TW201605641A - Transparent electroconductive film - Google Patents

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 which has good conductivity and transparency and has high durability.

In recent years, transparent conductive films have been used for 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, chromium, or the like, or In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , TiO are known. ₂ , an oxide semiconductor such as SnO ₂ , ZnO, or ITO (indium tin oxide).

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

In recent years, in the product group of smart phones, etc., static capacitance The popularity of the touch panel display device of the quantity method is seeking to further reduce the surface resistance of the transparent conductive film. However, the conventional ITO film has a problem that the surface resistance cannot be sufficiently lowered.

Therefore, a vapor deposition film of silver has been studied as a transparent conductive film (see, for example, Patent Document 1). Further, in order to improve the light transmittance of the transparent conductor, a film having a high refractive index of a vapor deposited film of silver (for example, yttrium oxide (Nb ₂ O ₅ ), IZO (indium zinc oxide), or ICO (indium bismuth) has been proposed. Oxide), a film composed of a-GIO (amorphous oxide containing gallium, indium, and oxygen) is held (for example, refer to Patent Documents 2 to 4). Furthermore, it is proposed to hold the deposited film of silver as a film of zinc sulfide (see, for example, Non-Patent Documents 1 and 2).

As a problem in the case where the above silver thin film is provided 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 with sulfides in the atmosphere to color.

This coloring phenomenon is understood to be a phenomenon in which a silver sulfide film is formed on the surface of a large amount of silver. However, as described above, a transparent conductive film which is used in the form of a film obtained by vapor deposition or the like is used as a film. The features that are featured become significant and significant issues.

That is, the film obtained by vapor deposition or sputtering is characterized by extremely small thickness (depth) and extremely remarkable microporousity as compared with a large amount of solid. Therefore, various components that invade sulfide and silver in the atmosphere are easily diffused throughout the silver film, and are not only the interface of the silver film structure but also the modified silver film as a whole. Therefore, the characteristics required for the constituent members of the transparent conductive film, that is, the wavelength uniformity of conductivity, transparency, and optical characteristics are all impaired.

When a silver thin film is used as the transparent conductive layer, the requirement for ensuring the light transmittance is compared with the case where the mirror or the surface decoration is intended, and the film thickness used is limited to be thinner, so that the above air composition is changed. The qualitative impact is particularly large.

When silver is used in the form of a film, special measures must be taken to prevent deterioration due to atmospheric components. However, the conventional method represented by the above-mentioned literature mainly focuses on ensuring high conductivity and transmittance. The countermeasures we have taken to prevent the modification of the silver film as described above are not sufficient.

Further, in the technique of using a sulfur-containing material such as zinc sulfide in a material for holding a silver thin film, by the sulfur contained in the zinc sulfide, during the formation of the transparent conductive member, since the silver has been vulcanized, there is not only an increase in electrical resistance but also damage. The issue of transparency.

In addition, in recent years, the information equipment equipped with the touch panel has been designed to be large-screen, lightweight, and thin, and as a result of having to seek a higher level of image quality, motion accuracy, and reaction speed, both are high conductivity and high conductivity. The importance of transparency has increased a lot compared with the past, and as a result of the tendency to be widely used in people's livelihood, such as smart phones, it is resistant to all temperature and humidity environments or the atmospheric environment, and is strongly required to ensure long-term use. The above conductivity and transparency.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2011-508400

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-184849

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-15623

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-226581

[Non-patent literature]

[Non-Patent Document 1] Xuanjie Liu, et al, (2003). Thin Solid Films 441, 200-206

[Non-Patent Document 2] Optically transparent IR reflective heat mirror films of ZnS-Ag-ZnS, Bruce W. Smith, May 1989. Rochester Institute Of Technology Center For Imaging Science

The present invention has been made in view of the above problems and circumstances, and it is an object of the present invention to provide a transparent conductive film having high conductivity and uniform transparency through a visible light region and having high durability.

In order to solve the above problems, the present inventors have found that at least the first high refractive index layer, the transparent conductive layer, and the second high refractive index layer have a transparent conductive film in the course of the above-mentioned problem. It is characterized in that any of the high refractive index layers contains zinc sulfide, and the ratio of the number of sulfur atoms contained in the zinc sulfide is reduced to more than the number of zinc atoms. In other words, a silver thin film is used in addition to the transparent conductive layer of the transparent conductive film, and the silver thin film is protected from atmospheric components which deteriorate silver such as sulfide, and the transparent conductive member is optimized for light transmission in the entire visible light region. In addition to the rate, the present invention has been accomplished by providing a high refractive index layer of an appropriate composition to solve the above problems.

That is, the above problems related to the present invention are solved by the following means.

A transparent conductive film which is a transparent conductive film which is provided on a transparent resin support at least in the order of a first high refractive index layer, a transparent conductive layer and a second high refractive index layer, and is characterized in that said transparent conductive film The layer contains silver, and 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 to the number of zinc atoms is 100. 50 or more, and less than 100.

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

3. The transparent conductive film according to the first or second aspect, wherein the first vulcanization preventing layer is contained between the first high refractive index layer and the transparent conductive layer, and the first vulcanization preventing layer contains an oxide Or nitride.

4. The transparent conductive film according to the third aspect, wherein the first vulcanization preventing layer contains zinc oxide or gallium oxide as the oxide.

5. The transparent conductive film according to Item 1, wherein the first high refractive index layer contains zinc sulfide, an oxide or a nitride, and the oxidation The content of the substance or the nitride is in the range of 5 to 30% by volume based on the total volume of the first high refractive index layer.

6. The transparent conductive film according to Item 1, wherein the first high refractive index layer contains zinc sulfide and cerium oxide.

7. The transparent conductive film according to the first aspect, wherein the second high refractive index layer is selected from the group consisting of zinc sulfide, titanium oxide, indium tin oxide, zinc oxide, antimony oxide, and tin dioxide. Indium zinc oxide, aluminum zinc oxide, gallium zinc oxide, antimony tin oxide, indium antimony oxide, indium gallium zinc oxide, antimony oxide, tungsten trioxide, indium oxide and containing gallium. indium. And any one of oxygen amorphous oxides.

8. The transparent conductive film according to Item 1, 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 cerium oxide as the high refractive index material.

10. The transparent conductive film according to Item 1, wherein the second high refractive index layer contains gallium zinc oxide as the high refractive index material.

The transparent conductive film according to the first aspect, wherein the second vulcanization preventing layer is contained between the transparent conductive layer and the second high refractive index layer, and the second vulcanization preventing layer contains an oxide or a nitride.

The transparent conductive film according to the eleventh aspect, wherein the second vulcanization preventing layer contains zinc oxide or gallium zinc oxide as the oxide.

According to the above-described means of the present invention, it is possible to provide a transparent conductive film having excellent conductivity and transparency which is uniform in the entire visible light region and having high durability.

Although the performance mechanism to the action mechanism of the present invention has not been clarified, it is presumed to be as follows.

In general, films formed by vacuum processes exhibit low density and microvoid properties relative to large amounts of solids. Although the sputtering method can form a relatively large film in the dry coating method, it is low in density compared with a large amount of solid. Therefore, it can be said that the diffusion of the element is likely to occur. Therefore, even if the protective layer is provided for the sealing of the transparent conductive layer, it is presumed that there is an upper limit to the film thickness which is sufficiently practical from the viewpoint of adhesion, and the effect is limited.

In addition to the scientific background, the present inventors have made an effort to find a realistic and maximum conductive layer modification suppressing means, and infer as follows, and as a result, the effect of the present invention was found to complete the present invention. .

That is, among the element species contained in the atmosphere, the sulfur component is most adversely affected with respect to the silver constituting the transparent conductive layer, and if the zinc sulfide (ZnS) is contained in a stoichiometric composition ratio (containing zinc sulfide) The proportion of the number of sulfur atoms is the same as that of the zinc element 1 and the sulfur deficiency state is formed in the vicinity of the conductive layer. When exposed to the sulfur-containing component contained in the atmosphere, sulfur (S) is obtained from the atmospheric component, and Not from the strength of the covalent bond Further, it is released, but is a stoichiometric composition ratio, that is, a mechanism for expressing the effect of the present invention by suppressing the diffusion of the sulfur component to the silver-containing transparent conductive film layer by acting as a sulfur trapping film.

