WO2015053371A1

WO2015053371A1 - Transparent conductor

Info

Publication number: WO2015053371A1
Application number: PCT/JP2014/077094
Authority: WO
Inventors: 一成多田; 仁一粕谷
Original assignee: コニカミノルタ株式会社
Priority date: 2013-10-09
Filing date: 2014-10-09
Publication date: 2015-04-16
Also published as: JPWO2015053371A1

Abstract

The present invention addresses the problem of providing a transparent conductor having high humidity resistance and light transmittance. In order to solve this problem, this transparent conductor is configured so as to include, in this order, a transparent substrate, a first high-refractive-index layer containing a dielectric material or an oxide semiconductor material having a higher index of refraction of light having a wavelength of 570nm than that of the transparent substrate, a transparent metal film, and a second high-refractive-index layer containing a dielectric material or an oxide semiconductor material having a higher index of refraction of light having a wavelength of 570nm than that of the transparent substrate, wherein one or both of the first and second high-refractive-index layers is a zinc-sulfide-containing layer which contains ZnS, and a sulfidation-prevention layer containing a metal oxide, a metal fluoride, a metal nitride or Zn is present between the zinc-sulfide-containing layer and the transparent metal film.

Description

Transparent conductor

The present invention relates to a transparent conductor including a transparent metal film.

In recent years, transparent conductive films have been used for various devices such as electrode materials for display devices such as liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, electrode materials for inorganic and organic EL elements, touch panel materials, and solar cell materials. Has been.

As a material constituting such a transparent conductive film, metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, and Cr, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , and TiO _{2 are used.} , SnO ₂ , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.

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

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

Thus, it has been studied to use a vapor-deposited Ag film as a transparent conductive film (Patent Document 1). In order to increase the light transmittance of the transparent conductor, the Ag film is made of a film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium oxide / zinc oxide), ICO (indium cerium oxide), a- It has also been proposed that the film is sandwiched between GIO (a film made of gallium, indium, and oxygen) (Patent Documents 2 to 4 and Non-Patent Document 3). Further, it has been proposed to sandwich an Ag film between ZnS films (Non-patent Documents 1 and 2).

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

However, as shown in Patent Documents 2 to 4, a transparent conductor in which an Ag film 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 humidity environment, there is a problem that the Ag film is easily corroded.

On the other hand, 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, Ag is sulfided when the Ag layer is formed or the ZnS layer is formed. Is likely to occur. As a result, there is a problem that the light transmittance of the transparent conductor is lowered.

The present invention has been made in view of such a situation. An object of this invention is to provide a transparent conductor with high moisture resistance and light transmittance.

That is, this invention relates to the following transparent conductors.
[1] A transparent substrate, a first high refractive index layer containing a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate, and a transparent metal film And a second high refractive index layer including a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate in this order. And at least one of the first high-refractive index layer and the second high-refractive index layer is a zinc sulfide-containing layer containing ZnS, and the zinc sulfide-containing layer is interposed between the transparent metal film and the transparent metal film. A transparent conductor further comprising an anti-sulfurization layer comprising metal oxide, metal fluoride, metal nitride, or Zn.

[2] The transparent conductor according to [1], wherein the antisulfurization layer contains ZnO.
[3] The transparent conductor according to [1] or [2], wherein the zinc sulfide-containing layer further contains SiO ₂ .
[4] The transparent conductor according to any one of [1] to [3], wherein the transparent metal film is a metal pattern patterned into a predetermined shape.

According to the present invention, a transparent conductor having high moisture resistance and high light transmittance can be obtained.

