WO2015194320A1

WO2015194320A1 - Transparent conductor and touchscreen

Info

Publication number: WO2015194320A1
Application number: PCT/JP2015/064910
Authority: WO
Inventors: 一成多田; 仁一粕谷; 健一郎平田; 智一田口
Original assignee: コニカミノルタ株式会社
Priority date: 2014-06-17
Filing date: 2015-05-25
Publication date: 2015-12-23
Also published as: JP6536575B2; JPWO2015194320A1

Abstract

This invention addresses the problem of providing the following: a transparent conductor whereby electrical connectivity between a circuit board and a transparent metal layer that exhibits a high transmittance and resists moisture well is improved; and a touchscreen containing said transparent conductor. Said transparent conductor (1) comprises, at least, a transparent substrate (2), a first high-refractive-index layer (3A), a transparent metal layer (4), and a second high-refractive-index layer (3B), in that order, and is characterized in that: the transparent metal layer consists primarily of silver; the first high-refractive-index layer (3A) and the second high-refractive-index layer (3B) each contain either a dielectric material or an oxide-semiconductor material; the refractive indices of the first high-refractive-index layer (3A) and the second high-refractive-index layer (3B) are higher than that of the transparent substrate (2) with respect to light having a wavelength of 570 nm; the first high-refractive-index layer (3A) contains a sulfur component; and the second high-refractive-index layer (3B) contains a sulfur component in an amount between 0.1 and 10 at.%.

Description

Transparent conductor and touch panel

The present invention relates to a transparent conductor and a touch panel. More specifically, the present invention relates to a transparent conductor with improved electrical connection between a transparent metal layer having high light transmittance and high moisture resistance and a circuit board, and a touch panel including the transparent conductor.

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

In a touch panel type display device or the like, wiring including a transparent conductor is disposed on the image display surface of the display element. Therefore, the transparent conductor is required to have high light transmittance. In such various display devices, a transparent conductor using ITO having a high light transmittance is often used.

In recent years, a capacitive touch panel display device has been developed, and it is required to further reduce the surface electrical resistance of the transparent conductor. However, the conventional ITO film has a problem that the surface electric resistance cannot be sufficiently lowered.

Then, using the layer formed by vapor-depositing silver for a transparent metal layer (henceforth Ag layer) is examined (for example, refer patent document 1). In order to increase the light transmittance of the transparent conductor, the Ag layer is formed of a film having a high refractive index (for example, Nb ₂ O ₅ (niobium oxide), IZO (indium / zinc oxide), ICO (indium / cerium oxide)). And a-GIO (a film made of gallium / indium oxide) or the like) (see Non-Patent Document 1, for example). Further, it has been proposed to sandwich the Ag layer with a layer containing zinc sulfide (hereinafter also referred to as a ZnS layer or a zinc sulfide-containing layer) (see, for example, Non-Patent Document 2).

However, as shown in Non-Patent Document 2, a transparent conductor in which an Ag layer is sandwiched between dielectric layers such as niobium oxide and IZO has not been sufficiently moisture-resistant. As a result, when a transparent conductor is used in a high humidity environment, there is a problem that the Ag layer is easily corroded.

Further, in the transparent conductor in which the Ag layer is sandwiched between the ZnS layers, although the moisture resistance of the transparent conductor is sufficiently high, when the Ag layer is formed or the ZnS layer is formed, silver is sulfided and sulfided. Silver is likely to occur. As a result, there is a problem that the light transmittance of the transparent conductor is lowered.

JP 2007-250430 A

The present invention has been made in view of the above problems and situations. The problem to be solved is to provide a transparent conductor having improved electrical connection between a transparent metal layer having high light transmittance and high moisture resistance and a circuit board, and a touch panel including the transparent conductor.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the high refractive index layer contains a dielectric material or an oxide semiconductor material, higher than the refractive index of the transparent substrate, The inventors have found that it is effective to contain a sulfur component at a content within a predetermined range, and have reached the present invention.
That is, the said subject which concerns on this invention is solved by the following means.

1. A transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order;
The transparent metal layer contains silver as a main component,
The first high refractive index layer and the second high refractive index layer each contain a dielectric material or an oxide semiconductor material;
For light with a wavelength of 570 nm, the refractive index of the first high refractive index layer and the second high refractive index layer is higher than the refractive index of the transparent substrate,
The first high refractive index layer contains a sulfur component, and
The transparent conductor, wherein the second high refractive index layer contains a sulfur component in a range of 0.1 to 10 at%.

2. 2. The transparent conductor according to item 1, wherein the sulfur component contained in the first high refractive index layer is derived from zinc sulfide.

3. 3. The transparent conductor according to

item

1 or 2, wherein the sulfur component contained in the second high refractive index layer is derived from zinc sulfide.

4. The transparent conductor according to any one of Items 1 to 3, wherein the first high refractive index layer contains silicon dioxide.

5. The second high refractive index layer is made of titanium (Ti), indium (In), zinc (Zn), cerium (Ce), tungsten (W), gallium (Ga), tin (Sn), hafnium (Hf), zirconium. Containing a metal oxide containing at least one element selected from the group consisting of (Zr), niobium (Nb), tantalum (Ta), aluminum (Al), bismuth (Bi), and germanium (Ge). 5. The transparent conductor according to any one of items 1 to 4, which is characterized.

6. 6. The sulfidation prevention layer further containing a zinc component is provided between the first high refractive index layer and the transparent metal layer. Transparent conductor.

7. The sulfidation prevention layer further containing a zinc component is provided between the second high refractive index layer and the transparent metal layer, wherein any one of items 1 to 6 is provided. Transparent conductor.

8. The transparent conductor according to any one of claims 1 to 7, wherein the transparent metal layer is patterned into a predetermined shape.

9. A touch panel comprising the transparent conductor according to any one of items 1 to 8.

By the above means of the present invention, there is provided a transparent conductor in which electrical connection between a transparent metal layer having high light transmittance and high moisture resistance and a circuit board is improved, and a touch panel including the transparent conductor. it can.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
As described above, when the transparent metal layer and the ZnS-containing layer are formed adjacent to each other, there is a problem that metal sulfide is easily generated and the light transmittance of the transparent conductor is likely to be lowered. The metal sulfide is presumed to be produced as follows.

When a transparent metal layer is formed on the first high refractive index layer as a layer containing at least zinc sulfide (hereinafter also referred to as a zinc sulfide-containing layer) by a vapor deposition method such as sputtering, the zinc sulfide-containing layer The unreacted sulfur component is expelled into the layer formation atmosphere by the transparent metal layer material (metal material). Then, the ejected sulfur component reacts with the metal, and metal sulfide is deposited on the zinc sulfide-containing layer. Moreover, when forming a zinc sulfide content layer and a transparent metal layer continuously, the sulfur component contained in the atmosphere of layer formation of a zinc sulfide content layer remains in a transparent metal layer atmosphere. And this sulfur component and the metal derived from a transparent metal layer react, and a metal sulfide deposits on the 1st high refractive index layer containing a zinc sulfide.

On the other hand, when the second high refractive index layer (zinc sulfide-containing layer) is formed on the transparent metal layer, the metal in the transparent metal layer is expelled into the layer formation atmosphere by the material of the second high refractive index layer. . The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer. Furthermore, a metal sulfide is generated on the surface of the transparent metal layer also when the surface of the transparent metal layer comes into contact with the sulfur component in the layer forming atmosphere.

Therefore, even if the first high refractive index layer and the transparent metal layer are continuously formed by setting the content ratio of the sulfur component contained in the first high refractive index layer to a predetermined range, the first high refractive index. The sulfur component contained in the layer forming atmosphere of the layer reacts with the component of the first antisulfurization layer or is adsorbed by the component of the first antisulfuration layer. Therefore, it is presumed that the atmosphere in which the transparent metal layer is formed does not easily contain sulfur, and the generation of metal sulfide is suppressed.

Furthermore, in the transparent metal layer according to the present invention, it is preferable that the first antisulfurization layer is laminated on the first high refractive index layer. In the said structure, since a 1st high refractive index layer is protected by a 1st sulfurization prevention layer, when forming a transparent metal layer, it is guessed that the sulfur component in a 1st high refractive index layer is hard to be expelled.

In addition, by providing a high refractive index layer, the affinity between silver and sulfur atoms is strengthened, and since water permeability is hindered, corrosion of silver can be prevented and the moisture resistance of the transparent conductor can be improved. it is conceivable that.
Furthermore, the first high refractive index layer contains a sulfur component, and the second high refractive index layer contains the sulfur component in a range of 0.1 to 10 at%, thereby causing moisture of the transparent metal layer. It is assumed that deterioration can be suitably prevented and high conductivity can be maintained.

Schematic sectional view showing an example of the configuration of the transparent conductor of the present invention Schematic sectional view showing an example of the configuration of the transparent conductor of the present invention Schematic sectional view showing an example of the configuration of the transparent conductor 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 conductor of this invention. An example of the relationship between silver layer thickness and light absorption The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method The schematic diagram which shows an example which patterns the electrode of the transparent conductor of this invention by the photolithographic method A perspective view showing an example of composition of a touch panel provided with a transparent conductor which has a patterned electrode

The transparent conductor of the present invention is a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order, and the transparent metal layer mainly contains silver. And the first high refractive index layer and the second high refractive index layer each contain a dielectric material or an oxide semiconductor material, and the first high refractive index layer with respect to light having a wavelength of 570 nm. And the refractive index of the second high refractive index layer is higher than the refractive index of the transparent substrate, the first high refractive index layer contains a sulfur component, and the second high refractive index layer contains a sulfur component. In the range of 0.1 to 10 at%. This feature is a technical feature common to the inventions according to claims 1 to 9.

Further, from the viewpoint of manifesting the effect of the present invention, it is preferable that the sulfur component contained in the first high refractive index layer is derived from zinc sulfide.

Further, from the viewpoint of manifesting the effects of the present invention, it is preferable that the sulfur component contained in the second high refractive index layer is derived from zinc sulfide.

Further, it is preferable that the first high refractive index layer contains silicon dioxide. Thereby, the film | membrane which comprises a 1st high refractive index layer becomes amorphous form, and it can resist a crack, and can improve flexibility.

In the transparent conductor according to the present invention, the second high refractive index layer may be titanium (Ti), indium (In), zinc (Zn), cerium (Ce), tungsten (W), gallium (Ga), tin. At least one element selected from the group consisting of (Sn), hafnium (Hf), zirconium (Zr), niobium (Nb), tantalum (Ta), aluminum (Al), bismuth (Bi), and germanium (Ge). It is preferable to contain the metal oxide to contain. As a result, the second high refractive index layer can have sufficient conductivity to connect the transparent metal layer and the external circuit.

As an embodiment of the present invention, it is preferable that an antisulfurization layer containing a zinc component is further provided between the first high refractive index layer and the transparent metal layer. This is because the reaction between silver contained in the transparent metal layer and sulfur contained in the first high refractive index layer can be suppressed.

Further, it is preferable that an antisulfurization layer containing a zinc component is further provided between the second high refractive index layer and the transparent metal layer. This is because the reaction between silver contained in the transparent metal layer and sulfur contained in the second high refractive index layer can be suppressed.

Further, it is preferable that the transparent metal layer is patterned into a predetermined shape. This is because the conductivity can be improved.

Further, the transparent conductor of the present invention can be suitably provided in a touch panel.

Hereinafter, the present invention, its constituent elements, 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 value and an upper limit value.

《Basic structure of transparent conductor》
1A to 1C are schematic sectional views showing an example of the configuration of the transparent conductor of the present invention.
The transparent conductor 1 of the present invention has at least a transparent substrate 2, a first high refractive index layer 3A, a transparent metal layer 4, and a second high refractive index layer 3B in this order.

In FIG. 1A, a transparent metal layer 4 is provided between the first high refractive index layer 3A and the second high refractive index layer 3B. Thus, when a high refractive index layer containing a sulfur component is provided adjacent to the transparent metal layer 4, the silver atoms in the transparent metal layer 4 and the sulfur atoms of ZnS have a high affinity. The transparent metal layer 4 can be obtained with a thin film. And since this silver thin film is stable, it is excellent also in moisture resistance.