Further, the refractive index of the layer containing zinc sulfide obtained in the present invention becomes a very high value. Thus, by appropriately controlling the film thickness of the layer containing zinc sulfide, the result of a decrease in the transmission strength by reflection of silver (Ag) can be remarkably alleviated. A transparent conductive film which is excellent in visibility and high in transparency can be formed.

100‧‧‧Transparent conductive film

1‧‧‧Transparent resin support

2‧‧‧1st high refractive index layer

3‧‧‧Transparent conductive layer

4‧‧‧2nd high refractive index layer

5a‧‧‧1st vulcanization prevention layer

5b‧‧‧2nd vulcanization prevention layer

6‧‧‧Resist film

6A‧‧‧Removed resist film

7‧‧‧ mask

8‧‧‧Exposure machine

EU‧‧‧Transparent electrode unit

A‧‧‧conductive area

b‧‧‧Insulated area

Fig. 1 is a schematic cross-sectional view showing an example of a layer configuration of a transparent conductive film of the present invention.

Fig. 2 is a schematic view showing an example of a pattern formed by a conduction region and an insulating region of the transparent conductive film of the present invention.

Fig. 3 is a schematic view showing an example of an electrode pattern composed of a conduction region and an insulating region of the transparent conductive film of the present invention.

Fig. 4 is a flow chart showing the steps of forming an electrode pattern by photolithography in the transparent conductor of the present invention.

The transparent conductive film of the present invention is a transparent conductive film which is provided on the transparent resin support at least in the order of the first high refractive index layer, the transparent conductive layer and the second high refractive index layer, and is characterized by the transparent conductive film. The layer contains silver, and 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 to the number of zinc atoms is 100. 50 or more, and less than 100. This feature is a common feature common to the invention of claim 1 from claim 1 to claim 12.

From the viewpoint of exhibiting the effects of the present invention, the zinc sulfide-containing layer is preferably a first high refractive index layer, but is preferably obtained by a high degree of effect of preventing vulcanization of silver in the transparent conductive layer.

Further, the first vulcanization preventing layer is provided between the first high refractive index layer and the transparent conductive layer, and the first vulcanization preventing layer contains an oxide or a nitride, but the elemental result in the oxide or nitride is The form of trapping removes sulfur remaining only in the chamber atmosphere, and then forms a transparent conductive layer containing silver. Since the residual of sulfur is not a problem, a transparent conductive layer can be formed in a good atmosphere. Therefore, it is better.

Further, the first vulcanization preventing layer contains zinc oxide or gallium oxide as the oxide, but the metal in the zinc oxide or the gallium oxide is removed in a trapped form to remove only sulfur remaining in the atmosphere of the chamber, and then formed. In the case of a transparent conductive layer containing silver, since the residual of sulfur is not a problem, it is preferable to form a layer in a favorable atmosphere.

Further, the first high refractive index layer contains zinc sulfide, an oxide or a nitride, and the content of the oxide or the nitride is in the range of 5 to 30% by volume based on the total volume of the first high refractive index layer. However, since the internal structure of the first high refractive index layer is nearly amorphous, the flexibility can be improved. good.

Further, the first high refractive index layer contains zinc sulfide and ceria. However, since the internal structure of the first high refractive index layer is nearly amorphous, the flexibility can be improved.

Further, as the high refractive index material, the second high refractive index layer may be selected from the group consisting of zinc sulfide (ZnS), titanium oxide (TiO ₂ ), indium tin oxide (ITO), zinc oxide (ZnO), and cerium oxide (Nb). ₂ O ₅ ), tin dioxide (SnO ₂ ), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), antimony tin oxide (ATO), indium antimony oxide ( ICO), indium gallium zinc oxide (IGZO), bismuth oxide (Bi ₂ O ₃ ), tungsten trioxide (WO ₃ ), indium oxide (In ₂ O ₃ ), and gallium. indium. And any of the amorphous oxides of oxygen (a-GIO), but in addition to lowering the surface resistance, it is also preferable to make the conduction during patterning easier.

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

Further, as the high refractive index material, the second high refractive index layer further contains ceria, but the internal structure of the second high refractive index layer is nearly amorphous, and the flexibility can be improved.

Further, as the high refractive index material, the second high refractive index layer contains gallium zinc oxide, but it is preferable because it is suitable for patterning and a silver protection function.

Further, a second vulcanization preventing layer is provided between the transparent conductive layer and the second high refractive index layer, and the second vulcanization preventing layer contains an oxide Or nitride, but it is preferable because it has an effect of preventing vulcanization of silver of the transparent conductive layer.

Further, as the oxide, the second vulcanization preventing layer contains zinc oxide or gallium zinc oxide, but it is preferable because it has a high effect of preventing vulcanization of silver in the transparent conductive layer.

Hereinafter, constituent elements of the present invention, and the present embodiment and aspects will be described in detail. In the present case, the "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

≪Transparent conductive film≫

The transparent conductive film of the present invention is a transparent conductive film which is provided on the transparent resin support at least in the order of the first high refractive index layer, the transparent conductive layer and the second high refractive index layer, and is characterized by the transparent conductive layer. Silver is contained, and 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 50 with respect to 100 zinc atoms. Above, and not up to 100.

One embodiment of the layer configuration of the transparent conductive film of the present invention is shown in Figs. 1 and 2 .

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

Further, between the first high refractive index layer 2, the second high refractive index layer 4, and the transparent conductive layer 3, it is preferable to have at least one of the vulcanization preventing layers 5a or 5b. Further, the layers are formed from a film, and the vulcanization preventing 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, the first high refractive index layer 2 or the second high refractive index layer 4 and a transparent conductive layer. Between 3, it is preferable to provide the vulcanization preventing layer 5 (the vulcanization preventing layer 5a or 5b containing zinc oxide).

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

When a high refractive index layer containing zinc sulfide is formed before the transparent conductive layer containing silver, the partial or integral vulcanization of the transparent conductive layer containing silver is caused by the following two reasons, which is presumed to be significantly transparent. The properties and conductivity are lowered, and the background of the technique can be eliminated by setting the vulcanization preventing layer to a layer thickness of 0.1 to 5 nm, and the following description will be made.

First, when a high refractive index layer is provided on the support side of the transparent conductive layer, that is, when a layer containing zinc is formed and a layer containing silver is formed, when a layer containing zinc sulfide is formed, it is released in the film forming chamber. The sulfur component forms a layer containing silver only in a state of remaining. As a result, vulcanization reforming of the transparent conductive layer is caused by the time point of formation of the transparent conductive member. Needless to say, this is only solved by the exhaust performance of the device or the cold trap function. Very difficult thing.

For this problem, when a layer containing zinc sulfide is formed to form a layer containing zinc oxide or gallium oxide, zinc or gallium in zinc oxide is removed in a trapped form to remove only sulfur remaining in the atmosphere of the chamber, and then formed. In the case of a layer containing silver, since the residual of sulfur is not a problem, film formation in a good atmosphere is likely to be preferable.

Next, when a transparent conductive layer containing silver is formed to form a high refractive index layer containing zinc sulfide, the surface of the silver layer existing on the support is in direct contact with a high concentration of sulfur component, and the transparent conductive member is formed. At the time of formation, the vulcanization of the transparent conductive layer is still produced.

Further, when the transparent conductive member is formed by sputtering, not only the exposure of the sulfur component of silver, but also the component containing sulfur has a high incident energy for incidence, and the silver surface is slightly reverse-sputtered simultaneously with the vulcanization modification, sometimes Will roughen the surface traits. In order to improve the permeability, the silver transparent conductive layer is provided in an extremely thin film thickness, but when the surface properties are deteriorated as described above, the conductive network portion is cut, not only the conductivity is lowered, but also the cut portion is cut. The rough island-like structure is exhibited, and since the plasmon absorption is generated from the characteristics of the shape, scattering occurs due to the situation, and the transparency is also impaired.

In order to solve this problem, when a layer containing zinc oxide or gallium oxide is formed before the zinc sulfide is provided, it is still preferable to prevent both the vulcanization modification and the reverse sputtering of the silver generated when the layer containing zinc sulfide is formed.