It is a schematic sectional drawing which shows an example of the laminated constitution of the transparent conductor of this invention. It is a schematic sectional drawing which shows the other example of the laminated constitution of the transparent conductor of this invention. It is a schematic diagram which shows an example of the pattern which consists of a conduction area | region and an insulation area | region of the transparent conductor of this invention. 4 is a graph showing an admittance locus of a wavelength of 570 nm of the transparent conductor produced in Example 1. 3 is a graph showing spectral characteristics of a transparent conductor produced in Example 1. FIG. 4 is a graph showing spectral characteristics of a transparent conductor produced in Example 2. 4 is a graph showing spectral characteristics of a transparent conductor produced in Example 3. 6 is a graph showing spectral characteristics of a transparent conductor produced in Example 4. 10 is a graph showing spectral characteristics of a transparent conductor produced in Example 5. 7 is a graph showing spectral characteristics of a transparent conductor produced in Example 6. 7 is a graph showing spectral characteristics of a transparent conductor produced in Example 7. 6 is a graph showing spectral characteristics of a transparent conductor produced in Example 8. 6 is a graph showing spectral characteristics of a transparent conductor produced in Example 9. 6 is a graph showing spectral characteristics of a transparent conductor produced in Example 10. FIG. 10 is a graph showing spectral characteristics of a transparent conductor produced in Example 11. 14 is a graph showing spectral characteristics of a transparent conductor produced in Example 12. 14 is a graph showing the spectral characteristics of the transparent conductor produced in Example 13. 14 is a graph showing spectral characteristics of the transparent conductor produced in Example 14. 16 is a graph showing spectral characteristics of a transparent conductor produced in Example 15. 10 is a graph showing spectral characteristics of a transparent conductor produced in Example 16. 14 is a graph showing spectral characteristics of a transparent conductor produced in Example 17. 14 is a graph showing spectral characteristics of a transparent conductor produced in Example 18. FIG. 14 is a graph showing spectral characteristics of a transparent conductor produced in Example 19. 5 is a graph showing spectral characteristics of a transparent conductor produced in Comparative Example 1. 10 is a graph showing spectral characteristics of a transparent conductor produced in Comparative Example 3.

Examples of the layer structure of the transparent conductor of the present invention are shown in FIGS. As shown in FIGS. 1 and 2, the transparent conductor 100 of the present invention includes a transparent substrate 1 / first high refractive index layer 2 / transparent metal film 3 / second high refractive index layer 4. In the transparent conductor 100 of the present invention, either one or both of the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers containing ZnS. Between the zinc sulfide-containing

layers

2 and 4 and the transparent metal film 3, an antisulfurization layer 5 (5a and 5b) is included.

Here, when either one of the first high-refractive index layer 2 and the second high-refractive index layer 4 is a zinc sulfide-containing layer, the zinc sulfide-containing

layer

2 or 4 and the transparent metal film 3 are interposed. In addition, an antisulfurization layer 5 is included. On the other hand, when both the first high-refractive index layer 2 and the second high-refractive index layer 4 are zinc sulfide-containing layers, the sulfide is interposed between any one of the zinc sulfide-containing

layers

2 or 4 and the transparent metal film 3. The prevention layer 5 may be included, but from the viewpoint of sufficiently increasing the light transmittance of the transparent conductor 100, the sulfide prevention layer 5 is provided between the zinc sulfide-containing

layers

2 and 4 and the transparent metal film 3, respectively. Is preferably included. That is, it is preferable that the sulfidation preventing layer 5 is included between the first high refractive index layer 2 and the transparent metal film 3 and between the transparent metal film 3 and the second high refractive index layer 4.

As described above, when the transparent metal film and the layer containing ZnS 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 film is formed on a zinc sulfide-containing layer (first high refractive index layer) by a vapor deposition method such as sputtering, unreacted sulfur components in the zinc sulfide-containing layer It is blown out into the film forming atmosphere by the material (metal material). Then, the ejected sulfur component reacts with the metal, and metal sulfide is deposited on the zinc sulfide-containing layer. Further, when the zinc sulfide-containing layer and the transparent metal film are continuously formed, the sulfur component contained in the film formation atmosphere of the zinc sulfide-containing layer remains in the transparent metal film atmosphere. And this sulfur component and a metal react, and a metal sulfide deposits on a zinc sulfide content layer.

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

On the other hand, in the transparent conductor 100 of the present invention, for example, as shown in FIG. 1, the first antisulfurization layer 5 a is laminated on the first high refractive index layer 2. In this configuration, since the first high refractive index layer 2 is protected by the first antisulfurization layer 5a, it is difficult for the sulfur component in the first high refractive index layer 2 to be ejected when the transparent metal film 3 is formed. Further, even if the first high refractive index layer 2 and the transparent metal film 3 are continuously formed, the sulfur component contained in the film formation atmosphere of the first high refractive index layer 2 is not contained in the first sulfurization preventing layer 5a. It reacts with the component and is adsorbed by the component of the first sulfidation prevention layer 5a. Therefore, it is difficult for sulfur to be contained in the film forming atmosphere of the transparent metal film 3, and the generation of metal sulfide is suppressed.