In FIG. 1B, a first sulfidation preventing layer 5A is provided between the transparent metal layer 4 and the first high refractive index layer 3A. With this configuration, when the first sulfurization preventing layer 5A containing a zinc component is provided adjacent to the transparent metal layer 4, silver in the transparent metal layer is sulfided by sulfur contained in the high refractive index layer. Can be suppressed.

In FIG. 1C, a second antisulfurization layer 5B is also provided between the transparent metal layer 4 and the second high refractive index layer 3B. With this configuration, when the second sulfurization preventing layer 5B containing the zinc component is provided adjacent to the transparent metal layer 4, silver in the transparent metal layer is sulfided by sulfur contained in the high refractive index layer. This can be further suppressed.

In the transparent conductor 1 of the present invention, the transparent metal layer 4 may be laminated on the entire surface of the transparent substrate 2 as shown in FIGS. 1A to 1C. For example, as shown in FIG. It is preferable that the transparent electrode unit EU including the index layer 3A, the first antisulfurization layer 5A, the transparent metal layer 4, and the second high refractive index layer 3B is patterned into a desired shape.
In the transparent conductor 1 of the present invention, the region a where the transparent electrode unit EU 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 that does not have the transparent electrode unit EU 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 conductor 1. Details of the pattern applied to the electrostatic touch panel will be described later.

Further, the transparent conductor 1 of the present invention includes a transparent substrate 2, a first high refractive index layer 3A, a first antisulfurization layer 5A, a transparent metal layer 4, a second antisulfurization layer 5B, and a second high refractive index layer 3B. In addition, a known functional layer may be provided as necessary.

The layers included in the transparent conductor 1 of the present invention are preferably layers made of an inorganic material except for the transparent substrate 2. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 3B, the laminated body from the transparent substrate 2 to the second high refractive index layer 3B is the transparent conductor 1 of the present invention. Define that there is.

<< Each component of transparent conductor >>
The transparent conductor of the present invention is a transparent conductor 1 having at least a transparent substrate 2, a first high refractive index layer 3A, a transparent metal layer 4, and a second high refractive index layer 3B in this order, and the first high refractive index. The refractive index layer 3A and the second high refractive index layer 3B each contain a dielectric material or an oxide semiconductor material, and the first high refractive index layer 3A and the second high refractive index layer 3B with respect to light having a wavelength of 570 nm. Is higher than the refractive index of the transparent substrate 2, the first high refractive index layer 3 A contains a sulfur component, and the second high refractive index layer 3 B contains 0.1 to 10 at% of the sulfur component. It is contained within the range. Further, the first high refractive index layer 3A preferably contains a sulfur component within a range of 0.1 to 50 at%, and the second high refractive index layer 3B contains a sulfur component within a range of 0.1 to 5 at%. It is more preferable to contain within.
Further, between the first high refractive index layer 3A and the transparent metal layer 4 and / or between the second high refractive index layer 3B and the transparent metal layer 4, the first antisulfurization layer 5A and the second antisulfurization layer. It is a preferable aspect to have 5B.

[Transparent substrate]
As the transparent substrate 2 applicable to the transparent conductor 1 of the present invention, materials applied to transparent substrates of various display devices can be used.
The transparent substrate 2 is a glass substrate, cellulose ester resin (for example, triacetylcellulose (abbreviation: TAC), diacetylcellulose, acetylpropionylcellulose, etc.), polycarbonate resin (for example, Panlite, Multilon (above, manufactured by Teijin Limited)). , Cycloolefin resins (for example, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resins (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex) (Manufactured by Sumitomo Chemical Co., Ltd.)), polyimide, phenol resin, epoxy resin, polyphenylene ether (abbreviation: PPE) resin, polyester resin (for example, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN)), polyether Ruhon resin, acrylonitrile / butadiene / styrene resin (abbreviation: ABS resin) / acrylonitrile / styrene resin (abbreviation: AS resin), methyl methacrylate / butadiene / styrene resin (abbreviation: MBS resin), polystyrene, methacrylic resin, polyvinyl alcohol / ethylene It may be a transparent resin film made of vinyl alcohol resin (abbreviation: EVOH), styrene block copolymer resin, or the like. When the transparent substrate 2 is a transparent resin film, the film may contain two or more kinds of resins.

From the viewpoint of achieving high light transmittance, the transparent substrate 2 applied to the present invention includes a glass substrate, cellulose ester resin, polycarbonate resin, polyester resin (particularly polyethylene terephthalate), triacetyl cellulose, and cycloolefin resin. Resin such as phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin A film composed of the components is preferred.

The transparent substrate 2 preferably has a high light transmittance with respect to visible light. The average light transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and 85%. More preferably, it is the above. When the average light transmittance of light of the transparent substrate 2 is 70% or more, the light transmittance of the transparent conductor 1 is likely to be increased. Further, the average light absorptance of light having a wavelength of 450 to 800 nm of the transparent substrate 2 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

The average light 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 substrate 2. On the other hand, the average light absorptance is measured by measuring the average light reflectance of the transparent substrate 2 by making light incident from the same angle as the average light transmittance.
Average light absorption rate (%) = 100- (average light transmittance + average light reflectance) (%)
Calculate as The average light transmittance and the average light reflectance can be measured using a spectrophotometer (for example, U4100; manufactured by Hitachi High-Technologies Corporation).

The refractive index of light having a wavelength of 570 nm of the transparent substrate 2 is preferably in the range of 1.40 to 1.95, more preferably in the range of 1.45 to 1.75, and still more preferably 1.45. Within the range of ~ 1.70. The refractive index of the transparent substrate 2 is usually determined by the material of the transparent substrate 2. The refractive index of the transparent substrate 2 can be determined by measuring in an environment of 25 ° C. using an ellipsometer.

The haze value of the transparent substrate 2 is preferably in the range of 0.01 to 2.5%, more preferably in the range of 0.1 to 1.2%. When the haze value of the transparent substrate is 2.5% or less, the haze value as the transparent conductor can be suppressed, which is preferable. The haze value can be measured using a haze meter.

The thickness of the transparent substrate 2 is preferably in the range of 1 μm to 20 mm, more preferably in the range of 10 μm to 2 mm. If the thickness of the transparent substrate is 1 μm or more, the strength of the transparent substrate 2 is increased, and it is possible to prevent the first high refractive index layer 3A from being cracked or torn during production. On the other hand, if the thickness of the transparent substrate 2 is 20 mm or less, sufficient flexibility of the transparent conductor 1 can be obtained. Furthermore, the thickness of the electronic device apparatus etc. which comprised the transparent conductor 1 can be made thin. Moreover, the electronic device apparatus etc. which used the transparent conductor 1 can also be reduced in weight.

In the present invention, the transparent substrate 2 to be used is formed by removing moisture contained in the substrate and remaining solvent in advance using a cryopump or the like before forming each constituent layer. It is preferable to use in the process.

Further, a known clear hard coat layer may be provided on the transparent substrate applied to the present invention from the viewpoint of obtaining the smoothness of the first high refractive index layer formed thereafter.

(High refractive index layer)
The transparent conductor 1 of the present invention has a first high refractive index layer 3A and a second high refractive index layer 3B, the first high refractive index layer 3A being closer to the transparent substrate 2 and the second being the second higher refractive index layer 3B. This is referred to as a high refractive index layer 3B (see FIG. 1A).
Each of the first high refractive index layer 3A and the second high refractive index layer 3B contains a dielectric material or an oxide semiconductor material, and the first high refractive index layer 3A and the second high refractive index layer 3A with respect to light having a wavelength of 570 nm. The refractive index of the refractive index layer 3B is higher than the refractive index of the transparent substrate 2, the first high refractive index layer 3A contains a sulfur component, and the second high refractive index layer 3B contains a sulfur component of 0. It is contained within the range of 1 to 10 at%.
The first high refractive index layer 3A preferably contains a sulfur component in the range of 0.1 to 50 at%.
Since the second high refractive index layer 3B contains the sulfur component within the range, it is possible to achieve both high conductivity and moisture resistance, and the first high refractive index layer 3A is sulfur within the range. It has been found that the inclusion of a component is more preferable for exhibiting the effect.
This is preferable in that the sulfur component contained in the first high-refractive index layer is 50 at% or less, so that it is possible to prevent the target from being difficult to produce due to excessive sulfur. Moreover, it is preferable at 0.1 at% or more in that silver migration can be easily suppressed.
When the sulfur component contained in the second high refractive index layer is 10 at% or less, poor electrical connection between the external circuit and silver can be suppressed. Moreover, by setting it as 0.1 at% or more, it can be made easy to suppress silver migration similarly to the first high refractive index layer.
As the sulfur component contained in the first high refractive index layer and the second high refractive index layer, those derived from zinc sulfide and single sulfur can be used, but those derived from zinc sulfide are particularly preferable. . Since the sulfur component derived from zinc sulfide can exist stably in the high refractive index layer, it is easy to prevent the sulfur component from diffusing and reacting in an undesired place.

The first high refractive index layer 3 </ b> A is a layer that adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor, that is, the region where the transparent metal layer 4 is formed, and at least the conduction of the transparent conductor 1. Formed in region a. The first high-refractive index layer 3A may be formed also in the insulating region b of the transparent conductor 1, but is illustrated in FIG. 2 from the viewpoint of making it difficult to visually recognize the pattern including the conductive region a and the insulating region b. Thus, it is preferably formed only in the conduction region a.

The first high refractive index layer 3 </ b> A has a refractive index higher than that of the transparent substrate 2. The first high refractive index layer 3A includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate 2 described above. The refractive index of the dielectric material or oxide semiconductor material with respect to light having a wavelength of 570 nm is preferably 0.1 to 1.1 larger than the refractive index of the transparent substrate, and more preferably 0.4 to 1.0 larger.
The refractive index according to the present invention is a measured value at a temperature of 25 ° C. and a relative humidity of 25%.

On the other hand, the refractive index of the dielectric material or the oxide semiconductor material included in the first high refractive index layer with respect to light having a wavelength of 570 nm is preferably higher than 1.5, more preferably 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 higher than 1.5, the optical admittance of the conductive region a of the transparent conductor is sufficiently adjusted by the first high refractive index layer. The refractive index of the first high refractive index layer is adjusted by the refractive index of the material included in the first high refractive index layer and the density of the material included in the first high refractive index layer. Similarly to the transparent substrate, the refractive index of the high refractive index layer can be determined by measuring in an environment of 25 ° C. using an ellipsometer.

The dielectric material or the oxide semiconductor material included in the first high refractive index layer 3A may be an insulating material or a conductive material. The dielectric material or the oxide semiconductor material may be a metal oxide having the above refractive index.
Examples of the metal oxide having the refractive index include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti _4. O ₇ , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), ATO (antimony) Tin oxide), ICO (indium cerium oxide), IGZO (indium gallium zinc oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , In ₂ O ₃ , a-GIO (gallium indium oxide) and the like are included. The first high refractive index layer may be a layer containing only one kind of the metal oxide or a layer containing two or more kinds.
In particular, a mixture of SiO ₂ and ZnS is preferable in terms of stability and high flexibility. Furthermore, the above-described two or more types of high refractive index layers may be laminated to form a first high refractive index layer comprising a plurality of layers.

The second high refractive index layer 3B has a higher refractive index than the refractive index of the transparent substrate 2 like the first high refractive index layer 3A. The second high refractive index layer includes a material having a refractive index higher than that of the transparent substrate 2 described above. The refractive index of the material with respect to light having a wavelength of 570 nm is preferably 0.1 to 1.1 larger than the refractive index of the transparent substrate, and more preferably 0.4 to 1.0 larger.
On the other hand, the refractive index of the material contained in the second high refractive index layer with respect to light having a wavelength of 570 nm is preferably greater than 1.5, more preferably 1.7 to 2.5, and even more preferably 1.8. ~ 2.5. When the refractive index of the material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor is sufficiently adjusted by the second high refractive index layer. The refractive index of the second high refractive index layer is adjusted by the refractive index of the material included in the second high refractive index layer and the density of the material included in the second high refractive index layer.