In the transparent conductive film of the present invention, as shown in FIG. 1, the transparent conductive layer 3 can be laminated on the entire surface of the transparent resin support 1, as shown in FIG. As shown, the transparent conductive layer 3 can be patterned into a desired shape. In the transparent conductive film of the present invention, the region a in which the transparent conductive layer 3 is laminated is an electrically conductive region (hereinafter also referred to as "conductive region"). Further, as shown in FIG. 2, the region b not including the transparent conductive layer 3 is an insulating region.

The pattern formed by the conduction region a and the insulating region b is appropriately selected in accordance with 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, a plurality of conductive regions a and a linear insulating region b which is different from the above may be included.

Further, the transparent conductive film 100 of the present invention may include a transparent resin support 1, a first high refractive index layer 2, a transparent conductive layer 3, a second high refractive index layer 4, and a layer other than the vulcanization preventing layer 5. . For example, when the transparent conductive layer 3 is formed, it can be a base layer of a growth core, and can be included between the transparent conductive layer and the first high refractive index layer 2 adjacent to the transparent conductive layer 3.

≪ Layer composition for transparent conductive film≫ <1. Transparent resin support>

The transparent resin support 1 used for the transparent conductive film 100 is exemplified by a cellulose ester resin (for example, triacetyl cellulose (ZeroTack), diethyl fluorenyl cellulose, and B.醯-acrylonitrile-based cellulose, etc., polycarbonate resin (for example, Panlite, Multilon (manufactured by Teijin Co., Ltd.)), and cycloolefin resin (for example, ZEONOR (manufactured by Zeon Corporation, Japan), Arton (manufactured by JSR), Appel (Mitsui) Chemical Silicone resin (for example, polymethyl methacrylate, Acrylite (manufactured by Mitsubishi Rayon Co., Ltd.), SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.)), and the resin is preferably 50% by mass or more of the transparent resin support. . These resins may be used in two or more types.

Among these resins, preferred are cellulose ester resins, cyclic olefin resins and polycarbonate resins.

Further, as a resin which can be mixed with others, may be selected from the group consisting of polyimine, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (for example, polyethylene terephthalate (PET), Ethylene naphthalate, polyether oxime, ABS/AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol/EVOH (Ethylene vinyl alcohol resin), and styrene One or more resins of block copolymer resins and the like.

Further, when the transparent resin support 1 used in the present invention is a cellulose ester, a lower fatty acid ester is preferred, and cellulose acetate, cellulose acetate propionate, and cellulose B are preferably used. Acid ester butyrate or cellulose acetate propionate butyrate. The cellulose ester used in the present invention has a degree of substitution of the thiol group of 2.85 to 3.00, which is preferable because the surface alignment degree is kept lower, and particularly preferably 2.92 to 3.00.

The method for determining the degree of substitution of the thiol group can be determined in accordance with the provisions of ASTM-D817-96.

It is preferred to use a cellulose ester having a degree of polymerization of from 250 to 400, particularly preferably using cellulose triacetate. The number average molecular weight Mn of the cellulose ester of the present invention is 70,000 to 250,000, which is mechanically strong. The degree is excellent, and it is preferably a moderate doping viscosity, and more preferably 80,000 to 150,000. Further, it is preferred to use a cellulose ester having a ratio Mw/Mn of from 1.0 to 5.0 with respect to the weight average molecular weight Mw.

When the transparent resin support contains at least one selected from the group consisting of a cellulose ester resin, a cycloolefin resin, and a polycarbonate resin, the in-plane retardation value Ro can be adjusted to 0 at a measurement wavelength of 589 nm of the transparent resin support. In the range of 150 nm, that is, it is preferably obtained as a low retardation film which is often used for a display of the main use form of the present invention.

Further, the retardation value of the transparent resin support can be controlled by the selection of the resin material, the draw ratio at the time of film formation, and the like. Specifically, by appropriately selecting the drawing magnification in the longitudinal direction and the transverse direction, it is possible to control at any value, the in-plane retardation value Ro and the thickness direction retardation value Rt at 23 ° C. In the environment of 55% RH, it can be measured by the phase difference measuring device "KOBRA-21ADH" (manufactured by Oji Scientific Instruments Co., Ltd.).

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, still more preferably 85% or more. When the average transmittance of light of the transparent resin support 1 is 70% or more, the light transmittance of the transparent conductive film 100 is easily improved. Further, the average absorption ratio 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, still more preferably 3% or less.

The average transmittance is measured by incident light from an angle of 5° with respect to the normal line of the surface of the transparent resin support 1 . In addition, the average The absorptance was measured by inputting light at the same angle as the average transmittance, and the average reflectance of the transparent substrate 1 was measured and calculated as an average absorptivity=100-(average transmittance + average reflectance) (%). The average transmittance and the average reflectance were measured by a spectrophotometer.

In addition, the surface roughness Ra of the transparent resin support is preferably 3.5 nm or less, and more preferably 3.0 nm or less, on both surfaces of the transparent resin support in order to set the transmittance of the transparent resin support within the above range. 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 transparent resin support body which has a haze value and is excellent in transparency can be obtained. Here, the surface roughness Ra means the arithmetic mean roughness in JIS B0601:2001.

The haze value of the transparent resin support 1 of the present invention is preferably from 0.01 to 2.5 (%), more preferably from 0.1 to 1.2 (%). When the haze value of the support is 2.5 (%) or less, the haze value of the transparent conductive film is suppressed.

In addition, the haze value of the transparent resin support was measured by haze meter "type: NDH 2000" (made by Nippon Denshoku Co., Ltd.).

The refractive index of the light having a wavelength of 570 nm of the transparent resin support 1 is preferably from 1.40 to 1.95, more preferably from 1.45 to 1.75, still more preferably from 1.45 to 1.70. The refractive index of the transparent resin support generally varies depending on the material of the support. The refractive index of the transparent resin support is at 23 ° C. 55% RH was measured with an ellipsometer.

The thickness of the transparent resin support 1 is preferably 1 μm~ 20mm, more preferably 10μm~2mm. When the thickness of the transparent resin support is 1 μm or more, the strength of the transparent resin support 1 is increased, and it is difficult to crack or crack the first high refractive index layer 2 during production. In addition, when the thickness of the transparent resin support 1 is 20 mm or less, the flexibility of the transparent conductive film 100 is sufficient. Further, the thickness of the machine using the transparent conductive film 100 can be reduced. Further, it is also possible to reduce the weight of the machine using the transparent conductive film 100.

<2. First high refractive index layer>

The term "high refractive index layer" as used in the present invention means a layer having a higher refractive index than the transparent resin support 1 in a layer containing a high refractive index material.

The first high refractive index layer 2 adjusts the conduction region a of the transparent conductive film, that is, the layer that adjusts the light transmittance (optical admittance) of the region in which the transparent conductive layer 3 is formed, and is formed at least in the conduction region of the transparent conductive film 100. a. The first high refractive index layer 2 is preferably formed in the insulating region b of the transparent conductive film 100 because it has a function of protecting the transparent conductive layer from moisture or sulfide or sulfur-containing components in the atmosphere.

In the present invention, 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 first high refractive index and the second high refractive index layer have a first high refractive index. Rate layer 2 is a preferred layer containing zinc sulfide (ZnS). When the first high refractive index layer 2 contains zinc sulfide, it is difficult to permeate moisture from the side of the transparent resin support 1 and the corrosion of the transparent conductive layer 3 is suppressed. In the first high refractive index layer 2, another dielectric material or an oxide semiconductor material may be contained together with the zinc sulfide. Together with zinc sulfide The refractive index of light having a wavelength of 570 nm including the dielectric material or the oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent resin support 1, and more preferably 0.4 to 1.0. Further, the specific refractive index of the light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material contained in the first high refractive index layer 2 is preferably 1.5, more preferably 1.7 to 2.5, still more preferably 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 conduction region a of the transparent conductor 100 is sufficiently adjusted by the first high refractive index layer 2. Further, the refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material contained in the first high refractive index layer 2 or the density of the material contained in the first high refractive index layer 2. The above refractive index is at 23 ° C. It was measured by an ellipsometer in an environment of 55% RH.

In the present invention, the first high refractive index layer is preferably a layer containing zinc sulfide, and the composition ratio of the number of sulfur atoms is 50 or more and less than 100 with respect to the number of zinc atoms. The number of sulfur atoms is preferably 83 or more and 90 or less with respect to 100 zinc atoms. In the range of this, the silver contained in the transparent conductive layer is excellent in the vulcanization preventing effect, and has excellent conductivity and transparency, and the light transmittance is uniform throughout the visible light region, and the effect of improving durability is obtained.