In the transparent conductor 100 of the present invention, for example, as shown in FIG. 1, the second sulfidation preventing layer 5 b is laminated on the transparent metal film 3. In this configuration, since the transparent metal film 3 is protected by the second antisulfurization layer 5b, the metal in the transparent metal film 3 is not easily ejected when the second high refractive index layer 4 is formed. Further, the sulfur component in the film formation atmosphere of the second high refractive index layer 4 is difficult to come into contact with the surface of the transparent metal film 3. Therefore, it is difficult for metal sulfides to be generated on the surface of the transparent metal film 3.

In the transparent conductor 100 of the present invention, the transparent metal film 3 may be laminated on the entire surface of the transparent substrate 1 as shown in FIG. 1, and the transparent metal film 3 is desired as shown in FIG. It may be patterned into a shape. In the transparent conductor 100 of the present invention, the region a where the transparent metal film 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, as shown in FIG. 2, the region b not including the transparent metal film 3 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 100. For example, when the transparent conductor 100 is applied to an electrostatic touch panel, as shown in FIG. 3, the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. sell.

The transparent conductor 100 of the present invention includes layers other than the transparent substrate 1, the first high refractive index layer 2, the transparent metal film 3, the second high refractive index layer 4, and the antisulfurization layer 5. Also good. For example, an underlayer that can be a growth nucleus when forming the transparent metal film 3 may be included between the transparent metal film 3 and the first high refractive index layer 2 adjacent to the transparent metal film 3. However, the layers included in the transparent conductor 100 of the present invention are all layers made of an inorganic material except for the transparent substrate 1. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 4, the laminated body from the transparent substrate 1 to the second high refractive index layer 4 is the transparent conductor 100 of the present invention. .

1. 1. Layer Configuration of Transparent Conductor 1-1) Transparent Substrate The transparent substrate 1 included in the transparent conductor 100 can be the same as the transparent substrate of various display devices. The transparent substrate 1 includes a glass substrate, a cellulose ester resin (for example, triacetylcellulose, diacetylcellulose, acetylpropionylcellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Limited)), a cycloolefin resin (for example, ZEONOR (manufactured by Nippon Zeon), Arton (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resin (eg polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex (manufactured by Sumitomo Chemical)) Polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate), polyethersulfone, ABS / AS resin, MBS resin, polystyrene Emissions, methacrylic resins, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resins), may be a transparent resin film comprising a styrene block copolymer resin. When the transparent substrate 1 is a transparent resin film, the film may contain two or more kinds of resins.

From the viewpoint of transparency, the transparent substrate 1 is a glass substrate, or a cellulose ester resin, a polycarbonate resin, a polyester resin (particularly polyethylene terephthalate), a triacetyl cellulose, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether (PPE) resin, A film made of polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), or styrene block copolymer resin is preferable.

The transparent substrate 1 preferably has high transparency to visible light; the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and 85% or more. More preferably it is. When the average light transmittance of the transparent substrate 1 is 70% or more, the light transmittance of the transparent conductor 100 is likely to be increased. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the transparent substrate 1 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

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

The refractive index of light having a wavelength of 570 nm of the transparent substrate 1 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. . The refractive index of the transparent substrate is usually determined by the material of the transparent substrate. The refractive index of the transparent substrate is measured with an ellipsometer.

The haze value of the transparent substrate 1 is preferably 0.01 to 2.5, more preferably 0.1 to 1.2. When the haze value of the transparent substrate is 2.5 or less, the haze value of the transparent conductor is suppressed. The haze value is measured with a haze meter.

The thickness of the transparent substrate 1 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the transparent substrate is 1 μm or more, the strength of the transparent substrate 1 is increased, and it is difficult to crack or tear the first high refractive index layer 2 during production. On the other hand, when the thickness of the transparent substrate 1 is 20 mm or less, the flexibility of the transparent conductor 100 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductor 100 can be reduced. Moreover, the apparatus using the transparent conductor 100 can also be reduced in weight.

1-2) First High Refractive Index Layer The first high refractive index layer 2 adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor, that is, the region where the transparent metal film 3 is formed. It is a layer and is formed at least in the conduction region a of the transparent conductor 100. The first high refractive index layer 2 may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of making it difficult to visually recognize the pattern formed of the conductive region a and the insulating region b, only the conductive region a. It is preferable to be formed.

The first high refractive index layer 2 includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 described above. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable. On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably larger than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the first high refractive index layer 2. The refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material included in the first high refractive index layer 2 and the density of the material included in the first high refractive index layer 2.