When the transparent conductor has such a refractive index, reflection due to silver contained in the transparent metal layer can be offset.
Specifically, as the refractive index of the first high refractive index layer is higher than that of the base material, the reflection at the interface between the base material and the first high refractive index layer is increased, and therefore, it is contained in the transparent metal layer. It becomes easy to cancel the reflection generated from silver.
Similarly, the higher the refractive index of the second high refractive index layer, the higher the reflection generated on the surface of the second high refractive index layer, and it becomes possible to cancel the reflected light of silver. Therefore, it is desirable that the refractive index of the high refractive index layer is higher than the refractive index of the substrate.

The second high-refractive index layer 3B is a layer that also has conductivity in order to ensure electrical connectivity. In the present invention, in order to ensure good electrical connectivity, a material having a specific resistance of 1000 Ω · cm or less is preferable. More preferably, it is 0.1Ω · cm or less. By adopting such a configuration, electrical connection between the terminal provided outside through the second high refractive index layer and the transparent metal layer can be obtained, and current can be passed through the transparent metal layer. Sexually improves.

The material included in the second high refractive index layer preferably includes an oxide semiconductor material among the materials included in the first high refractive index layer. Of these, metal oxides are preferable.

Examples of metal oxides include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti _2. O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), ATO (antimony tin oxide) , ICO (indium cerium oxide), IGZO (indium gallium zinc oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , In ₂ O ₃ , a-GIO (gallium) -Indium oxide) and the like. The first high refractive index layer may be a layer containing only one kind of the metal oxide or a layer containing two or more kinds. Alternatively, a second high refractive index layer composed of a plurality of layers may be formed by laminating the two or more types of high refractive index layers.

The thickness of the first high refractive index layer 3A and the second high refractive index layer 3B is preferably in the range of 10 to 150 nm, more preferably in the range of 10 to 80 nm. When the thickness of these high refractive index layers is 10 nm or more, the optical admittance of the conductive region a of the transparent conductor 1 is sufficiently adjusted by the high refractive index layer. On the other hand, when the thickness of the high refractive index layer is 150 nm or less, the light transmittance of the region including the high refractive index layer is unlikely to decrease. The thickness of the high refractive index layer is measured with an ellipsometer.

The high refractive index layer is preferably formed by vapor deposition or sputtering. Deposition methods applicable to the present invention include resistance heating vapor deposition, electron beam vapor deposition, ion plating, and ion beam vapor deposition. As the vapor deposition apparatus, for example, a BMC-800T vapor deposition machine manufactured by SYNCHRON Co., Ltd. can be used. Sputtering methods include magnetron sputtering and counter sputtering.

Further, when the high refractive index layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The high refractive index layer may be, for example, a layer formed in a pattern by a vapor phase forming method by placing a mask having a desired pattern on the surface to be formed. It may be a layer patterned by a lithography method.

In the present invention, the first high refractive index layer and the second high refractive index layer contain a sulfur component. Specifically, the first high refractive index layer contains a sulfur component, and the second high refractive index layer contains a sulfur component in the range of 0.1 to 10 at%. By containing a sulfur component in the said range, deterioration by the humidity of a transparent metal layer can be prevented suitably, and high electroconductivity can be maintained.

Thus, when a transparent metal layer containing silver as a main component is formed on the high refractive index layer, silver atoms constituting the transparent metal layer are contained in the high refractive index layer. It interacts with the sulfur atom of zinc sulfide having an affinity for the atom, the diffusion distance of the silver atom on the surface of the high refractive index layer is reduced, and the aggregation of silver at a specific location is suppressed.

That is, the silver atoms first form a two-dimensional nucleus on the surface of the high refractive index layer containing silver atoms and zinc sulfide, and a two-dimensional single crystal layer is formed around the two-dimensional nucleus (Frank). -Van der Merwe (FM type) film growth.

In general, silver atoms attached on the surface of the high refractive index layer are combined while diffusing the surface to form three-dimensional nuclei and grow into three-dimensional islands (Volumer). -Weber: VW type) is considered to be easily formed into islands, but in the present invention, zinc sulfide contained in the high refractive index layer prevents islands of this type. It is assumed that layer growth is promoted.

Therefore, a conductive layer having a uniform film thickness can be obtained even though the film thickness is small. Therefore, even if the transparent metal layer 4 is thin, plasmon absorption hardly occurs. As a result, it is possible to obtain a transparent conductor in which conductivity is ensured while maintaining light transmittance with a thinner film thickness.

In addition, by providing this layer, the affinity between silver and sulfur atoms is strengthened, and since water permeability is hindered, silver corrosion is prevented and the moisture resistance of the transparent conductor can be improved. It is done.

FIG. 3 is an example showing the relationship between the thickness of the silver layer and light absorption. 4 is a graph showing the relationship between the film thickness of silver and the average light absorption of visible light (400 to 800 nm) when silver is deposited on a thin layer of glass, ITO and zinc sulfide to form a silver thin film. When silver is deposited on zinc sulfide, the absorption of silver can be reduced more than when silver is deposited on glass or ITO.

Examples of the metal oxide that can be used in the first high refractive index layer together with a sulfur component such as zinc sulfide include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , and CeO _2. , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , (indium / zinc oxide), AZO (aluminum / zinc oxide), GZO (gallium / zinc oxide), ATO (antimony / tin oxide), ICO (indium / cerium oxide), Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , a-GIO (gallium indium oxide), and the like. Among the above metal oxides, silicon dioxide (SiO ₂ ) is particularly preferable. This is because the film constituting the first high refractive index layer becomes amorphous and is resistant to cracking and can improve flexibility.

The second high refractive index layer is made of titanium (Ti), indium (In), zinc (Zn), cerium (Ce), tungsten (W), gallium (Ga), tin (Sn), hafnium (Hf), Containing a metal oxide containing at least one element selected from the group consisting of zirconium (Zr), niobium (Nb), tantalum (Ta), aluminum (Al), bismuth (Bi), and germanium (Ge). Is preferred.
Specifically, for the second high refractive index layer, the same compound as the metal oxide that can be used together with the sulfur component can be used. This is preferable because the second high refractive index layer can secure sufficient conductivity to connect the transparent metal layer and the external circuit.

Examples of the metal fluoride include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like. Can do.

Further, examples of the metal nitride include boron nitride, aluminum nitride, chromium nitride, silicon nitride, tungsten nitride, magnesium nitride, molybdenum nitride, lithium nitride, and titanium nitride.

[Sulfurization prevention layer]
The transparent conductor of the present invention preferably has an antisulfurization layer containing a zinc component between the high refractive index layer and the transparent metal layer.
As the anti-sulfurization layer, a metal oxide, metal nitride, metal fluoride, metal or semiconductor can be used. For example, a layer containing a zinc component such as ZnO, GZO and AZO is preferable. Only two or more kinds may be included.
A plurality of antisulfurization layers may be provided, and the one closer to the transparent substrate is referred to as a first antisulfurization layer, and the far side is referred to as a second antisulfation layer.

When the transparent metal layer and the high refractive index layer containing ZnS are formed adjacent to each other, the metal in the transparent metal layer is formed when the transparent metal layer 4 is formed or when the second high refractive index layer 3B is formed. May be sulfided to produce metal sulfide, which may reduce the light transmittance of the transparent conductor. On the other hand, when an antisulfurization layer is included between the first high refractive index layer 3A and the transparent metal layer 4 or between the transparent metal layer 4 and the second high refractive index layer 3B, the metal sulfide Generation is suppressed.

Examples of metal oxides include TiO ₂ , ITO, ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO _2. , La ₂ Ti ₂ O ₇ , IZO, AZO, GZO, ATO, ICO, Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO _{3 and the} like are included.
Examples of metal fluorides include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like. .
Examples of the metal nitride include Si ₃ N ₄ , AlN, and the like.

The thickness of the sulfidation preventive layer is not particularly limited as long as the transparent metal layer 4 can be prevented from being sulfidized during the formation of the transparent metal layer 4 or the second high refractive index layer 3B. Not limited. However, ZnS contained in the first high refractive index layer 3 </ b> A and the second high refractive index layer 3 </ b> B has high affinity with the metal contained in the transparent metal layer 4. Therefore, when the thickness of the sulfurization preventing layer is very thin, a portion where the transparent metal layer 4 and the first high refractive index layer 3A or the transparent metal layer 4 and the second high refractive index layer 3B are in contact with each other is generated. Adhesion tends to increase. That is, the antisulfurization layer is preferably relatively thin, preferably 0.1 to 10 nm, more preferably 0.1 to 5 nm, and further preferably 0.1 to 3 nm. The thickness of the sulfidation prevention layer is measured with an ellipsometer. In particular, an antisulfurization layer containing Zn or Ga metal is preferable because it does not deteriorate moisture resistance and has strong interaction with silver.

The anti-sulfurization layer 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 antisulfurization layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The sulfidation prevention layer 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 patterned by a known etching method. It may be a layer formed.

(Transparent metal layer)
The transparent metal layer 4 containing silver as a main component is a layer for conducting electricity in the transparent conductor 1. The transparent metal layer 4 may be formed on the entire surface of the transparent substrate 2 as shown in FIGS. 1A to 1C, and is preferably patterned into a predetermined shape as shown in FIG.

In the present invention, “containing silver as a main component” means that the silver thin film electrode content ratio of the metal layer is 60 at% (atomic%) or more. Preferably, the silver content is 90 at% or more from the viewpoint of conductivity, more preferably 95 at% or more, and the transparent electrode is preferably made of only silver.

The metal combined with silver can be zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, platinum, titanium, chromium, or the like. For example, when silver and zinc are combined, the sulfide 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 plasmon absorption rate of the transparent metal layer 4 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. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region a of the transparent conductor 1 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 4 is measured by the following procedure.

(I) On the glass substrate, platinum palladium is formed at a thickness of 0.1 nm by a BMC-800T vapor deposition apparatus manufactured by SYNCHRON. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the vapor deposition apparatus. Thereafter, a layer made of metal is formed to a thickness of 20 nm on the substrate to which platinum palladium is adhered by a vacuum deposition method.

(Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal film, and the light transmittance and light reflectance of the metal film are measured. Then, light absorptance (%) = 100− (light transmittance + light reflectance) (%) is calculated from the light transmittance and light reflectance at each wavelength, and this is used as reference data. The light transmittance and light reflectance are measured with a spectrophotometer.

(Iii) Subsequently, a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, light transmittance and light reflectance are measured similarly. The reference data is subtracted from the obtained light absorption rate, and the calculated value is defined as the plasmon absorption rate.

The thickness of the transparent metal layer 4 is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm. In the transparent conductor 1, when the thickness of the transparent metal layer 4 is 10 nm or less, the original reflection of metal hardly occurs in the transparent metal layer 4. Furthermore, when the thickness of the transparent metal layer 4 is 10 nm or less, the optical admittance of the transparent conductor 1 is easily adjusted by the first high refractive index layer 3A and the second high refractive index layer 3B, and the surface of the conductive region a The reflection of light is easy to be suppressed. The thickness of the transparent metal layer 4 can be determined by measurement using an ellipsometer.

The transparent metal layer 4 may be a layer formed by any forming method, but is preferably a layer formed by a vacuum evaporation method or a sputtering method.

If it is a sputtering method or a vacuum evaporation method, a transparent metal layer with high planarity can be formed at a very high formation rate. Further, when a metal layer is formed on a high refractive index layer containing ZnS, if the formation speed of the layer is high, a metal sulfide is difficult to be generated. Therefore, the transparent metal layer containing silver as a main component The formation rate is preferably 0.3 nm / second or more. The formation rate is more preferably in the range of 0.5 to 30 nm / second, and particularly preferably in the range of 1.0 to 15 nm / second. The temperature during film formation is preferably in the range of −25 to 25 ° C.
The counter sputtering method is preferable because the smoothness of silver is increased and transparency and conductivity are improved.

Further, when the transparent metal layer 4 is a film patterned in a desired shape, the patterning method is not particularly limited. For example, the transparent metal layer 4 may be a layer formed by arranging a mask having a desired pattern, or may be a film patterned by a known etching method.