<Analysis method of sulfur number and zinc atom number>

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

In the quantitative analysis of the elements of zinc and sulfur, a specific ZnS thin layer was formed as a reference sample on a BK7 glass in a single layer. For these samples, ultra-high purity hydrogen peroxide (manufactured by Kanto Chemical Co., Ltd.) was used to make ZnS. The layer was sufficiently dissolved, and each element contained in a 20 ml solution obtained by dilution with ultrapure water was subjected to matrix matching using an ICP emission spectroscopic analyzer "SPS3520UV" manufactured by Hitachi High-tech Science.

For the purpose of quantification, 1000 mg/l of zinc standard solution for atomic absorption analysis (manufactured by Kanto Chemical Co., Ltd.) and sulfur standard solution Sulfur 1000 mg/l (SPEX) were used for zinc. The wavelength was measured, zinc was 213.924 nm, and sulfur was 180.734 nm.

In the measurement, the analysis of the solution sample obtained by subjecting the cleaned BK7 glass to the same treatment was carried out, and it was confirmed that the zinc and sulfur components which are the background noise which hindered the test were below the detection limit.

<Control method of sulfur content>

In the present invention, the ratio of the number of zinc atoms to the number of sulfur atoms contained in the first high refractive index layer is co-evaporated or co-sputtered with zinc sulfide and zinc, and can be controlled by adjusting individual conditions.

Further, in order to obtain a composition containing a large amount of sulfur, a reactive sputtering method may be used. For example, hydrogen sulfide (H ₂ S) gas diluted with Ar gas may be blown into the vacuum chamber, and zinc sulfide (ZnS) may be used. It is controlled by sputtering as a target.

When the layer is formed by sputtering, the layer formed Among them, by obtaining a desired composition, a sputtering target which is adjusted to an appropriate elemental composition ratio and mainly used as a sintered body is used, and the sputtering target is used as a simple one, and the production step affinity is high and excellent. Such a sintered body having a different elemental composition ratio can be obtained as a commercial product.

The first high refractive index layer is preferably an oxide or a nitride as the material to be used together with the above zinc sulfide. As the oxide, it is particularly preferably cerium oxide (SiO ₂ ). Examples of the nitride include tantalum nitride (Si ₃ N ₄ , SiN), aluminum nitride (A1N), and titanium nitride (TiN).

As a method of controlling the composition of zinc sulfide (ZnS) and cerium oxide (SiO ₂ ), for example, a sputtering method using a target of zinc sulfide (ZnS) containing cerium oxide (SiO ₂ ) in an appropriate concentration can be used and used simultaneously. Co-sputtering of a target of cerium oxide (SiO ₂ ) and zinc sulfide (ZnS) is carried out.

When the high refractive index layer containing zinc sulfide (ZnS) contains cerium oxide at a concentration of 5 to 30% by volume or less, the internal structure of the layer is nearly amorphous, and flexibility can be improved.

When zinc sulfide (ZnS) is a material having strong covalent bond properties, when the stoichiometric composition ratio is obtained from a state of deviation, it is considered that the internal structure of the layer is a crystal having a large number of grain boundaries. The properties of the layer obtained at this time become hard and brittle, and also deteriorate in adhesion strength.

In addition, since the transparent conductive film is often repeatedly unwound, wound, and operated between the steps of roll-to-roll, when the process is crystalline, fine cracking occurs due to the grain boundary as a starting point, and the transparency is impaired. The sealing property of the conductive layer is optimal for imparting flexibility.

In addition, the softness obtained by containing cerium oxide Since the layer is excellent in tracking the trajectory of thermal expansion of the support made of resin, it is possible to reduce the occurrence of fine cracks and to improve the reliability under temperature and pressure, and it is still preferable.

It is necessary to maintain the refractive index for adjusting the optical characteristics of the transparent conductive film, and to adjust to such an extent that the aforementioned sulfur trapping function is not impaired. From this point of view, the cerium oxide is preferably contained in a concentration of 5 to 30% by volume 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 conduction region a of the transparent conductive film 100 is sufficiently adjusted by the first high refractive index layer 2. In addition, when the layer 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 hardly lowered. The layer thickness of the first high refractive index layer 2 was measured by an ellipsometer "Multi-incident angle spectroscopic ellipsometer VASE (registered trademark)" (manufactured by J.A. Woollam Co., Ltd.).

The first high refractive index layer 2 may be a general vapor phase deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method (the deposition method is also called a vapor phase growth method). The layer formed. From the viewpoint of increasing the refractive index (density) of the first high refractive index layer 2, the first high refractive index layer 2 is preferably a layer formed by an electron beam evaporation method or a sputtering method. In the electron beam evaporation method, in order to increase the density of the layer, assistance such as IAD (ion assist) is expected.

Further, when the first high refractive index layer 2 is patterned into a layer having a desired shape, the patterning method is not particularly limited. First high refractive index layer 2, For example, a mask having a desired pattern or the like is disposed on the film formation surface, and a layer formed in a pattern by a vapor phase film formation method may be used, and the layer may be patterned by a well-known etching method.

<3. First vulcanization preventing layer>

The first high refractive index layer 2 contains zinc sulfide, and as shown in FIG. 1, the first vulcanization prevention is contained between the first high refractive index layer 2 and the transparent conductive layer 3, and contains an oxide or a nitride. The layer 5a is preferably used, and the vulcanization preventing layer 5a is preferably a first vulcanization preventing layer 5a containing zinc oxide or gallium oxide. The first vulcanization preventing layer 5a has a function of preventing diffusion of sulfide or sulfur-containing components from the first high refractive index layer. Further, the first vulcanization preventing layer 5a may be formed in the insulating region b of the transparent conductive film 100. In this case, it is preferable to protect the transparent conductive layer from moisture or sulfide or sulfur-containing components in the atmosphere. The function of the conductive layer can also be formed in the insulating region b.

The first vulcanization preventing layer 5a is preferably a layer containing zinc oxide or gallium oxide, and may further include a layer of a metal oxide, a metal nitride, a metal fluoride or the like. In the first vulcanization preventing layer 5a, these may be contained alone or in combination of two or more. However, when the first high refractive index layer 2, the first vulcanization preventing layer 5a, and the transparent conductive layer 3 are continuously formed, a compound in which a metal oxide can react with sulfur or which can adsorb sulfur is preferable. When the metal oxide is a compound which reacts with sulfur, the reactant of the metal oxide and sulfur preferably has high visible light permeability.

In the example of the metal oxide, in addition to zinc oxide (ZnO) and gallium oxide (Ga ₂ O ₃ ), titanium oxide (TiO ₂ ), indium tin oxide (ITO), niobium oxide (Nb ₂ O ₅ ), Zirconia (ZrO ₂ ), cerium oxide (CeO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), titanium oxide (Ti ₃ O ₅ ), titanium oxynitride (Ti ₄ O ₇ ), titanium oxide (Ti _{2 )} O ₃ ), titanium oxide (TiO), tin dioxide (SnO ₂ ), barium oxide (La ₂ Ti ₂ O ₇ ), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), antimony tin oxide (ATO), indium antimony oxide (ICO), bismuth oxide (Bi ₂ O ₃ ), amorphous oxide (a-GIO) composed of gallium, indium, and oxygen, Cerium oxide (GeO ₂ ), cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), cerium oxide (HfO ₂ ), cerium oxide (SiO), magnesium oxide (MgO), cerium oxide (Y ₂ O _{3 )} ) and 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 ), and aluminum fluoride (AlF ₃ ). , magnesium fluoride (MgF _2), calcium fluoride (CaF _2), barium fluoride (BaF _2), cerium fluoride (CeF _3), neodymium fluoride (NdF ₃₎ and yttrium fluoride (YF ₃₎ and the like.

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

Among these, a layer containing zinc oxide or gallium oxide is preferred. When the first vulcanization preventing layer is divided into a layer of two components such as zinc oxide and gallium oxide or zinc oxide or tantalum nitride, an individual material can be formed into a layer by a sputtering method using a target mixed in a desired ratio. Layers can also be formed by co-sputtering using simultaneous use of individual targets.