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. Examples of metal oxides include 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 oxide / zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ATO (Sb-doped SnO), ICO (indium cerium oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , IGZO (indium gallium zinc oxide), a-GIO (amorphous oxide composed of gallium, indium and oxygen), etc. It is. The first high refractive index layer 2 may contain only one kind of the metal oxide or two or more kinds.

In addition, the dielectric material or the oxide semiconductor material included in the first high refractive index layer 2 may be ZnS. When ZnS is contained in the first high refractive index layer 2, it becomes difficult for moisture to permeate from the transparent substrate 1 side, and corrosion of the transparent metal film 3 is suppressed. The first high refractive index layer 2 may contain only ZnS or may contain other materials together with ZnS. Materials included with ZnS is a metal oxide or SiO ₂ or the like, which may be the dielectric material or an oxide semiconductor material, particularly preferably SiO _2. When SiO ₂ is contained together with ZnS, the first high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.

When the first high refractive index layer 2 contains other materials together with ZnS, the amount of ZnS is 0.1% by mass or more and 95% by mass with respect to the total number of moles of the material constituting the first high refractive index layer 2. % Is preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. When the ratio of ZnS is high, the sputtering rate is increased, and the deposition rate of the first high refractive index layer 2 is increased. On the other hand, when many components other than ZnS are contained, the amorphousness of the first high refractive index layer 2 is increased, and cracking of the first high refractive index layer 2 is suppressed.

The thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm. When the thickness of the first high refractive index layer 2 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the first high refractive index layer 2. On the other hand, if the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease. The thickness of the first high refractive index layer 2 is measured with an ellipsometer.

The first high refractive index layer 2 can 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. From the viewpoint of increasing the refractive index (density) of the first high refractive index layer 2, the first high refractive index layer 2 is preferably a layer formed by an electron beam evaporation method or a sputtering method. In the case of the electron beam evaporation method, it is desirable to have assistance such as IAD (ion assist) in order to increase the film density.

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

1-3) First anti-sulfurization layer ZnS is contained in the first high-refractive index layer; that is, when the first high-refractive index layer 2 is a zinc sulfide-containing layer, as shown in FIG. It is preferable that the first sulfidation preventing layer 5 a is included between the high refractive index layer 2 and the transparent metal film 3. The first sulfidation preventing layer 5a may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a is formed. Preferably it is formed.

The first sulfidation preventing layer 5a may be a metal oxide, metal nitride, metal fluoride or the like, or a layer containing Zn. Only one of these may be included in the first sulfurization prevention layer 5a, or two or more thereof may be included. However, when the first high-refractive index layer 2, the first antisulfurization layer 5a, and the transparent metal film 3 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. Preferably. In the case where the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Examples of metal oxides include 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 , In ₂ O ₃ , IGZO 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. Among these, it is preferable that ZnO capable of adsorbing sulfur is contained.

Here, the thickness of the first sulfidation preventing layer 5a is preferably a thickness capable of protecting the surface of the first high refractive index layer 2 from an impact during the formation of the transparent metal film 3 described later. On the other hand, ZnS that can be contained in the first high refractive index layer 2 has high affinity with the metal contained in the transparent metal film 3. Therefore, if the thickness of the first sulfidation preventing layer 5a is very thin and a part of the first high refractive index layer 2 is slightly exposed, a transparent metal film grows around the exposed part, and the transparent metal film 3 tends to be dense. That is, the first sulfidation preventing layer 5a is preferably relatively thin, preferably 0.1 nm to 10 nm, more preferably 0.5 nm to 5 nm, and further preferably 1 nm to 3 nm. The thickness of the first sulfurization preventing layer 5a is measured with an ellipsometer.

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

1-4) Transparent Metal Film The transparent metal film 3 is a film for conducting electricity in the transparent conductor 100. The transparent metal film 3 may be formed on the entire surface of the transparent substrate 1 as described above, or may be patterned into a desired shape.

The metal contained in the transparent metal film 3 is not particularly limited as long as it is a highly conductive metal, and may be, for example, silver, copper, gold, platinum group, titanium, chromium, or the like. The transparent metal film 3 may contain only one kind of these metals or two or more kinds. From the viewpoint of high conductivity, the transparent metal film is preferably made of silver or an alloy containing 90 at% or more of silver. The metal combined with silver can be zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, and the like. For example, when silver and zinc are combined, the sulfidation resistance of the transparent metal film is enhanced. 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 film 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 nm to 800 nm, more preferably 7% or less, and further preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 nm to 800 nm, the transmitted light of the conductive region a of the transparent conductor 100 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 nm to 800 nm of the transparent metal film 3 is measured by the following procedure.
(I) A platinum palladium film is formed to a thickness of 0.1 nm on a glass substrate using a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the film forming speed and the like of the manufacturer's nominal value of the sputtering apparatus. Thereafter, a film made of metal is formed to a thickness of 20 nm on the substrate to which platinum palladium is adhered by sputtering.