[Other component layers]
(Adhesion layer)
The transparent conductor 1 of the present invention may have an adhesion layer on the transparent substrate in order to improve adhesion between the transparent substrate and the first high refractive index layer. The adhesion layer may be any layer as long as the first high refractive index layer is firmly adhered to the transparent substrate.
The adhesion layer may contain a dielectric material, an oxide semiconductor material, an insulating or conductive material.
The dielectric material or oxide semiconductor material is preferably a metal oxide, metal sulfide, or metal nitride. The refractive index is not limited. In particular, when the first high refractive index layer is formed by vapor deposition, it is preferable that there is an adhesion layer. Although the clear mechanism of action has not been clarified, the energy required for film formation is smaller when the film is formed by the vapor deposition method than when the film is formed by the sputtering method. It is considered that it depends on the compatibility of the material of the first high refractive index layer.
For example, SiO ₂ film, and a ZnS-SiO ₂ film formed by sputtering. The thickness of the layer is not particularly limited, and is preferably in the range of 0.01 to 15 nm, more preferably in the range of 0.1 to 3 nm.

(Low refractive index layer)
The transparent conductor 1 of the present invention has a low refractive index layer (not shown) that adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor on the second high refractive index layer 3B. It may be. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 1 or may be formed in both the conductive region a and the insulating region b of the transparent conductor 1.

In the low refractive index layer, the refractive index of light is lower than the refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material included in the first high refractive index layer 3A and the second high refractive index layer 3B. Dielectric materials or oxide semiconductor materials are included. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is the light of wavelength 570 nm of the above material contained in the first high refractive index layer 3A and the second high refractive index layer 3B. The refractive index is preferably 0.2 or more lower and more preferably 0.4 or more lower.

(Third high refractive index layer)
The transparent conductor 1 of the present invention may further include a third high refractive index layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor on the second high refractive index layer. . The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 1, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 1.

The third high refractive index layer preferably contains a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 2 and the refractive index of the low refractive index layer.
The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the third high refractive index layer is preferably larger than 1.5, more preferably 1.7 to 2.5. 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 1 is sufficiently adjusted by the third high refractive index layer.
The refractive index of the third high refractive index layer is adjusted by the refractive index and density of the material contained in the third high refractive index layer.

The dielectric material or the oxide semiconductor material included in the third high refractive index layer may be an insulating material or a conductive material. The dielectric material or the oxide semiconductor material is preferably a metal oxide, a metal sulfide, or a metal nitride. Examples of the metal oxide or metal sulfide include the metal oxide or metal sulfide contained in the first high refractive index layer 3A or the second high refractive index layer 3B. The third high refractive index layer may contain only one kind of the metal oxide or metal sulfide, or may contain two or more kinds.

The thickness of the third high refractive index layer is not particularly limited, and is preferably 1 to 40 nm, and more preferably 5 to 20 nm. When the thickness of the third high refractive index layer is within the above range, the optical admittance of the conductive region a of the transparent conductor 1 is sufficiently adjusted. The thickness of the third high refractive index layer is measured with an ellipsometer.

The film formation method of the third high refractive index layer is not particularly limited, and may be a layer formed by the same method as the first high refractive index layer 3A and the second high refractive index layer 3B.

[Physical properties of transparent conductor]
The average light transmittance of light with a wavelength of 400 to 1000 nm of the transparent conductor of the present invention is preferably 88% or more, more preferably 90% or more, and still more preferably in both the conduction region a and the insulation region b. 93% or more. If the average light transmittance of light having a wavelength of 400 to 1000 nm is 88% or more, the transparent conductor is also used in applications requiring light transmittance with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. Can be applied.

On the other hand, the average optical absorptance of light having a wavelength of 400 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and even more preferably in both the conduction region a and the insulation region b. Is 7% or less. In addition, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 to 800 nm is preferably 15% or less, more preferably 10% or less, both in the conduction region a and the insulation region b. Preferably it is 9% or less. On the other hand, the average light reflectance of light having a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, both in the conduction region a and the insulation region b. Preferably it is 10% or less. The lower the average light absorptance and average light reflectance of the transparent conductor, the higher the above-mentioned average light transmittance.

The average light transmittance, average light absorption rate, and average light reflectance are preferably an average light transmittance, an average light absorption rate, and an average light reflectance measured in an environment where the transparent conductor is used. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to measure the average light transmittance and the average light reflectance by disposing a layer made of the organic resin on the transparent conductor. . On the other hand, when the transparent conductor is used in the air, it is preferable to measure the average light transmittance and the average light reflectance in the air. The light transmittance and the light reflectance are measured with a spectrophotometer by allowing measurement light to enter from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductor. The light absorptance (%) is calculated from a calculation formula of 100− (light transmittance + light reflectance).

Further, when the transparent conductor 1 has the conductive region a and the insulating region b as shown in FIG. 2, it is preferable that the reflectance of the conductive region a and the reflectance of the insulating region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conduction region a and the luminous reflectance of the insulating region b is preferably 5% or less, more preferably 3% or less, and still more preferably It is 1% or less, particularly preferably 0.3% or less. On the other hand, the luminous reflectances of the conductive region a and the insulating region b are each preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation).

When the transparent conductor 1 includes the conduction region a and the insulation region b, the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are preferably within ± 30 in any region. More preferably, it is within ± 5, more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are within ± 30, both the conduction region a and the insulation region b are observed as colorless and transparent. The a ^* value and b ^* value in the L ^* a ^* b ^* color system are measured with a spectrophotometer.

The surface electrical resistance value of the conductive region a of the transparent conductor is preferably 50Ω / □ or less, and more preferably 30Ω / □ or less. A transparent conductor having a surface electric resistance value of 50 Ω / □ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the conduction region a is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the conduction region a is measured in accordance with, for example, JIS K7194, ASTM D257, or the like. It is also measured by a commercially available surface electrical resistivity meter.

[Method of forming transparent conductor having patterned electrode]
A method of forming a pattern composed of a conductive region and an insulating region as shown in FIG. 2 will be described for the transparent conductor of the present invention. In forming the pattern, a commercially available laser etching apparatus (manufactured by Takei Electric Industry Co., Ltd.) can be used. The wavelength is particularly preferably 1064 nm, 532 nm or 355 nm. The line width is preferably 5 to 30 μm.
In the transparent conductor of the present invention, for example, the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are laminated in this order on the transparent substrate by the method as described above. After that, it is preferable to form a metal electrode obtained by patterning the transparent metal layer into a predetermined shape. Specifically, for example, the patterning as shown in FIG. It is preferable to form an electrode. The line width of the electrode to be formed is preferably 50 μm or less, and particularly preferably 20 μm or less.

(Manufacturing process)
Hereinafter, an electrode patterning method 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 metal layer is processed into a desired pattern.

In the present invention, a conventionally known general photolithography method can be appropriately used. 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 predetermined 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 the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pretreated or post-baked as necessary, and then etched with an etching solution containing an organic solvent to dissolve the high refractive index layer in a region not protected by the resist and to form silver. The thin film electrode is removed. After etching, the remaining resist is peeled to obtain a transparent electrode having a predetermined pattern.
As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and a specific application mode thereof can be easily selected by a person skilled in the art according to a predetermined purpose. Can do.

Next, an electrode patterning method applicable to the present invention will be described with reference to the drawings.
4A to 4F are schematic views showing an example of patterning the electrode of the transparent conductor of the present invention by a photolithography method.

As a first step, as shown in FIG. 4A, on the transparent substrate 2, the first high refractive index layer 3A, the first antisulfurization layer 5A, the transparent metal layer 4, the second antisulfurization layer 5B, the second high refractive index. The transparent conductor 1 in which the layers 3B are laminated in this order is produced.
Next, it is preferable to subject the transparent conductor 1 to ultrasonic cleaning before forming the resist film in FIG. 4B. As the ultrasonic cleaning, for example, ultrasonic cleaning and water washing with pure water are performed several times using a detergent clean-through KS-3030 manufactured by Kao Corporation, and then water is blown off with a spin coater and dried in an oven.

Next, in the resist film forming step shown in FIG. 4B, a resist film 7 made of a photosensitive resin composition or the like is uniformly coated on the transparent conductor 1. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used. As the resist, for example, OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.

As a coating method, it is applied on the transparent conductor 1 by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and heated by a hot plate, oven or the like. It can be pre-baked in the apparatus. 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 step shown in FIG. 4C, 10 to 4000 J / m using an exposure machine 9 such as a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner through a mask 8 produced by predetermined patterning. ^The resist film 7A to be removed in the next step is irradiated with light of about 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 conductor is immersed in a developing solution to dissolve the resist film 7A in the region irradiated with light. As the developer, for example, when a positive photosensitive resin composition is used as a resist, a developer for positive photoresist “Tokuso SD” series (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation should be used. Can do.

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 an aqueous solution 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.

Next, as shown in FIG. 4E, an etching process using the etching solution 10 is performed.
As an etching solution applicable to the present invention, a solution containing an inorganic acid or an organic acid is preferable, and formic acid, acetic acid, oxalic acid, citric acid, hydrochloric acid, phosphoric acid, nitric acid and the like can be mentioned, and in particular, oxalic acid Acetic acid and phosphoric acid are preferred. Commercially available products can also be used as the etchant. For example, Pure Etch DE100 (oxalic acid) manufactured by Hayashi Junyaku Kogyo Co., Ltd., “Mixed Solution SEA-5” manufactured by Kanto Chemical Co. (phosphoric acid: 55% by mass, Acetic acid: 30% by mass, water and other components: 15% by mass) and the like can be used.

Specifically, for example, the transparent conductor 1 having the resist film 7 is immersed in an etching solution containing an organic acid or the like, and the electrode unit EU in the insulating region b that is not protected by the resist film 7 is dissolved. The electrode unit EU of the conductive region a protected by 7 is formed as a predetermined patterned electrode (hereinafter also referred to as an electrode pattern). The etching time varies depending on the type of acid to be applied, but is preferably adjusted within a range of 30 to 120 seconds.

Finally, as shown in FIG. 4F, an etched transparent conductor is used by using, for example, acetone, sodium hydroxide solution, N-300 manufactured by Nagase ChemteX Corp. as a resist film stripping solution, as a resist film stripping solution. The resist film 7 is removed by dipping, and a transparent conductor having a patterned electrode can be produced.

《Field of application of transparent conductors》
The transparent conductor of the present invention having the above-described configuration includes various displays such as a liquid crystal system, a plasma system, an organic electroluminescence system, a field emission system, a touch panel, a mobile phone, electronic paper, various solar cells, and various electroluminescence light control elements. It can preferably be used for substrates of various optoelectronic devices.

At this time, the surface of the transparent conductor (for example, the surface opposite to the transparent substrate) may be bonded to another member via an adhesive layer or the like. In this case, it is preferable that the equivalent admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the adhesive layer are approximated respectively. Thereby, reflection at the interface between the transparent conductor and the adhesive layer is suppressed. Specifically, it is preferable to adjust the admittance coordinates on the surface of the transparent conductor so that the reflectance at a wavelength of 550 nm is 1% or less. This is because the refractive index of the adhesive is generally difficult to adjust largely.

On the other hand, when used in a configuration in which the surface of the transparent conductor is in contact with air, it is preferable that the admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the air approximate each other. Thereby, reflection of light at the interface between the transparent conductor and air is suppressed. Specifically, it is preferable to adjust the admittance coordinates on the surface of the transparent conductor so that the reflectance at a wavelength of 550 nm is 1% or less.

Hereinafter, an example in which the transparent conductor of the present invention is applied to a touch panel will be described.
FIG. 5 is a perspective view illustrating an example of a configuration of a touch panel including a transparent conductor having patterned electrodes.
The touch panel 21 shown in FIG. 5 is a projected capacitive touch panel. In the touch panel 21, a first transparent electrode unit EU-1 and a second transparent electrode unit EU-2 are arranged in this order on one main surface of the transparent substrates 2-1 and 2-2. Covered with a face plate 13.

The first transparent electrode unit EU-1 and the second transparent electrode unit EU-2 are respectively transparent conductors 1 on which the patterned electrodes described with reference to FIGS. 2 and 4A to F are formed. . Therefore, the first transparent electrode unit EU-1 includes the first high refractive index layer 3A, the first sulfidation preventing layer 5A, the transparent metal layer 4, the second sulfidation preventing layer 5B, the second on the transparent substrate 2-1. The high refractive index layer 3B is laminated in this order. The second transparent electrode unit EU-2 has the same configuration.