Here, the layer thickness of the first vulcanization preventing layer 5a is preferably an impact at the time of formation of the transparent conductive layer 3 to be described later, and the surface of the first high refractive index layer 2 has a layer thickness that can be protected. In addition, it can be included in the first high refraction The zinc oxide or gallium oxide of the rate layer has high affinity with the metal contained in the transparent conductive layer 3. Therefore, the first vulcanization preventing layer 5a has a very small layer thickness, and when only a part of the first high refractive index layer 2 is exposed, the exposed portion is a transparent metal film in which the transparent conductive layer is grown, and the transparent conductive layer 3 is easily densified. That is, the first vulcanization preventing layer 5a is preferably relatively thin, preferably 0.1 to 5.0 nm, more preferably 0.5 to 2.0 nm.

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

When the first vulcanization preventing layer 5a is patterned into a layer having a desired shape, the patterning method is not particularly limited. The first vulcanization preventing layer 5a may be, for example, a mask having a desired pattern or the like disposed on the film formation surface, and may be a layer formed by a vapor phase film formation method, or may be a well-known etching method. The layer of the type.

<4. Transparent conductive layer>

The transparent conductive layer 3 is used in the transparent conductive film 100 to conduct an electrical layer. As described above, the transparent conductive layer 3 can be formed on the entire surface of the transparent resin support 1, or can be patterned into a desired shape.

The transparent conductive layer 3 is a layer containing silver and may contain other metals. The metal to be 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, lanthanum, cerium, lanthanum, and molybdenum are preferable.

Among these, gold, palladium, rhodium, iridium, copper, etc. are preferred. Platinum, rhodium and ruthenium. In the transparent conductive layer 3, these metals may be contained alone or in combination of two or more. From the viewpoint of conductivity, the transparent conductive layer preferably contains an alloy containing 90 atm or more of silver. When the silver content is 90 atm% or more, excellent electrical conductivity and high durability can be obtained.

Further, when at least one of the above-mentioned metals having high transparent conductivity is contained in the above range, even if the thickness of the thin transparent conductive layer is thin, specific conductivity can be ensured, and the deterioration of silver contained in the transparent conductive layer can be improved. The reliability of the effect. For example, when silver and zinc are combined, the sulfidation resistance of the transparent metal layer is improved. When combining silver and gold, the salt tolerance (NaCl) is improved. Further, when silver and copper are combined, oxidation resistance is improved.

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. By this layer thickness, the desired transparency and plasmon absorption rate can be guaranteed.

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

The transparent conductive layer 3 may be a layer formed by any of the forming methods. However, in order to change the average transmittance of the transparent conductive layer, it is preferably formed by a layer formed by a sputtering method or a base layer to be described later. Floor.

In the sputtering method, when the layer is formed, the material collides with the film formation body at a high speed, and a dense and smooth layer is easily obtained, and the light transmittance of the transparent conductive layer 3 is easily improved. Further, when the transparent conductive layer 3 is a layer formed by a sputtering method, the transparent conductive layer 3 is hard to corrode even in an environment of high temperature and low humidity.

The type of sputtering method is not particularly limited, and may be ion beam sputtering, magnetron sputtering, reactive sputtering, 2-pole sputtering, bias (Bias) sputtering, or opposite sputtering. Plating method, etc. The transparent conductive layer 3 is preferably a layer formed by a counter sputtering method. When the transparent conductive layer 3 is a layer formed by the opposite sputtering method, the transparent conductive layer 3 becomes dense and the surface smoothness is easily improved. As a result, the surface resistance of the transparent conductive layer 3 is changed low, and the transmittance of light is also easily improved.

<5. Second vulcanization preventing layer>

When the second high refractive index layer to be described later is a zinc sulfide-containing layer, as shown in FIG. 1, between the transparent conductive layer 3 and the second high refractive index layer 4, zinc oxide, gallium zinc oxide or gallium oxide is contained. The second vulcanization preventing layer 5b is preferred. The second vulcanization preventing layer 5b may be formed in the insulating region b of the transparent conductive film 100. However, from the viewpoint of being difficult to recognize the pattern formed by the conductive region a and the insulating region b, it is preferable to form only the Conduction area a.

The second vulcanization preventing layer 5b is a layer containing zinc oxide, gallium zinc oxide or gallium oxide, and may be a layer containing a metal oxide, a metal nitride, a metal fluoride or the like. In addition to zinc oxide, the second vulcanization preventing layer 5b may be contained alone or in combination of two or more. The metal oxide, the metal nitride, and the metal fluoride may be the same as the metal oxide, metal nitride, or metal fluoride contained in the first high refractive index layer 2 described above. Among these, a layer containing zinc oxide is preferred.

Dividing the second vulcanization preventing layer into zinc oxide and gallium oxide or oxygen When a layer of two components such as zinc and tantalum nitride is used, an individual material may be formed into a layer by a sputtering method using a target mixed in a desired ratio. Layers can also be formed by co-sputtering using a separate target simultaneously.

In addition, the thickness of the second vulcanization preventing layer 5b is preferably a thickness that protects the surface of the transparent conductive layer 3 from the viewpoint of damage at the time of formation of the second high refractive index layer 4 to be described later. Further, the metal included in the transparent conductive layer 3 has high affinity with the ZnS contained in the second high refractive index layer 4. Therefore, when the thickness of the second vulcanization preventing layer 5b is extremely thin and only one portion of the transparent conductive layer 3 is exposed, the adhesion between the transparent conductive layer 3 or the second vulcanization preventing layer 5b and the second high refractive index layer 4 is easily improved. . Accordingly, the specific layer thickness of the second vulcanization preventing layer 5b is preferably from 0.1 to 5.0 nm, more preferably from 0.5 to 2.0 nm. The layer thickness of the second vulcanization preventing layer 5b is measured by an ellipsometer.

The second vulcanization preventing layer 5b may be a layer formed by a general vapor phase film formation method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method.

When the second vulcanization preventing layer 5b is patterned into a layer having a desired shape, the patterning method is not particularly limited. The second vulcanization preventing layer 5b may be, for example, a mask having a desired pattern or the like disposed on the film formation surface, and may be a layer formed by a vapor phase film formation method, or may be a well-known etching method. The layer of the type.

<6. Second high refractive index layer>

The second high refractive index layer 4 adjusts the conduction of the transparent conductive film 100 The region a, that is, a layer for adjusting the light transmittance (optical admittance) of the region in which the transparent conductive layer 3 is formed, is formed at least in the conduction region a of the transparent conductive film 100. Although the second high refractive index layer 4 can be formed in the insulating region b of the transparent conductive film 100, it is preferably formed only from the viewpoint that the pattern formed by the conductive region a and the insulating region b is difficult to be recognized. Conduction area a. Since the second high refractive index layer 4 is hard to permeate water molecules and sulfide molecules from the atmosphere side, it has an effect of suppressing corrosion of the transparent conductive layer 3.

The second high refractive index layer 4 is a layer having a high refractive index material and is a layer having a refractive index higher than that of the transparent resin support 1 described above, and the layer of any of the first high refractive index layers is A layer containing zinc sulfide (ZnS). The second high refractive index layer 4 may contain zinc sulfide or another dielectric material or an 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 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1, and more preferably 0.4 to 1.0.

Further, the dielectric material or the oxide semiconductor material contained in the second high refractive index layer 4 preferably has a refractive index of more than 1.5, more preferably 1.7 to 2.5, still more preferably 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 conduction region a of the transparent conductive film 100 is sufficiently adjusted by the second high refractive index layer 4. Further, the refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material contained in the second high refractive index layer 4 or the density of the material included in the second high refractive index layer 4.

The dielectric material or the oxide semiconductor material included in the second high refractive index layer 4 may be an insulating material and may be a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. Examples of the metal oxide include cerium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), ITO (indium tin oxide), zinc oxide (ZnO), cerium oxide (Nb ₂ O ₅ ), and zirconium oxide (ZrO). ₂ ), cerium oxide (CeO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), titanium oxide (Ti ₃ O ₅ ), titanium oxynitride (Ti ₄ O ₇ ), titanium oxide (Ti ₂ O ₃ ), titanium oxide (TiO), tin dioxide (SnO _2), lanthanum oxide _{(La 2 Ti 2 O 7)} , indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), Antimony tin oxide (ATO), indium antimony oxide (ICO), indium gallium zinc oxide (IGZO), bismuth oxide (Bi ₂ O ₃ ), gallium oxide (Ga ₂ O ₃ ), germanium oxide (GeO ₂ ), Tungsten trioxide (WO ₃ ), yttrium oxide (HfO ₂ ), by gallium. An amorphous oxide (a-GIO) composed of indium and oxygen. The second high refractive index layer 4 may contain only one type of the metal oxide, or may contain two or more types.