(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 transmittance and reflectance of the metal film are measured. Then, from the transmittance and reflectance at each wavelength, absorption rate = 100− (transmittance + reflectance) is calculated and used as reference data. The transmittance and reflectance are measured with a spectrophotometer.

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

The thickness of the transparent metal film 3 is 10 nm or less, preferably 3 to 9 nm, and more preferably 5 to 8 nm. In the transparent conductor 100 of the present invention, since the transparent metal film 3 has a thickness of 10 nm or less, the metal reflection is hardly generated in the transparent metal film 3. Furthermore, when the thickness of the transparent metal film 3 is 10 nm or less, the optical admittance of the transparent conductor 100 is easily adjusted by the first high-refractive index layer 2 and the second high-refractive index layer 4, so Light reflection is easily suppressed. The thickness of the transparent metal film 3 is measured with an ellipsometer.

The transparent metal film 3 can be a film formed by any film forming method, but in order to increase the average transmittance of the transparent metal film, a film formed by a sputtering method; or an underlayer described later It is preferable that the film is formed in the same manner.

In the sputtering method, since the material collides with the deposition target at high speed during film formation, a dense and smooth film is easily obtained; the light transmittance of the transparent metal film 3 is likely to increase. Moreover, when the transparent metal film 3 is a film formed by sputtering, the transparent metal film 3 is hardly corroded even in an environment of high temperature and low humidity. The type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like. The transparent metal film 3 is particularly preferably a film formed by a counter sputtering method. When the transparent metal film 3 is a film formed by the facing sputtering method, the transparent metal film 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent metal film 3 becomes lower and the light transmittance is likely to increase.

On the other hand, when the transparent metal film 3 is a film formed on an underlayer described later, the underlayer becomes a growth nucleus when the transparent metal film 3 is formed, so that the transparent metal film 3 tends to be a smooth film. . As a result, even if the transparent metal film 3 is thin, plasmon absorption hardly occurs. In this case, the method for forming the transparent metal film 3 is not particularly limited, and may be 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.

Further, when the transparent metal film 3 is a film patterned into a desired shape, the patterning method is not particularly limited. The transparent metal film 3 may be, for example, a film formed by arranging a mask having a desired pattern; it may be a film patterned by a known etching method.

1-5) Second anti-sulfurization layer When the second high-refractive index layer to be described later is a zinc sulfide-containing layer, as shown in FIG. 1, between the transparent metal film 3 and the second high-refractive index layer 4 It is preferable that the second sulfidation preventing layer 5b is included. The second sulfidation preventing layer 5b may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a. Preferably it is formed.

The second antisulfurization layer 5b is a layer containing metal oxide, metal nitride, metal fluoride or the like or Zn. Only one of these may be included in the second sulfidation preventing layer 5b, or two or more thereof may be included. The metal oxide, metal nitride, and metal fluoride can be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2 described above.

On the other hand, the thickness of the second sulfidation preventing layer 5b is preferably a thickness capable of protecting the surface of the transparent metal film 3 from an impact during film formation of the second high refractive index layer 4 described later. On the other hand, the metal contained in the transparent metal film 3 and the ZnS contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second sulfidation preventing layer 5b is very thin and a part of the transparent metal film 3 is slightly exposed, the transparent metal film 3 or the second sulfidation preventing layer 5b and the second high refractive index layer 4 are exposed. Adhesiveness is likely to increase. Accordingly, the specific thickness of the second antisulfurization layer 5b is preferably 0.1 nm to 10 nm, more preferably 0.5 nm to 5 nm, and further preferably 1 nm to 3 nm. The thickness of the second sulfidation preventing layer 5b is measured with an ellipsometer.

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

When the second sulfidation preventing layer 5b is a layer patterned into a desired shape, the patterning method is not particularly limited. The second sulfidation preventing layer 5b may be, for example, a layer formed in a pattern by a vapor deposition method by disposing a mask having a desired pattern on the film formation surface; It may be a layer patterned by a method.