The transparent conductor of the present invention can be applied to various types of touch panel touch sensors (hereinafter also referred to as “touch sensor electrode portions”) in addition to a projected capacitive touch panel. For example, it can be used in a surface capacitive touch panel, a resistive touch panel, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented. “S content” in the table represents the content of the sulfur component.
The composition ratio of the oxide used in the present invention is as follows: IGZO is In: Ga: Zn: O = 1: 1: 1: 4 (at% ratio), ITO is In ₂ O ₃ : SnO ₂ = 90: 10 (mass% ratio), ZTO is ZnO: SnO ₂ = 70: 30 (mass% ratio), AZO is Zn: Al = 96: 4 (at% ratio), IZO is In ₂ O ₃ : ZnO = 90:10 (mass% ratio).
In addition, regarding ZnO ^{* 1} and GZO ^{* 2} to GZO ^{* 7} , the compositions of oxides marked with * 1 to * 7 are as shown in Table 3. The layer thickness was adjusted by adjusting the sputtering time or the deposition time.

[Example 1]
<< Production of transparent conductor >>
[Preparation of transparent conductor 1]
A polyethylene terephthalate (abbreviation: PET) film (“Cosmo Shine A4300”, 50 μm thick, manufactured by Toyobo Co., Ltd.) is used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / transparent on the PET film according to the following method. A metal layer (Ag) / second anti-sulfurization layer (AZO) / second high refractive index layer (ITO) were laminated in this order.
In addition, the thickness and refractive index of each layer shown below are J.P. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS—SiO ₂ was RF (alternating current) sputtered so that The target-substrate distance was 86 mm. The target ZnS—SiO ₂ was prepared by mixing SiO ₂ with ZnS and sintering. The content rate of the sulfur component contained in the first high refractive index layer was 15 at%.

The content of the sulfur component in the first high refractive index layer was 15 at% as a result of measurement using X-ray photoelectron spectroscopy (XPS). The content rate of the sulfur component was similarly confirmed about the following examples.

(Formation of transparent metal layer (Ag))
Using Anelva's L-430S-FHS, Ar (20 sccm), sputtering pressure (0.25 Pa), room temperature, formation rate 0.7 nm / s, and silver (hereinafter referred to as Ag) layer thickness is 7.4 nm. DC sputtering was performed. The target-substrate distance was 86 mm.

(Formation of second anti-sulfurization layer (AZO))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / sec using an L-430S-FHS sputtering apparatus manufactured by Anelva. AZO was RF sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (ITO))
The PET film on which the second anti-sulfuration layer was produced was subjected to an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second. ITO was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target ITO was prepared by mixing ZnS with ITO and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 0.4 at%.
Thus, the transparent conductor 1 was produced.

[Production of transparent conductors 2 and 3]
In the production of the transparent conductor 1, as shown in Table 1, the materials of the second antisulfurization layer and the second high refractive index layer and the sulfur component contained in the first high refractive index layer and the second high refractive index layer The transparent conductors 2 and 3 were produced in the same manner as the production of the transparent conductor 1 by changing the content rate.

[Preparation of transparent conductor 4]
A 50 μm PET film was used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second on the PET film according to the following method. Two anti-sulfurization layers (GZO) / second high refractive index layer (GZO (5.7 mass%)) were laminated in this order.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS—SiO ₂ was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS—SiO ₂ was prepared by mixing SiO ₂ with ZnS and sintering. The content rate of the sulfur component contained in the first high refractive index layer was 24 at%.

(Formation of first antisulfurization layer (GZO))
Next, the PET film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC (direct current) sputtered to a layer thickness of 1.0 nm. The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Next, the PET film on which the first anti-sulfurization layer was formed was made using Anelva L-430S-FHS, Ar 20 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 2.0 nm / s, and layer thickness 7 Ag was DC sputtered to a thickness of 4 nm. The target-substrate distance was 86 mm.

(Formation of second anti-sulfurization layer (GZO))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / sec using an L-430S-FHS sputtering apparatus manufactured by Anelva. GZO was DC sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (GZO (5.7% by mass))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, GZO (5.7 mass%) was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. As shown in Table 1, the target GZO was prepared by mixing ZnS with GZO and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 1.0 at%.
Thus, the transparent conductor 4 was produced.

[Preparation of transparent conductor 5]
In the production of the transparent conductor 4, a transparent conductor 5 was produced in the same manner as the production of the transparent conductor 4 except that the first antisulfurization layer was not provided as shown in Table 1.

[Preparation of transparent conductor 6]
In the production of the transparent conductor 5, the transparent conductor 6 was produced in the same manner as the production of the transparent conductor 5 except that the second sulfidation preventing layer was not provided as shown in Table 1.

[Preparation of transparent conductor 7]
In the production of the transparent conductor 6, as shown in Table 1, the content of the sulfur component contained in the second high refractive index layer was changed to 5 at%, and the transparent conductor 6 was produced in the same manner as the production of the transparent conductor 6. A body 7 was produced.

[Preparation of transparent conductor 8]
In the production of the transparent conductor 4, as shown in Table 1, the content of the sulfur component contained in the first high refractive index layer was changed to 25 at%, and 10 mass of GZO used for the second high refractive index layer was obtained. The transparent conductor 8 was produced in the same manner as the production of the transparent conductor 4.

[Preparation of transparent conductor 9]
In the production of the transparent conductor 4, as shown in Table 1, the second antisulfurization layer is not provided, and the GZO used for the second high refractive index layer is changed to 23% by mass, so that the transparent conductor 4 A transparent conductor 9 was produced in the same manner as the production.

[Preparation of transparent conductor 10]
Using PET of 50 μm as a transparent substrate, a first high refractive index layer (ZnS) / transparent metal layer (Ag) / second antisulfuration layer (GZO) / second high refractive index on a PET film according to the following method. Layers (AZO) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
As a vacuum deposition device, a BMC-800T deposition device manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and the resistance heating boat was energized and heated. The current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed on the PET film under the condition of a formation rate of 2.0 nm / second to form a first high refractive index layer having a layer thickness of 40 nm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 35 at%.

(Formation of transparent metal layer (Ag))
Using an L-430S-FHS manufactured by Anelva, Ag was sputtered to form a layer thickness of 7.4 nm at an Ar of 20 sccm, a sputtering pressure of 0.25 Pa, a room temperature, and a formation rate of 0.7 nm / s. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (AZO))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, AZO was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target AZO was prepared by mixing AZO with ZnS and sintering. The content rate of the sulfur component contained in the second high refractive index layer was 4 at%.
Thus, the transparent conductor 10 was produced.

[Preparation of transparent conductor 11]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second high refraction is formed on the PET film according to the following method. The rate layer (GZO (10 mass%)) was laminated in this order.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 45 at%.

(Formation of first antisulfurization layer (GZO))
Next, the PET film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC sputtered to a layer thickness of 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO (10% by mass))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the transparent metal layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second, layer thickness GZO (10 mass%) was DC sputtered so that the thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target GZO (10 mass%) was prepared by mixing ZnS with GZO and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 1 at%.
Thus, the transparent conductor 11 was produced.

[Preparation of transparent conductor 12]
Using a PET film of 50 μm as a transparent substrate, the first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second antisulfuration is formed on the PET film according to the following method. Layer (GZO) / second high refractive index layer (TiO ₂ ) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 50 at%.

(Formation of second high refractive index layer (TiO ₂ ))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, TiO ₂ was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target TiO ₂ was prepared by mixing TiO ₂ with ZnS and sintering. The content rate of the sulfur component contained in the second high refractive index layer was 4 at%.
Thus, the transparent conductor 12 was produced.

[Preparation of transparent conductor 13]
Using a PET film of 50 μm as a transparent substrate, the first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second antisulfuration is formed on the PET film according to the following method. Layer (GZO) / second high refractive index layer (WO ₃ ) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 40 at%.

(Formation of second high refractive index layer (WO ₃ ))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, WO ₃ was RF sputtered to a layer thickness of 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target WO ₃ was prepared by mixing WO ₃ with ZnS and sintering. The content rate of the sulfur component contained in the second high refractive index layer was 9.8 at%.
In this way, a transparent conductor 13 was produced.

[Preparation of transparent conductor 14]
In the preparation of the transparent conductor 13, to change the content of sulfur component contained in the first high refractive index as shown in Table 1, by changing the material used for the second high refractive index layer ZrO ₂ Thus, a transparent conductor 14 was produced in the same manner as the production of the transparent conductor 13.

[Preparation of transparent conductor 15]
In the production of the transparent conductor 10, as shown in Table 1, with respect to AZO, which is a target used for the second high refractive index layer, the point of production is changed by mixing AZO with simple sulfur and sintering. Thus, a transparent conductor 15 was produced in the same manner as the production of the transparent conductor 10.

[Preparation of transparent conductor 16]
In the production of the transparent conductor 11, as shown in Table 1, ZTO, which is a target used for the second high refractive index layer, is produced by mixing and sintering ZTO alone with ZTO. The transparent conductor 16 was produced in the same manner as the production of the transparent conductor 11 by changing the content of the sulfur component contained in the refractive index layer to 4 at%.

[Preparation of transparent conductor 17]
In the preparation of the transparent conductor 12, the TiO ₂ is a target used in the second high refractive index layer as shown in Table 1, the point of making by mixing the elemental sulfur in the TiO _2, is sintered In the same manner as in the production of the transparent conductor 12, the transparent conductor 17 was produced.

[Preparation of transparent conductor 18]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (ZnS) / first antisulfuration layer (ZnO) / transparent metal layer (Ag) / second high refraction is formed on the PET film according to the following method. Rate layers (WO ₃ ) were laminated in this order.

(Formation of first antisulfurization layer (ZnO))
Next, the PET film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, ZnO was RF sputtered to a layer thickness of 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (WO ₃ ))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the transparent metal layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second, layer thickness WO ₃ was RF sputtered to a thickness of 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target WO ₃ was prepared by mixing WO ₃ with sulfur alone and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 9.8 at%.
In this way, a transparent conductor 18 was produced.

[Preparation of transparent conductor 19]
Using a 50 μm PET film as the transparent substrate, the first high refractive index layer (ZnS) / first anti-sulfurization layer (ZnO) / transparent metal layer (Ag) / second anti-sulfurization layer is formed on the PET film according to the following method. Layer (ZnO) / second high refractive index layer (ZrO ₂ ) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 43 at%.

(Formation of second anti-sulfurization layer (ZnO))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / sec using an L-430S-FHS sputtering apparatus manufactured by Anelva. ZnO was RF sputtered to have a layer thickness of 1.0 nm. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZrO ₂ ))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, ZrO ₂ was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 1, the target ZrO ₂ was prepared by mixing and sintering a single element of sulfur in ZrO ₂ . The content rate of the sulfur component contained in the second high refractive index layer was 9.8 at%.
In this way, a transparent conductor 19 was produced.

[Production of transparent conductor 20]
A 50 μm PET film was used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second on the PET film according to the following method. A disulfide prevention layer (GZO) / second high refractive index layer (ZnO ^{* 1} ) were laminated in this order.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS—SiO ₂ was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS—SiO ₂ was prepared by mixing SiO ₂ with ZnS and sintering. The content rate of the sulfur component contained in the first high refractive index layer was 25 at%.

(Formation of Second High Refractive Index Layer (ZnO ^{* 1} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, ZnO ^{* 1} was RF sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The composition of ZnO ^{* 1} corresponds to * 1 shown in Table 3. Further, as shown in Table 1, the target ZnO ^{* 1} was prepared by mixing ZnS and ITO in ZnO and sintering. The content rate of the sulfur component contained in the second high refractive index layer was 0.5 at%.
Thus, the transparent conductor 20 was produced.

[Preparation of transparent conductor 21]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (ZnS—SiO ₂ ) / transparent metal layer (Ag) / second high refractive index layer (GZO ^{* 2} ) is formed on the PET film according to the following method. ) Were laminated in this order.