In the present invention, among the metal oxides, indium zinc oxide (ITO), indium zinc oxide (IZO), gallium zinc oxide (GZO), or indium gallium zinc oxide (IGZO) is preferable. In addition to being suitable for patterning and obtaining silver protection function, these materials can reduce the surface resistance value of the transparent conductive film by using such a wide-gap semiconductor. The removal becomes easy.

Further, in the present invention, the dielectric material or the oxide semiconductor material contained in the second high refractive index layer 4 is particularly preferably zinc sulfide (ZnS). When the second high refractive index layer 4 contains zinc sulfide (ZnS), it is difficult to permeate water molecules or sulfide molecules 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). With respect to the number of zinc atoms of 100, the composition ratio of the sulfur atom at this time is 50 or more and less than 100. The number of sulfur atoms is preferably 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). The material contained together with zinc sulfide (ZnS) may be a metal oxide of the above dielectric material or oxide semiconductor material or cerium oxide (SiO ₂ ), etc., particularly preferably cerium oxide (SiO ₂ ). When cerium oxide (SiO ₂ ) is contained together with zinc sulfide (ZnS), the second high refractive index layer tends to be amorphous, and the flexibility of the transparent conductor is easily increased. When the composition ratio at this time is only in the case of the above zinc sulfide (ZnS), the composition of the sulfur atom is preferably 50 or more and less than 100 with respect to the number of zinc atoms of 100. The number of sulfur atoms is preferably 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 preferably 0.1 to 95% by volume based on the total volume of the second high refractive index layer 4, Preferably, it is 50 to 90% by volume, and more preferably 60 to 85% by volume. When the ratio of ZnS is high, the sputtering rate is increased, and the formation speed of the second high refractive index layer 4 is also increased. When a large amount of components other than ZnS are contained, the amorphousness of the second high refractive index layer 4 is improved, and the crack of the second high refractive index layer 4 is suppressed.

As a method of zinc sulfide and silicon dioxide (SiO ₂₎ to control the composition within the above range, for example, may be utilized: sputtering using a target of silicon dioxide containing an appropriate concentration (SiO ₂₎ of zinc sulfide (Zns) plating method It is carried out by co-sputtering using a target of cerium oxide (SiO ₂ ) and zinc sulfide (ZnS).

When the cerium oxide (SiO ₂ ) is contained in the above range together with the zinc sulfide, the second high refractive index layer tends to be amorphous, and the flexibility of the transparent conductive film is easily improved.

When the ratio of ZnS is high, the sputtering rate is increased, and the formation speed of the second high refractive index layer 4 is increased. When the amount of components other than ZnS is increased, the amorphous property of the second high refractive index layer 4 is improved, and the crack 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, more preferably 20 nm 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 conduction region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. When 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 hardly lowered. The layer thickness of the second high refractive index layer 4 is measured by an ellipsometer.

The method for forming the second high refractive index layer 4 is not particularly limited, and may be formed by a general vapor phase deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method. Floor. From the viewpoint of lowering the moisture permeability of the second high refractive index layer 4, 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 patterned into a layer having a desired shape, the patterning method is not particularly limited. For example, a mask having a desired pattern or the like is disposed on the film formation surface, and the second high refractive index layer 4 may be formed into a pattern by a vapor phase film formation method, and may be formed by a well-known etching method. The layer of patterning.

<7. Hard coating>

In the production of the transparent conductive film, in order to prevent the surface of the transparent resin support from being scratched, it is preferable to provide a hard coat layer on at least one side of the transparent resin support, preferably on the side of the transparent conductive layer.

By providing a hard coat layer on the surface of at least one side of the transparent resin support, it is possible to prevent the winding of the transparent conductive film of the present invention during film formation from the transparent resin support. Transfer. The effect of the occurrence of a flaw caused by pressure or friction on the surface between the unwound film surfaces.

The hard coat layer is coated with a dry ultraviolet curable acrylate-based resin and then cured by an ultraviolet light source.

When the layer thickness of the hard coat layer is preferably in the range of 0.2 to 5.0 μm, and the layer thickness of the hard coat layer is within the above range, since sufficient scratch resistance is obtained, occurrence of scratches in the manufacturing process can be prevented, as transparent conductivity. Sufficient transparency is obtained when the film is used.

In addition to coating, the hard coat layer may be formed by laminating a SiO ₂ film such as a CVD method, a sputtering method, or a vapor deposition method to a layer thickness of 100 nm or less.

<8. Anti-caking layer>

It is preferable to provide an anti-caking layer having a ten-point average roughness Rz of 50 nm or less on the surface opposite to the surface of the transparent conductive layer on which the transparent conductive support of the transparent conductive film of the present invention is provided. The so-called anti-caking layer, although it is In order to prevent the film from sticking to each other when the film is wound, this method is provided with any roughness on the surface of the film, and the gap is buried in the air to prevent unwinding. The films are attached to each other during the winding operation.

The ten-point average roughness Rz refers to Rz prescribed in JIS B0601:1994.

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

In the transparent conductive film of the present invention, each of the high refractive index layer, the vulcanization preventing layer, and the transparent conductive layer provided on the transparent resin support is preferably formed by a sputtering method or a vapor deposition method. When each of the thin film layers provided on the transparent resin support is formed by a sputtering method or a vapor deposition method, the productivity is improved and an effect suitable for mass production is obtained. However, even if all other thin layer manufacturing methods such as chemical vapor deposition (CVD) are used, the value obtained by the present invention is not impaired.

图Transformation of transparent conductive layer≫

When the transparent conductive film of the present invention is used, for example, to form a touch panel of a capacitance type, as shown in FIG. 3, it is preferable that the transparent conductive layer includes a plurality of conductive regions a and a linear insulating region different from the above. b is patterned into a specific shape.

As a deterioration factor of a transparent conductive layer containing silver, it can be listed Give water or sulfide contained in the atmosphere. These penetrate into the transparent resin support or hard coat layer and pass through the hard coat layer to reach the transparent conductive layer. Accordingly, since only the transparent resin support and the hard coat layer and the protective function of the silver of the transparent conductive layer are insufficient, the first high refractive index layer preferably contains the vulcanization preventing layer when the first vulcanization preventing layer is provided. The pattern is formed on the transparent resin support and remains, and is preferable from the viewpoint of preventing deterioration of the transparent conductive layer.

As a method of patterning the transparent conductive layer, a well-known method can be used, and as such a method of patterning, specifically, it can be performed as follows.

(graphical step)

Hereinafter, a method of forming an electrode pattern by a photolithography method will be described.

The lithography method to which the present invention is applied is subjected to resist coating such as curable resin, preliminary heating, exposure, development (removal of uncured resin), cleaning, etching treatment by an etching solution, In each step of resist stripping, the transparent conductive layer is processed into a desired pattern as shown in FIG.

In the present invention, a conventional microlithography method known in the art can be suitably used. For example, any of the resists of the resist type, positive type or negative type can be used. Further, after the resist coating, preliminary heating or prebaking may be performed if necessary. At the time of exposure, a pattern mask having a desired pattern is disposed, and light having a wavelength suitable for the resist to be used is irradiated thereon, and generally, ultraviolet rays, electron beams, or the like may be used. After the exposure, development was carried out with a developing solution suitable for the resist used.

After the development, the development is stopped by washing with water or the like, and the pattern is formed by washing. Next, if the formed resist pattern is subjected to pre-treatment or post-baking, the etching of the etching solution containing the organic solvent is performed to dissolve the silver in the intermediate layer of the unprotected region and silver. Removal of the film electrode.

After the etching, a transparent electrode having a desired pattern is obtained by peeling off the remaining resist. Thus, the lithography method to which the present invention is applied is a method generally recognized by those skilled in the art, and the specific application aspect thereof can be easily selected according to the desired purpose if it is a general knowledge in the field of the invention. .

