lowest in any of the three types of evaluation of conductivity, transparency, and appearance by performing a reliability acceleration test. This is in contrast to the fact that the transparent conductive films 1 to 36 of the present invention maintain a high evaluation after the reliability test.

The main factor is presumed to be the sulfur trapping function of the high refractive index layer, which is a feature of the present invention, and the protective function of the conductive layer by the antisulfurization layer. The above comparative example is a transparent conductive layer provided by the present invention. It clearly shows the effect and superiority of the protective film.

The transparent conductive film of the present invention has good conductivity and transparency and high durability, and is used in various devices such as liquid crystal displays, plasma displays, inorganic and organic EL displays, touch panels, and solar cells. It can be suitably used.

DESCRIPTION OF SYMBOLS 100 Transparent conductive film 1 Transparent resin support body 2 1st high refractive index layer 3 Transparent conductive layer 4 2nd high refractive index layer 5a 1st sulfidation prevention layer 5b 2nd sulfidation prevention layer 6 Resist film 6A Resist film 7 to remove 8 Exposure unit EU Transparent electrode unit a Conduction area b Insulation area

Claims

On the transparent resin support, a transparent conductive film having at least a first high refractive index layer, a transparent conductive layer and a second high refractive index layer in this order,
The transparent conductive layer contains silver;
At least one of the first high refractive index layer or the second high refractive index layer is a layer containing zinc sulfide,
The ratio of the number of sulfur atoms contained in the zinc sulfide is 50 or more and less than 100 with respect to 100 zinc atoms.
The transparent conductive film according to claim 1, wherein the layer containing zinc sulfide is a first high refractive index layer.
The first sulfidation prevention layer is provided between the first high refractive index layer and the transparent conductive layer, and the first sulfidation prevention layer contains an oxide or a nitride. The transparent conductive film according to claim 2.
The transparent conductive film according to claim 3, wherein the first sulfidation preventing layer contains zinc oxide or gallium oxide as the oxide.
The first high refractive index layer contains zinc sulfide and an oxide or nitride, and the content of the oxide or nitride is 5 to 30 volumes of the total volume of the first high refractive index layer. % In the range of%, The transparent conductive film as described in any one of Claim 1- Claim 4 characterized by the above-mentioned.
The transparent conductive film according to any one of claims 1 to 5, wherein the first high refractive index layer contains zinc sulfide and silicon dioxide.
The second high refractive index layer is made of zinc sulfide, titanium dioxide, indium tin oxide, zinc oxide, niobium oxide, tin dioxide, indium zinc oxide, aluminum zinc oxide, gallium. Selected from zinc oxide, antimony / tin oxide, indium / cerium oxide, indium / gallium / zinc oxide, bismuth oxide, tungsten trioxide, indium oxide and amorphous oxide containing gallium / indium / oxygen The transparent conductive film according to any one of claims 1 to 6, comprising any one of the above.
The transparent conductive film according to any one of claims 1 to 7, wherein the second high refractive index layer contains zinc sulfide as a high refractive index material.
The transparent conductive film according to claim 8, wherein the second high refractive index layer further contains silicon dioxide as the high refractive index material.
The transparent conductive film according to any one of claims 1 to 7, wherein the second high refractive index layer contains gallium / zinc oxide as a high refractive index material.
The second sulfidation prevention layer is provided between the transparent conductive layer and the second high refractive index layer, and the second sulfidation prevention layer contains an oxide or a nitride. The transparent conductive film according to any one of 10 to 10.
The transparent conductive film according to claim 11, wherein the second antisulfurization layer contains zinc oxide or gallium / zinc oxide as the oxide.