(Formation of transparent metal layer (Ag))
Next, the PET film on which the first high refractive index layer was formed was Ln430S-FHS manufactured by Anelva, Ar 20 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 2.0 nm / s, and layer thickness. Ag was DC sputtered to a thickness of 7.4 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO ^{* 2} ))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a formation rate of 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. GZO ^{* 2} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The composition of GZO ^{* 2} corresponds to * 2 shown in Table 3. Further, as shown in Table 2, the target GZO ^{* 2} was prepared by mixing ZnS with GZO (5.7 mass%) and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 4.2 at%.
Thus, the transparent conductor 21 was produced.

[Preparation of transparent conductor 22]
In the preparation of the transparent conductor 21, the material used for the second high refractive index layer as shown in Table 1 by changing the GZO * ³ shown in Table 3, the sulfur components contained in GZO * ³ A transparent conductor 22 was produced in the same manner as the production of the transparent conductor 21 except that the content rate was 2.0 at%.

[Preparation of transparent conductor 23]
In the production of the transparent conductor 21, the material used for the second high refractive index layer is changed to GZO ^{* 4} shown in Table 3 as shown in Table 1, and contained in the second high refractive index layer. A transparent conductor 23 was prepared in the same manner as the transparent conductor 21 except that the content of the sulfur component was 1.8 at%.

[Preparation of transparent conductor 24]
In the production of the transparent conductor 20, the material used for the second high refractive index layer is changed to GZO ^{* 5} shown in Table 3 as shown in Table 1, and contained in the second high refractive index layer. A transparent conductor 24 was prepared in the same manner as the transparent conductor 20 except that the content of the sulfur component was 0.8 at%.

[Preparation of transparent conductor 25]
In the production of the transparent conductor 20, as shown in Table 1, the material used for the second high refractive index layer is changed to GZO ^{* 6} shown in Table 3, and is contained in the second high refractive index layer. A transparent conductor 25 was prepared in the same manner as the transparent conductor 20 except that the content of the sulfur component was 0.7 at%.

[Preparation of transparent conductor 26]
In the production of the transparent conductor 20, as shown in Table 1, the material used for the second high refractive index layer is changed to GZO ^{* 7} shown in Table 3 and contained in the second high refractive index layer. A transparent conductor 26 was prepared in the same manner as the transparent conductor 20 except that the content of the sulfur component was 0.6 at%.

[Preparation of transparent conductor 27]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (ITO) / transparent metal layer (Ag) / second antisulfuration layer (GZO) / second high refraction is formed on the PET film according to the following method. The rate layer (ITO) was laminated in this order.

(Formation of first high refractive index layer (ITO))
On a transparent substrate (PET), using an Anelva L-430S-FHS sputtering system, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, ITO layer thickness Was RF sputtered to a thickness of 46 nm. The target-substrate distance was 86 mm. The target ITO was prepared by mixing ZnS in ITO and sintering it. The content rate of the sulfur component contained in the first high refractive index layer was 0.7 at%.

(Formation of second high refractive index layer (ITO))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, ITO was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm. As shown in Table 2, the target ITO was prepared by mixing ZnS with ITO and sintering it. The content rate of the sulfur component contained in the second high refractive index layer was 0.7 at%.
In this manner, a transparent conductor 27 was produced.

[Preparation of transparent conductor 28]
Using a 50 μm PET film as the transparent substrate, the first high refractive index layer (ZnO ^{* 1} ) / transparent metal layer (Ag) / second antisulfuration layer (GZO) / second on the PET film according to the following method. A high refractive index layer (ZnO ^{* 1} ) was laminated in this order.

(Formation of the first high refractive index layer (ZnO ^{* 1} ))
On a transparent substrate (PET), using an L-430S-FHS sputtering apparatus manufactured by Anelva, ZnO ^{* 1} was formed at an Ar of 20 sccm, O _{2 of} 0 sccm, a sputtering pressure of 0.25 Pa, a room temperature, and a formation rate of 0.15 nm / s. RF sputtering was performed so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the first high refractive index layer was 0.5 at%.

(Formation of Second High Refractive Index Layer (ZnO ^{* 1} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, ZnO ^{* 1} was RF sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.5 at%.
In this way, a transparent conductor 28 was produced.

[Preparation of transparent conductor 29]
Using a 50 μm PET film as the transparent substrate, the first high refractive index layer (GZO ^{* 2} ) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second on the PET film according to the following method. A high refractive index layer (GZO ^{* 2} ) was laminated in this order.

(Formation of first high refractive index layer (GZO ^{* 2} ))
On a transparent substrate (PET), using an Anelva L-430S-FHS sputtering apparatus, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, GZO ^{* 2} DC sputtering was performed so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the first high refractive index layer was 4.2 at%.

(Formation of second high refractive index layer (GZO ^{* 2} ))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a formation rate of 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. GZO ^{* 2} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 4.2 at%.
In this way, a transparent conductor 29 was produced.

[Preparation of transparent conductor 30]
In the production of the transparent conductor 29, as shown in Table 2, the material used for the first high refractive index layer and the second high refractive index layer was changed to GZO ^{* 3} shown in Table 3, A transparent conductor 30 was produced in the same manner as the production of the transparent conductor 29 except that the content of the sulfur component contained in the refractive index layer and the second high refractive index layer was 2.0 at%.

[Preparation of transparent conductor 31]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (GZO ^{* 4} ) / transparent metal layer (Ag) / second high refractive index layer (GZO ^{* 4} ) is formed on the PET film according to the following method. Were stacked in this order.

(Formation of first high refractive index layer (GZO ^{* 4} ))
On a transparent substrate (PET), using an Anelva L-430S-FHS sputtering apparatus, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, GZO ^{* 4} DC sputtering was performed so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the first high refractive index layer was 1.8 at%.

(Formation of second high refractive index layer (GZO ^{* 4} ))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a formation rate of 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. GZO ^{* 4} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 1.8 at%.
In this way, a transparent conductor 31 was produced.

[Production of Transparent Conductor 32]
In the production of the transparent conductor 28, as shown in Table 2, the material used for the first high refractive index layer and the second high refractive index layer is changed to GZO ^{* 5} shown in Table 3, A transparent conductor 32 was produced in the same manner as the production of the transparent conductor 28 except that the content of the sulfur component contained in the refractive index layer and the second high refractive index layer was 0.8 at%.

[Preparation of transparent conductor 33]
In the production of the transparent conductor 28, as shown in Table 2, the material used for the first high refractive index layer and the second high refractive index layer was changed to GZO ^{* 6} shown in Table 3, A transparent conductor 33 was prepared in the same manner as the transparent conductor 28 except that the content of the sulfur component contained in the refractive index layer and the second high refractive index layer was 0.7 at%.

[Preparation of transparent conductor 34]
In the production of the transparent conductor 28, as shown in Table 2, the material used for the first high refractive index layer and the second high refractive index layer was changed to GZO ^{* 7} shown in Table 3, A transparent conductor 34 was prepared in the same manner as the transparent conductor 28 except that the content of the sulfur component contained in the refractive index layer and the second high refractive index layer was 0.6 at%.

[Preparation of transparent conductor 35]
Using PET of 50 μm as a transparent substrate, a first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second antisulfurization layer on a PET film according to the following method (GZO) / second high refractive index layer (ZnO ^{* 1} ) was laminated in this order.

(Formation of first high refractive index layer (ZnS))
As a vacuum deposition device, a BMC-800T deposition device manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed on the PET film under the condition of a formation rate of 2.0 nm / second to form a first high refractive index layer having a layer thickness of 35 nm. The content rate of the sulfur component contained in the first high refractive index layer was 39 at%.

(Formation of first antisulfurization layer (GZO))
Next, the PET film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC sputtered to a layer thickness of 0.5 nm. The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Using an L-430S-FHS manufactured by Anelva, Ag was sputtered at a formation rate of 0.7 nm / s under a 20 sccm Ar, sputtering pressure of 0.25 Pa, room temperature, and a layer thickness of 6.0 nm. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZnO ^{* 1} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, ZnO ^{* 1} was RF sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.5 at%.
In this way, a transparent conductor 35 was produced.

[Preparation of transparent conductor 36]
Using a PET film of 50 μm as a transparent substrate, the first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second antisulfuration is formed on the PET film according to the following method. Layer (Si) / second high refractive index layer (GZO ^{* 2} ) were laminated in this order.

(Formation of second anti-sulfurization layer (Si))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / sec using an L-430S-FHS sputtering apparatus manufactured by Anelva. Si was RF-sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO ^{* 2} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, GZO ^{* 2} was DC sputtered to have a layer thickness of 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 4.2 at%.
In this way, a transparent conductor 36 was produced.

[Preparation of transparent conductor 37]
In the production of the transparent conductor 35, as shown in Table 2, the transparent substrate was changed to a polycarbonate polymer (abbreviation: PC) film (“Elmec R40 # 140 film”, 40 μm thickness, manufactured by Kaneka), and the second high refractive index layer The transparent conductor 35 is manufactured except that the material used for is changed to GZO ^{* 3} shown in Table 3 and the content of the sulfur component contained in the second high refractive index layer is 2.0 at%. In the same manner, a transparent conductor 37 was produced.

[Preparation of transparent conductor 38]
Using a polycarbonate polymer (PC) film as a transparent substrate, a first high refractive index layer (ZnS-DC3) / first antisulfurization layer (GZO) / transparent metal layer (Ag) / A second antisulfurization layer (Si) / second high refractive index layer (GZO ^{* 4} ) was laminated in this order.

(Formation of first high refractive index layer (ZnS-DC3))
Using an L-430S-FHS sputtering apparatus manufactured by Anerva on a transparent substrate (PC), Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 1 nm / s, and layer thickness 35 nm ZnS-DC3 was DC sputtered. The target-substrate distance was 86 mm. The target, ZnS-DC3, was manufactured by JX Nippon Mining & Metals. The content rate of the sulfur component contained in the first high refractive index layer was 35 at%.

(Formation of first antisulfurization layer (GZO))
Next, the PC film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / _second using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC sputtered to a layer thickness of 0.5 nm. The target-substrate distance was 86 mm.

(Formation of second anti-sulfurization layer (Si))
Next, the PC film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / second using an Anelva L-430S-FHS sputtering apparatus. Si was RF-sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO ^{* 4} ))
Next, the PC film on which the second sulfidation preventing layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 4} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 1.8 at%.
In this way, a transparent conductor 38 was produced.

[Preparation of transparent conductor 39]
Using a cycloolefin polymer (abbreviation: COP) film (“ZEONOR Z14”, 50 μm thick, manufactured by Nippon Zeon Co., Ltd.) as the transparent substrate, the first high refractive index layer (ZnS) / first layer was formed on the COP film according to the following method. An antisulfurization layer (GZO) / transparent metal layer (Ag) / second antisulfurization layer (GZO) / second high refractive index layer (GZO ^{* 5} ) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
As a vacuum deposition device, a BMC-800T deposition device manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed on the COP film under the condition of a formation rate of 2.0 nm / second to form a first high refractive index layer having a layer thickness of 35 nm. The content rate of the sulfur component contained in the first high refractive index layer was 39 at%.

(Formation of first antisulfurization layer (GZO))
Next, the COP film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC sputtered to a layer thickness of 0.5 nm. The target-substrate distance was 86 mm.

(Formation of second anti-sulfurization layer (GZO))
Next, the COP film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a formation rate of 0.06 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. GZO was DC sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO ^{* 5} ))
Next, the COP film on which the second anti-sulfurization layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, and formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 5} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.8 at%.
In this way, a transparent conductor 39 was produced.

[Production of Transparent Conductor 40]
Using a cycloolefin polymer (abbreviation: COP) film (Zeonor Z14, 50 μm thick, manufactured by Nippon Zeon Co., Ltd.) as the transparent substrate, the first high refractive index layer (ZnS-DC3) / A first antisulfurization layer (GZO) / transparent metal layer (Ag) / second antisulfurization layer (GZO) / second high refractive index layer (GZO ^{* 6} ) were laminated in this order.

(Formation of first high refractive index layer (ZnS-DC3))
Using an L-430S-FHS sputtering system manufactured by Anelva on a transparent substrate (COP), Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 1 nm / s, and layer thickness 35 nm ZnS-DC3 was DC sputtered. The target-substrate distance was 86 mm. The target, ZnS-DC3, was manufactured by JX Nippon Mining & Metals. The content rate of the sulfur component contained in the first high refractive index layer was 35 at%.