Next, a method of forming an electrode pattern to which the present invention is applicable will be described with reference to Fig. 4 .

Fig. 4 is a flow chart showing the steps of forming an electrode pattern by photolithography in the transparent conductor of the present invention.

As a first step, as shown in FIG. 4( a ), the first high refractive index layer 2 , the first vulcanization preventing layer 5 a , the transparent conductive layer 3 , and the second vulcanization preventing layer 5 b are formed on the transparent resin support 1 . The laminated transparent conductive film 100 is produced in the order of the second high refractive index layer 4.

Next, in the step of forming the resist film shown in FIG. 4(b), the resist film 6 composed of a photosensitive resin composition or the like is uniformly applied onto 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, a well-known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, or the like is used. It is applied to the transparent conductive film 100, and may be prebaked by a heating device such as a hot plate or an oven. The prebaking can be carried out for 30 seconds to 30 minutes in a range of 50 ° C or more and 150 ° C or less, for example, using a hot plate or the like.

Next, in the exposure step shown in (c) of FIG. 4, using a mask 7 made by a specific electrode pattern, a stepper, a mirror projection mask locator (MPA), a parallel light mask positioning is used. The exposure machine of the apparatus or the like irradiates the light of 10 to 4000 J/m ² (converted by the exposure amount of 365 nm) to the resist film 6A removed by the following procedure. The exposure light source is not limited, and ultraviolet rays, electron beams, or KrF (wavelength 248 nm) lasers, ArF (wavelength 193 nm) lasers, or the like can be used.

Next, in the developing step shown in Fig. 4 (d), the exposed transparent conductive film is immersed in a developing liquid to dissolve the resist film 6A in the region irradiated with light.

As the developing method, it is preferred to immerse for 5 seconds to 10 minutes in a developing solution by a shower, dipping, paddle or the like. As the developing liquid, a well-known alkali developing solution can be used. Specific examples thereof include an inorganic base such as an alkali metal hydroxide, a carbonate, a phosphate, a citrate or a borate; an amine such as 2-diethylaminoethanol, monoethanolamine or diethanolamine; An aqueous solution containing one or two or more kinds of a fourth-order ammonium salt such as methylammonium hydroxide or choline. After development, it is preferably washed with water, and then dried and baked at a temperature of 50 ° C or more and 150 ° C or less.

Then, in order to remove the second high refractive index layer and the second vulcanization preventing layer, "PURE ETCH 100" manufactured by Ivy Pure Chemical Industries, Ltd. was used as an etching liquid. (Fig. 4(e))

Next, in order to dissolve only the transparent conductive layer and the first vulcanization preventing layer, "SEA-5" manufactured by Kanto Chemical Co., Ltd. was subjected to etching for a short period of time. (Fig. 4(f))

Finally, as shown in FIG. 4(g), it is immersed in a resist stripping liquid, for example, immersed in "N-300" manufactured by Nagase Contax, and the resist film 6 is removed to produce a residual first high refraction. A transparent conductive film of the electrode pattern of the layer 2.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

≪Preparation of transparent conductive film≫

In the production of the transparent conductive film, the following transparent resin support and conductive material are used.

(Material of transparent resin support)

Here, d is the thickness of the support, Ro is slow in the plane, 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: "KeroTac" manufactured by Konica Minolta Co., Ltd., d=50μm Ro=0nm Rt=0nm

2.TPS2: Konica Minolta Co., Ltd. "Konica Minolta Tac", thickness 50μm Ro=5nm Rt=30nm

3.PET: Polyethylene terephthalate film "Tosoh Shine A4300" is 50μm Ro=5000nm Rt=10000nm

4.PC: Zhongyuan polycarbonate film "Elmec R40#435 film" thickness 40μm Ro=435nm Rt=600nm

5.TPS3: Japan Zeon cycloolefin film "ZEONOR Z14 (50μm)" thickness 50μm Ro=1.5nm Rt=10nm

6.TPS4: Konica Minolta Co., Ltd. "VA-TAC" thickness 80μm Ro=50nm Rt=130nm

(conductive material)

7.APC: "Ag alloy" (including Pd, Cu) made of Gu Gu metal

8.APC-TR: "Ag alloy" made of Gu Gu metal (containing Pd, Cu)

9.APC-SR: "Ag alloy" made of Gu Gu metal (containing Pd, Cu)

The alloys of the above three grades have different compositions.

10.GB-100: Kobelco Scientific Research "Ag Alloy" Ag (99.0atm%) / Bi (1.0atm%)

11.GBR-15: Ag steel research and development "Ag alloy" Ag (98.35atm%) / Bi (0.35atm%) / Ge (0.3atm%) / Au (1.0atm%)

12.Ag: silver (purity of 99.9% or more)

13.Cu: copper (purity of 99.9% or more)

14.Au: Gold (purity of 99.9% or more)

The following materials are used in the high refractive index layer and the vulcanization preventing layer.

15.ITO: Indium Tin Oxide

16.SiN: tantalum nitride n=2.02 (n indicates refractive index)

17.Nb ₂ O ₅ : antimony pentoxide n=2.31

18.ZnO: zinc oxide n=1.95

19.IZO: Indium Zinc Oxide

20.GZO: gallium zinc oxide

21.IGZO: Indium gallium zinc oxide

22.TiN: titanium nitride

23.Ga ₂ O ₃ : gallium oxide

24.Bi ₂ O ₃ : yttrium oxide

25.ZnS: a sintered body that adjusts the composition of Zn and S

26.ZnS-SiO ₂ : a mixture of ZnS and SiO ₂

27.ZnO-Ga ₂ O ₃ : adjusting a mixture of the composition of ZnO and Ga ₂ O ₃

28.ZnO-SiN: adjusting the mixture of the composition of ZnO and SiN

29.Ga ₂ O ₃ -SiN: adjusting the mixture of the composition of Ga ₂ O ₃ and SiN

30. ZnS-ZnO: a mixture of ZnS and ZnO

31. ZnS-SiN: adjusting the mixture of the composition of ZnS and SiN

32. ZnS-TiN: adjusting the mixture of the composition of ZnS and TiN

33.ZnS-Bi ₂ O ₃ : adjusting a mixture of the composition of ZnS and Bi ₂ O ₃

Further, the ZnS of the above 26, 30 to 33 is the same as the 25, and a sintered body having a composition of Zn and S is used as a mixture.

<Production of Transparent Conductive Film 1> (first high refractive index layer)

As the transparent resin support, "ZeroTack" (TPS1) (Ro = 0 nm, Rt = 0 nm, d = 50 μm) manufactured by Konica Minolta Co., Ltd. having a square of 100 mm square was used. Splashing using a magnetron sputtering device from Osaka Vacuum Society Plating to form a first high refractive index layer.

The ZnS target having the adjusted composition was placed at the cathode, and the target side electric power was set to 150 W at a formation rate of 3.0 Å/sec (0.3 nm/sec) at an Ar20 sccm, a sputtering pressure of 0.2 Pa, and a room temperature, and a layer was formed. The first high refractive index layer having a thickness of 40.0 nm. RF power is supplied to the cathode.

The distance between the target and the substrate was 90 mm. According to the compositional analysis test described later, the composition ratio of Zn to S at this time was 83 with respect to the number of Zn atoms and the number of S atoms was 83.

(first vulcanization preventing layer)

Next, the target side electric power was set to 150 W at Ar 20 sccm, O ₂ 0 sccm, sputtering voltage 0.1 Pa, and room temperature, and the rate of formation of 1.1 Å/sec (0.11 nm/sec) of ZnO was 1.0 nm. RF sputtering.

(transparent conductive layer)

Next, on the first vulcanization preventing layer, a magnetron sputtering apparatus of Osaka Vacuum Co., Ltd. was used to form a sputtering speed of 14 Å/sec (1.4 nm/sec) at Ar 20 sccm, a sputtering pressure of 0.5 Pa, and room temperature. Silver plating was performed to form a transparent conductive layer having a layer thickness of 7.5 nm.

(second vulcanization preventing layer)

Further, RF sputtering was performed so that ZnO became a layer thickness of 1.0 nm at a formation rate of 1.1 Å/sec (0.11 nm/sec) at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure of 0.1 Pa, and room temperature.