(Formation of second high refractive index layer (GZO ^{* 6} ))
Next, the COP film on which the second anti-sulfurization layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, and formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 6} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.7 at%.
Thus, the transparent conductor 40 was produced.

[Preparation of transparent conductor 41]
Using a triacetyl cellulose (abbreviation: TAC) film (TAC film made by Konica Minolta, thickness 40 μm) as a transparent substrate, the first high refractive index layer (ZnS) / first anti-sulfurization is performed on the TAC film according to the following method. Layer (GZO) / transparent metal layer (Ag) / second antisulfurization layer (Si) / second high refractive index layer (GZO ^{* 7} ) were laminated in this order.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (TAC), an L-430S-FHS sputtering apparatus manufactured by Anelva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 35 nm ZnS was RF sputtered so that The target-substrate distance was 86 mm. The target ZnS was produced by sintering ZnS. The content rate of the sulfur component contained in the first high refractive index layer was 39 at%.

(Formation of first antisulfurization layer (GZO))
Next, the TAC film on which the first high refractive index layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / L using an Anelva L-430S-FHS sputtering apparatus. In a second, GZO was DC sputtered to a layer thickness of 0.5 nm. The target-substrate distance was 86 mm.

(Formation of second anti-sulfurization layer (Si))
Next, the TAC film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / second using an Anelva L-430S-FHS sputtering apparatus. Si was RF-sputtered so that the layer thickness was 1.0 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (GZO ^{* 7} ))
Next, the TAC film on which the second sulfidation prevention layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 7} was DC sputtered so that the layer thickness was 46 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.6 at%.
In this way, a transparent conductor 41 was produced.

[Preparation of transparent conductor 42]
A 50 μm PET film was used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (GZO) / transparent metal layer (Ag) / second on the PET film according to the following method. A disulfide prevention layer (GZO) / second high refractive index layer (ZnO) were laminated in this order.

(Formation of second high refractive index layer (ZnO))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the second sulfidation-preventing layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, at room temperature, at a formation rate of 0.03 nm / second, ZnO (manufactured by Toshima Seisakusho Co., Ltd.) was RF sputtered so that the layer thickness was 46 nm. The deposited film had a target-substrate distance of 86 mm.
In this way, a transparent conductor 42 was produced.

[Preparation of transparent conductor 43]
In the production of the transparent conductor 42, as shown in Table 2, the material used for the second high refractive index layer was changed to 5.7 mass% GZO (manufactured by Toshima Seisakusho Co., Ltd.), and the film was formed by DC sputtering. A transparent conductor 43 was produced in the same manner as the production of the transparent conductor 42 except that.

[Preparation of transparent conductor 44]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (ZnS) / transparent metal layer (Ag) / second high refractive index layer (ZnS) are laminated in this order on the PET film according to the following method. did.

(Formation of first high refractive index layer (ZnS))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZnS (Toyoshima Seisakusho Co., Ltd.) was RF sputtered so that The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the first high refractive index layer was 50 at%.

(Formation of transparent metal layer (Ag))
Using an L-430S-FHS manufactured by Anerva, Ag was sputtered at a formation rate of 0.7 nm / s under a 20 sccm Ar, sputtering pressure of 0.25 Pa, room temperature, and a layer thickness of 12 nm. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZnS))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the transparent metal layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second, layer thickness ZnS (manufactured by Toyoshima Seisakusho Co., Ltd.) was RF sputtered to a thickness of 40 nm. The deposited film had a target-substrate distance of 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 50 at%.
In this way, a transparent conductor 44 was produced.

[Preparation of transparent conductor 45]
Using a 50 μm PET film as a transparent substrate, a first high refractive index layer (Nb ₂ O ₅ ) / transparent metal layer (Ag) / second high refractive index layer (IZO) is formed on the PET film according to the following method. The layers were laminated in this order.

(Formation of the first high refractive index layer (Nb ₂ O ₅ ))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, layer thickness 27 Nb ₂ O ₅ (manufactured by Toshima Seisakusho Co., Ltd.) was RF sputtered to a thickness of 0.7 nm.

(Formation of transparent metal layer (Ag))
Using Anelva L-430S-FHS, DC sputtering of Ag was performed at a formation rate of 0.7 nm / s at an Ar of 20 sccm, a sputtering pressure of 0.25 Pa, a room temperature, and a layer thickness of 7.7 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (IZO))
Using an L-430S-FHS sputtering apparatus manufactured by Anerva on an transparent substrate, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, forming rate 0.03 nm / second, and layer thickness 36 nm IZO (manufactured by Toshima Seisakusho Co., Ltd.) was RF sputtered. The deposited film had a target-substrate distance of 86 mm.
In this way, a transparent conductor 45 was produced.

[Preparation of transparent conductor 46]
Using a 50 μm PET film as the transparent substrate, the first high refractive index layer (ZTO) / transparent metal layer (Ag) / second high refractive index layer (ZTO) are laminated in this order on the PET film according to the following method. did.

(Formation of first high refractive index layer (ZTO))
On a transparent substrate (PET), an L-430S-FHS sputtering apparatus manufactured by Anerva Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 40 nm ZTO (Toyoshima Seisakusho Co., Ltd.) was RF sputtered so that The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Using an L-430S-FHS manufactured by Anelva, Ag was RF-sputtered with an Ar of 20 sccm, a sputtering pressure of 0.25 Pa, a room temperature, and a formation rate of 0.7 nm / s to a layer thickness of 10 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (ZTO))
Using a Anelva L-430S-FHS sputtering apparatus, the PET film on which the transparent metal layer was formed was Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second, layer thickness ZTO (manufactured by Toshima Seisakusho Co., Ltd.) was RF sputtered so that the thickness was 40 nm. The deposited film had a target-substrate distance of 86 mm.
In this way, a transparent conductor 46 was produced.

[Preparation of transparent conductor 47]
In the production of the transparent conductor 37, the thickness of the second anti-sulfurization layer was changed to 0.5 nm, and the material used for the second high refractive index layer was changed to GZO ^{* 6} as shown in Table 2. A transparent conductor 47 was prepared in the same manner as the transparent conductor 37 except that the content of the sulfur component contained in the second high refractive index layer was 12.0 at%.

Details of the abbreviations and symbols used in the production of the above transparent conductors or in Tables 1 to 3 are as follows.
PET: Polyethylene terephthalate ITO: indium tin oxide GZO: gallium zinc oxide IGZO: indium gallium zinc oxide AZO: Aluminum Zinc oxide ZTO: zinc tin oxide A: mix SiO ₂ to ZnS Sintering B: Sintering ZnS C: Sintering by mixing ZnS in ITO D: Sintering by mixing ZnS in IGZO E: Mixing and sintering ZnS in ZnO F: Sintering by mixing ZnS in GZO G: Sintering by mixing ZnS with AZO H: Sintering by mixing ZnS with TiO ₂ I: Sintering by mixing ZnS with WO ₃ J: Sintering with ZnS mixed with ZrO ₂ K: Mixing single element of sulfur with AZO Sintering L: Sintered with ZTO in ZTO M: Sintered with mixed sulfur in TiO ₂ N: Sintered with mixed sulfur in WO ₃ P: Sintered with mixed sulfur in ZrO ₂ Q: ZnS and ITO mixed with ZnS and sintered R: GZO (5.7 mass%) mixed with ZnS and sintered S: GZO (5.7 mass%) mixed with ZnS and ITO and sintered T: GZO (10% by mass) mixed with ZnS and sintered U: manufactured by Toshima Seisakusho Co., Ltd. V: manufactured by JX Nippon Mining & Metals

<< Evaluation of transparent conductor >>
About each produced said transparent conductor, the following characteristic value was measured and evaluated.

(Measurement of average light absorption rate)
The average light absorptance is measured by measuring the average light transmittance and the average light reflectance of the transparent substrate 2 by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate.
Average light absorption rate (%) = 100- (average light transmittance + average light reflectance) (%)
Calculate as The average light transmittance and the average light reflectance can be measured using a spectrophotometer. It measured with the spectrophotometer (U4100; Hitachi High-Technologies company make).

[Measurement of sheet resistance]
A resistance meter “Loresta EP MCP-T360” manufactured by Mitsubishi Chemical Analytech Co., Ltd. was brought into contact with the conduction region a of each transparent conductor, and the sheet resistance value (Ω / □) of the conduction region a was measured.

[Corrosion evaluation]
The corrosion resistance of the transparent conductors obtained in Examples and Comparative Examples was evaluated. Corrosion resistance was evaluated by the appearance after storing the transparent conductors obtained in Examples or Comparative Examples, two by two in 85 ° C. and 85% Rh for 240 hours. Evaluation was based on the following criteria.
A: 0 in the region of 30 mm × 30 mm, no corrosion sites with a size of 20 μm or more ○: In a region of 30 mm × 30 mm, 1 or more and less than 10 corrosion sites in the size of 20 μm ×: In the region of 30 mm × 30 mm Tables 1 to 3 show the structure of the transparent conductor and the results obtained by the above evaluation, with 10 or more corrosion spots of 20 μm or more.

[Flexibility evaluation]
The transparent conductors obtained in Examples and Comparative Examples were placed on a flat support member, and one end was fixed. The transparent conductor was bent into a U shape. The curvature radius of the bent portion was 5 mm. And the other end of the transparent conductor was fixed to the sliding plate arrange | positioned in parallel with the supporting member. The sliding plate was reciprocated 1000 times in the length direction of the transparent conductor while keeping the sliding plate and the support member in parallel. Thereafter, it was visually confirmed whether cracks or the like occurred in each layer of the transparent conductor. The flexibility was evaluated as follows.
A: No crack was generated in a 30 mm × 30 mm region including the bent portion. ○: One to 50 cracks were generated in the 30 mm × 30 mm region including the bent portion. X: The bent portion was included. Over 50 cracks occurred in a 30mm x 30mm area

As is clear from the results shown in Table 4, the transparent conductors 1 to 41 of the present invention are superior in light transmittance, moisture resistance, and electrical connectivity as compared with the comparative transparent conductors 42 to 47. I understood.

[Example 2]
The transparent conductor shown in Example 2 is different in that an adhesive layer and a third high refractive index layer are provided on the transparent conductor shown in Example 1. The configuration of each transparent conductor is as shown in Table 5. Differences from the first embodiment will be described below.

[Production of transparent conductor 50]
Using a 50 μm PET film as a transparent substrate, an adhesion layer (SiO ₂ / ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (GZO) is formed on the PET film according to the following method. / Transparent metal layer (Ag) / second anti-sulfurization layer (GZO) / second high refractive index layer (ZnO ^{* 1} ) / third high refractive index layer (ZrO ₂ ) were laminated in this order.

(Formation of adhesion layer (SiO ₂ / ZnS—SiO ₂ ))
As a vacuum deposition apparatus, a BMC-800T deposition apparatus manufactured by SYNCHRON Co., Ltd. was used. After the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, SiO ₂ was deposited on the PET film at a rate of 2.0 nm / _second by EB ( Electron beam) was evaporated to form a layer having a thickness of 1 nm.
Next, on the SiO ₂ layer, using an L-430S-FHS sputtering apparatus manufactured by Anelva, Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s, and layer thickness 1 nm ZnS—SiO ₂ was RF sputtered so that The target-substrate distance was 86 mm.
An adhesion layer (SiO ₂ / ZnS—SiO ₂ ) having a layer thickness of 2 nm was formed.

(Formation of first high refractive index layer (ZnS))
As a vacuum deposition device, a BMC-800T deposition device manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed on the adhesion layer under the condition of a formation rate of 2.0 nm / second to form a first high refractive index layer having a layer thickness of 35 nm. The content rate of the sulfur component contained in the first high refractive index layer was 39 at%.

(Formation of second anti-sulfurization layer (GZO))
Next, the PET film on which the transparent metal layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature at a forming rate of 0.06 nm / sec using an L-430S-FHS sputtering apparatus manufactured by Anelva. GZO was DC sputtered so that the layer thickness was 0.5 nm. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZnO ^{* 1} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, ZnO ^{* 1} was RF sputtered so that the layer thickness was 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.5 at%.

(Formation of third high refractive index layer (ZrO ₂ ))
Next, using a BMC-800T vapor deposition device manufactured by Shincron as a vacuum vapor deposition device, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then ZrO ₂ was deposited on the PET film under the condition of a formation rate of 2.0 nm / _second . EB deposition was performed to form a layer with a layer thickness of 27 nm.
In this way, a transparent conductor 50 was produced.

[Preparation of transparent conductor 51]
Using a 50 μm PET film as a transparent substrate, an adhesion layer (SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal layer (on the PET film) Ag) / second anti-sulfurization layer (GZO) / second high refractive index layer (GZO ^{* 2} ) / third high refractive index layer (SnO ₂ ) were laminated in this order.

(Formation of adhesion layer (SiO ₂ ))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as the vacuum vapor deposition device, and after the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, SiO ₂ was deposited on the PET film by EB deposition at a formation rate of 2.0 nm / second. Thus, an adhesion layer having a layer thickness of 1 nm was formed.

In the transparent conductor 51, the steps (formation of the first high refractive index layer (ZnS)) to (formation of the second antisulfurization layer (GZO)) were produced in the same manner as the transparent conductor 50.

(Formation of second high refractive index layer (GZO ^{* 2} ))
Next, the PET film on which the second anti-sulfuring layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an Anelva L-430S-FHS sputtering apparatus. Then, GZO ^{* 2} was DC sputtered to have a layer thickness of 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 4.2 at%.

(Formation of third high refractive index layer (SnO ₂ ))
Next, using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and SnO ₂ was then deposited on the PET film at a formation rate of 2.0 nm / _second . EB deposition was performed to form a layer with a layer thickness of 27 nm.
In this way, a transparent conductor 51 was produced.

[Preparation of transparent conductor 52]
Using a polycarbonate polymer (PC) film as a transparent substrate, an adhesion layer (SiO ₂ / ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (on the PC film according to the following method) GZO) / transparent metal layer (Ag) / second anti-sulfurization layer (GZO) / second high refractive index layer (GZO ^{* 3} ) / third high refractive index layer (ZrO ₂ ) were laminated in this order.

In the transparent conductor 52, except for using PC as a transparent substrate, the steps of (formation of adhesion layer (SiO ₂ / ZnS—SiO ₂ )) to (formation of second anti-sulfurization layer (GZO)) are transparent. It was produced in the same manner as the conductor 50.

(Formation of second high refractive index layer (GZO ^{* 3} ))
Next, the PC film on which the second sulfidation preventing layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 3} was DC sputtered so that the layer thickness was 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 2.0 at%.

The step of (third high refractive index layer (ZrO ₂ ) formation) was prepared in the same manner as the transparent conductor 50.
In this way, a transparent conductor 52 was produced.

[Preparation of transparent conductor 53]
Using a polycarbonate polymer (PC) film as a transparent substrate, an adhesion layer (SiO ₂ / ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (on the PC film according to the following method) GZO) / transparent metal layer (Ag) / second antisulfurization layer (GZO) / second high refractive index layer (GZO ^{* 4} ) / third high refractive index layer (SnO ₂ ) were laminated in this order.

The steps of (adhesion layer (SiO ₂ / ZnS—SiO ₂ ) formation) to (formation of second anti-sulfurization layer (GZO)) in the transparent conductor 53 were produced in the same manner as the transparent conductor 50.

(Formation of second high refractive index layer (GZO ^{* 4} ))
Next, the PC film on which the second sulfidation preventing layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 4} was DC sputtered to have a layer thickness of 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 1.8 at%.

The step of (formation of third high refractive index layer (SnO ₂ ))) was produced in the same manner as the transparent conductor 51.
In this way, a transparent conductor 53 was produced.

[Preparation of transparent conductor 54]
Using a cycloolefin polymer (COP) film as a transparent substrate, an adhesion layer (ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (GZO) is formed on the COP film according to the following method. / Transparent metal layer (Ag) / second anti-sulfurization layer (GZO) / second high refractive index layer (GZO ^{* 5} ) / third high refractive index layer (ZrO ₂ ) were laminated in this order.

(Formation of adhesion layer (ZnS-SiO ₂ ))
Using an Anelva L-430S-FHS sputtering system, ZnS-SiO ₂ was formed so that the layer thickness would be 1 nm with Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.15 nm / s. RF sputtered. The target-substrate distance was 86 mm.

In the transparent conductor 54, the steps (formation of the first high refractive index layer (ZnS)) to (formation of the second antisulfurization layer (GZO)) were produced in the same manner as the transparent conductor 50.

(Formation of second high refractive index layer (GZO ^{* 5} ))
Next, the COP film on which the second anti-sulfurization layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, and formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 5} was DC sputtered to have a layer thickness of 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.8 at%.

The step of (third high refractive index layer (ZrO ₂ ) formation) was prepared in the same manner as the transparent conductor 50.
In this way, a transparent conductor 54 was produced.

[Preparation of transparent conductor 55]
Using a cycloolefin polymer (COP) film as a transparent substrate, an adhesion layer (SiO ₂ / ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer is formed on the COP film according to the following method. (GZO) / transparent metal layer (Ag) / second antisulfurization layer (GZO) / second high refractive index layer (GZO ^{* 6} ) / third high refractive index layer (SnO ₂ ) were laminated in this order.

In the transparent conductor 55, except for using COP as a transparent substrate, the steps of (formation of adhesion layer (SiO ₂ / ZnS—SiO ₂ )) to (formation of second anti-sulfurization layer (GZO)) are transparent. It was produced in the same manner as the conductor 50.

(Formation of second high refractive index layer (GZO ^{* 6} ))
Next, the COP film on which the second anti-sulfurization layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, and formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 6} was DC sputtered to have a layer thickness of 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.7 at%.

The step of (third high refractive index layer (SnO ₂ ) formation) was prepared in the same manner as the transparent conductor 51.
In this way, a transparent conductor 55 was produced.

[Preparation of transparent conductor 56]
Using a triacetyl cellulose (TAC) film as a transparent substrate, an adhesion layer (ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (GZO) is formed on the TAC film according to the following method. / Transparent metal layer (Ag) / second anti-sulfurization layer (GZO) / second high refractive index layer (GZO ^{* 7} ) / third high refractive index layer (SnO ₂ ) were laminated in this order.

In the transparent conductor 56, except for using TAC as the transparent substrate, the steps of (formation of adhesion layer (ZnS—SiO ₂ )) to (formation of second anti-sulfurization layer (GZO)) are as follows. It produced similarly.

(Formation of second high refractive index layer (GZO ^{* 7} ))
Next, the TAC film on which the second sulfidation prevention layer was formed was subjected to Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.03 nm / second using an L-430S-FHS sputtering apparatus manufactured by Anelva. Then, GZO ^{* 7} was DC sputtered to have a layer thickness of 20 nm. The target-substrate distance was 86 mm. The content rate of the sulfur component contained in the second high refractive index layer was 0.6 at%.

The step of (third high refractive index layer (SnO ₂ ) formation) was prepared in the same manner as the transparent conductor 51.
In this way, a transparent conductor 56 was produced.

[Preparation of transparent conductor 57]
Using a polyethylene terephthalate (PET) film as a transparent substrate, an adhesion layer (SiO ₂ / ZnS—SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfurization layer (on the PET film according to the following method) GZO) / transparent metal layer (APC-TR) / second anti-sulfurization layer (GZO) / second high refractive index layer (ZnO ^{* 1} ) / third high refractive index layer (ZrO ₂ ) were laminated in this order.

In the transparent conductor 57, in the steps of (adhesion layer (SiO ₂ / ZnS—SiO ₂ ) formation) to (third high refractive index layer (ZrO ₂ ) formation), except for the formation of the transparent metal layer, It produced similarly to the transparent conductor 50.

(Formation of transparent metal layer (APC-TR))
Using Anelva L-430S-FHS, Ar 20 sccm, sputtering pressure 0.25 Pa, room temperature, formation rate 0.7 nm / s, APC-TR (Furuya Metal Co., Ltd.) layer thickness becomes 6.0 nm DC sputtering was performed. The target-substrate distance was 86 mm.
In this way, a transparent conductor 57 was produced.

[Preparation of transparent conductor 58]
Using a polyethylene terephthalate (PET) film as a transparent substrate, an adhesion layer (SiO ₂ ) / first high refractive index layer (ZnS) / first antisulfuration layer (GZO) / transparent metal on the PET film according to the following method Layer (Ag-Bi) / second anti-sulfurization layer (GZO) / second high refractive index layer (GZO ^{* 2} ) / third high refractive index layer (SnO ₂ ) were laminated in this order.

In the transparent conductor 58, the steps of (formation of the adhesion layer (SiO ₂ )) to (formation of the third high refractive index layer (SnO ₂ )), except for the formation of the transparent metal layer, It produced similarly.

(Formation of transparent metal layer (Ag-Bi))
Using Anelva L-430S-FHS, the layer thickness of Ag-Bi (manufactured by Kobelco Research Institute, Inc.) is 6.0 nm at an Ar of 20 sccm, a sputtering pressure of 0.25 Pa, a room temperature, and a formation rate of 0.7 nm / s. DC sputtering was performed. The target-substrate distance was 86 mm.
In this way, a transparent conductor 58 was produced.

<< Evaluation of transparent conductor >>
About each produced said transparent conductor, the following characteristic value was measured and evaluated.
The evaluation method is the same as in Example 1.

As is clear from the results shown in Table 6, it was found that the transparent conductors 50 to 58 of the present invention were excellent in light transmittance, moisture resistance and electrical connectivity.

The present invention is used in the field of various optoelectronic devices such as liquid crystal, plasma, organic electroluminescence, field emission display, touch panel, mobile phone, electronic paper, various solar cells, various electroluminescence dimming elements there is a possibility.

DESCRIPTION OF SYMBOLS 1 Transparent conductor 2, 2-1, 2-2 Transparent substrate 3A 1st high refractive index layer 3B 2nd high refractive index layer 4 Transparent metal layer 5A 1st sulfidation prevention layer 5B 2nd sulfidation prevention layer 7 Resist film 7A Removal Resist film 8 Mask 9 Exposure machine 10 Etching solution 13 Front plate 21 Touch panel a Conduction area b Insulation area EU, EU-1, EU-2 Transparent electrode unit

Claims

A transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order;
The transparent metal layer contains silver as a main component,
The first high refractive index layer and the second high refractive index layer each contain a dielectric material or an oxide semiconductor material;
For light with a wavelength of 570 nm, the refractive index of the first high refractive index layer and the second high refractive index layer is higher than the refractive index of the transparent substrate,
The first high refractive index layer contains a sulfur component, and
The transparent conductor, wherein the second high refractive index layer contains a sulfur component in a range of 0.1 to 10 at%.
The transparent conductor according to claim 1, wherein the sulfur component contained in the first high refractive index layer is derived from zinc sulfide.
The transparent conductor according to claim 1 or 2, wherein the sulfur component contained in the second high refractive index layer is derived from zinc sulfide.
The transparent conductor according to any one of claims 1 to 3, wherein the first high refractive index layer contains silicon dioxide.
The second high refractive index layer is made of titanium (Ti), indium (In), zinc (Zn), cerium (Ce), tungsten (W), gallium (Ga), tin (Sn), hafnium (Hf), zirconium. Containing a metal oxide containing at least one element selected from the group consisting of (Zr), niobium (Nb), tantalum (Ta), aluminum (Al), bismuth (Bi), and germanium (Ge). The transparent conductor according to any one of claims 1 to 4, wherein the transparent conductor is characterized.
6. The sulfidation prevention layer further containing a zinc component is provided between the first high refractive index layer and the transparent metal layer. 6. Transparent conductor.
7. The sulfidation prevention layer further containing a zinc component is provided between the second high refractive index layer and the transparent metal layer. 8. Transparent conductor.
The transparent conductor according to any one of claims 1 to 7, wherein the transparent metal layer is patterned into a predetermined shape.
A touch panel comprising the transparent conductor according to any one of claims 1 to 8.