(second high refractive index layer)

Next, ZnS was sputtered in the same manner as in the first high refractive index layer to form a second high refractive index layer having a layer thickness of 40.0 nm, thereby producing a transparent conductive film 1. The composition ratio of Zn to S at this time is 83 with respect to the number of Zn atoms and 83.

<Production of Transparent Conductive Films 2 to 36 and 101 to 107>

Except for the structures of Tables 1 and 2, the transparent conductive films 2 to 36 of the present invention and the transparent conductive films 101 to 107 of the comparative examples were produced in the same manner as the transparent conductive film 1 described above. .

Here, in the first high refractive index layer and the second refractive index layer, the composition ratio of each element of zinc and sulfur is adjusted, and the formed layer is adjusted to have a desired composition ratio of the sintered body. It is used as a target by sputtering. Further, for the formation of the layers containing the two kinds of materials in the other layers, the individual materials were previously adjusted to have a mixture of the ratios shown in Tables 1 and 2 as a target, and the layer was formed by sputtering.

(analysis of composition ratio of zinc and sulfur atoms)

In the quantitative analysis of the elements of zinc and sulfur, a specific ZnS thin layer was formed into a single layer of the reference sample formed on BK7 glass. For these samples, ultra-high purity hydrogen peroxide (manufactured by Kanto Chemical Co., Ltd.) was used. The ZnS layer was sufficiently dissolved, and each element contained in a 20 ml solution obtained by dilution with ultrapure water was subjected to matrix matching using an ICP emission spectroscopic analyzer "SPS3520UV" manufactured by Hitachi High-tech Science.

For the purpose of quantification, 1000 mg/l of zinc standard solution for atomic absorption analysis (manufactured by Kanto Chemical Co., Ltd.) and sulfur standard solution Sulfur 1000 mg/l (SPEX) were used for zinc. The wavelength was measured, zinc was 213.924 nm, and sulfur was 180.734 nm. Further, analysis of a solution sample obtained by subjecting the cleaned BK7 glass to the same treatment was carried out, and it was confirmed that the zinc and sulfur components which are the background noises which hindered the test were below the detection limit.

Evaluation of ≪Transparent Conductive Film≫

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 examples were subjected to the following three evaluations of the reliability test before and after the reliability test.

<1. Conductivity evaluation (surface resistance)>

The conductivity evaluation of the transparent conductive film was carried out using a low resistivity meter "Loresta-EP" (manufactured by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation).

(Evaluation criteria)

◎: Less than 8Ω/□

○: 8 Ω / or more is 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 of the measurement wavelength of 400 to 800 nm using a spectrophotometer "U4100" (manufactured by Hitachi High-Tech Co., Ltd.).

This measurement is assumed to be applied to a transmissive electrostatic capacitance touch panel. In order to reflect a realistic system, a transparent conductive film composed of a support, a high refractive index layer, a vulcanization prevention layer, and a transparent conductive layer is used in an oil immersion optical system. The immersion oil "Type A (n = 1.515)" (manufactured by Nikon Co., Ltd.) was attached to a glass substrate and evaluated by measuring the above total transmittance.

The average transmittance is measured by incident light from an angle of 5° with respect to a normal line of the surface of the transparent conductive film on the side of the transparent resin support. In addition, the average absorptance was measured by inputting light from the same angle as the average transmittance, and the average reflectance of the transparent conductive film was measured and calculated as an average absorptivity=100-(average transmittance + average reflectance) (%). The average transmittance and the average reflectance were measured by a spectrophotometer.

(Evaluation criteria)

◎: The average transmittance is 92% or more

○: The average transmittance is 90% or more, and it is less than 92%.

△: The average transmittance is 85% or more, and it is less than 90%.

×: The average transmittance is less than 85%

<3. Appearance evaluation>

The evaluation of the appearance of the transparent conductive film was carried out by using a research solid microscope "SZX10" (manufactured by Olympus Co., Ltd.) at a magnification of 60 times in a range of 30 mm square at the center of the sample (transparent conductive film).

From this observation method, the number of occurrences of film breakage, film floating, and the like in the observation range in which the type appearance was poor was counted, and was evaluated by the following criteria.

(Evaluation criteria)

◎: There is a poor appearance below 4 points.

○: There is a poor appearance from 5 to 10 o'clock.

△: There is a poor appearance from 11 o'clock to 20 o'clock.

×: There is a poor appearance of 21 points or more.

<4. Reliability Accelerated Test>

The reliability acceleration test (durability test) was carried out for 168 hours in an environment of 80 ° C and 85% RH using a small environmental tester "SH-222" (manufactured by ESPEC Co., Ltd.). The above-described conductivity evaluation, transparency evaluation, and appearance evaluation were performed individually before and after this reliability acceleration test.

The evaluation after the initial stage and the reliability acceleration test was carried out in 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 is understood that the transparent conductive films 1 to 36 of the present invention can provide a transparent conductive film having excellent conductivity and transparency which is uniform throughout the visible light region and high in durability.

Further, in comparison with the effects of the present invention, the transparent conductive films 101 to 107 produced as comparative examples tend to have poor initial performance among various characteristics as compared with the present invention.

Further, in the transparent conductive films 101 to 107 of the comparative examples, by performing the reliability acceleration test, any of the three evaluations of conductivity, transparency, and appearance was the lowest evaluation. This is in sharp contrast to the fact that the transparent conductive films 1 to 36 of the present invention are also highly evaluated in the reliability test.

The main reason for this is presumed to be the feature of the present invention, that is, the sulfur trapping function of the high refractive index layer and the protective function of the conductive layer by the vulcanization preventing layer, and the above comparative examples clearly show the effect of the transparent conductive film provided by the present invention. And superiority.

100‧‧‧Transparent conductive film

1‧‧‧Transparent resin support

2‧‧‧1st high refractive index layer

3‧‧‧Transparent conductive layer

4‧‧‧2nd high refractive index layer

5a‧‧‧1st vulcanization prevention layer

5b‧‧‧2nd vulcanization prevention layer

A‧‧‧conductive area

Claims (12)

A transparent conductive film which is a transparent conductive film which is provided on a transparent resin support at least in the order of a first high refractive index layer, a transparent conductive layer and a second high refractive index layer, and is characterized in that the transparent conductive layer contains In the 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 to 50 or more is 50 or more. And not up to 100. The transparent conductive film of claim 1, wherein the layer containing zinc sulfide is a first high refractive index layer. The transparent conductive film according to claim 1 or claim 2, wherein the first vulcanization preventing layer is contained between the first high refractive index layer and the transparent conductive layer, and the first vulcanization preventing layer contains an oxide or nitrogen Compound. The transparent conductive film of claim 3, wherein the first vulcanization preventing layer contains zinc oxide or gallium oxide as the oxide. The transparent conductive film of claim 1, wherein the first high refractive index layer contains zinc sulfide, an oxide or a nitride, and the content of the oxide or the nitride is a total volume of the first high refractive index layer. Within the range of 5 to 30% by volume. The transparent conductive film of claim 1, wherein the first high refractive index layer contains zinc sulfide and cerium oxide. The transparent conductive film according to claim 1, wherein the second high refractive index layer is selected from the group consisting of zinc sulfide, titanium oxide, indium tin oxide, zinc oxide, cerium oxide, tin dioxide, and indium zinc. Oxidation Matter, aluminum zinc oxide, gallium zinc oxide, antimony tin oxide, indium antimony oxide, indium gallium zinc oxide, antimony oxide, tungsten trioxide, indium oxide and containing gallium. indium. And any one of oxygen amorphous oxides. The transparent conductive film of claim 1, wherein the second high refractive index layer contains zinc sulfide as a high refractive index material. The transparent conductive film of claim 8, wherein the second high refractive index layer further contains cerium oxide as the high refractive index material. The transparent conductive film of claim 1, wherein the second high refractive index layer contains gallium zinc oxide as the high refractive index material. The transparent conductive film of claim 1, wherein the second vulcanization preventing layer is provided between the transparent conductive layer and the second high refractive index layer, and the second vulcanization preventing layer contains an oxide or a nitride. The transparent conductive film of claim 11, wherein the second vulcanization preventing layer contains zinc oxide or gallium zinc oxide as the oxide.