1-6) Second High Refractive Index Layer The second high refractive index layer 4 adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor 100, that is, the region where the transparent metal film 3 is formed. And is formed at least in the conduction region a of the transparent conductor 100. The second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductor 100, but is formed only in the conductive region a from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b. It is preferable that

The second high refractive index layer 4 includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate 1 described above. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable. On the other hand, the specific refractive index of light with a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the second high refractive index layer 4 is preferably greater than 1.5, and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. The refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material included in the second high refractive index layer 4 and the density of the material included in the second high refractive index layer 4.

The dielectric material or oxide semiconductor material contained in the second high refractive index layer 4 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. The metal oxide can be the same as the metal oxide contained in the first high refractive index layer 2. The second high refractive index layer 4 may contain only one kind of the metal oxide or two or more kinds.

Further, the dielectric material or the oxide semiconductor material included in the second high refractive index layer 4 may be ZnS. When ZnS is contained in the second high refractive index layer 4, it becomes difficult for moisture to permeate from the second high refractive index layer 4 side, and corrosion of the transparent metal film 3 is suppressed. The second high refractive index layer 4 may contain only ZnS or may contain other materials together with ZnS. The material contained together with ZnS is a metal oxide that can be the dielectric material or the oxide semiconductor material, or SiO ₂ , and particularly preferably SiO ₂ . When SiO ₂ is contained together with ZnS, the second high refractive index layer 4 tends to be amorphous, and the flexibility of the transparent conductor is likely to increase.

When the second high refractive index layer 4 contains other materials together with ZnS, the amount of ZnS is 0.1% by mass or more and 95% by mass with respect to the total number of moles of components constituting the second high refractive index layer 4. % Is preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. When the ratio of ZnS is high, the sputtering rate is increased, and the deposition rate of the second high refractive index layer 4 is increased. On the other hand, when the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.

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

The film formation method of the second high refractive index layer 4 is not particularly limited, and is 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. Layer. From the viewpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a film formed by sputtering.

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

1-7) Underlayer As described above, the transparent conductor 100 may include an underlayer serving as a growth nucleus when the transparent metal film 3 is formed. The underlayer is a layer formed on the transparent substrate 1 side and adjacent to the transparent metal film 3 from the transparent metal film 3; that is, between the first high refractive index layer 2 and the transparent metal film 3, or the first sulfide. It may be a layer formed between the prevention layer 5 a and the transparent metal film 3. The underlayer is preferably formed at least in the conductive region a of the transparent conductor, and may be formed in the insulating region b of the transparent conductor 100.

If the transparent conductor 100 includes a base layer, the smoothness of the surface of the transparent metal film 3 is enhanced even if the transparent metal film 3 is thin. The reason is as follows.

When the material of the transparent metal film 3 is deposited on, for example, the first high refractive index layer 2 by a general vapor deposition method, atoms attached to the first high refractive index layer 2 are initially deposited. Migrate (move), and atoms gather together to form a lump (island structure). And a film grows clinging to this lump. Therefore, in the film at the initial stage of film formation, there is a gap between the lumps and it is not conductive. When a lump further grows from this state, a part of the lump is connected and barely conducted. However, since there is still a gap between the lumps, plasmon absorption occurs. As the film formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the intrinsic reflection of the metal occurs, and the light transmittance of the film decreases.

On the other hand, when a base layer made of a metal that is difficult to migrate is formed on the first high refractive index layer 2, the transparent metal film 3 grows using the base layer as a growth nucleus. That is, the material of the transparent metal film 3 is difficult to migrate, and the film grows without forming the island-like structure described above. As a result, it becomes easy to obtain a smooth transparent metal film 3 even if the thickness is small.

Here, the base layer contains palladium, molybdenum, zinc, germanium, niobium, or indium; or an alloy of these metals with other metals, or an oxide or sulfide of these metals (for example, ZnS). Is preferred. The underlayer may contain only one kind, or two or more kinds.

The amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When the metal is contained in the base layer in an amount of 20% by mass or more, the affinity between the base layer and the transparent metal film 3 is increased, and the adhesion between the base layer and the transparent metal film 3 is likely to be increased. It is particularly preferable that the underlayer contains palladium or molybdenum.

On the other hand, the metal that forms an alloy with palladium, molybdenum, zinc, germanium, niobium, or indium is not particularly limited, but may be a platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, chromium, or the like.

The thickness of the underlayer is 3 nm or less, preferably 0.5 nm or less, and more preferably a monoatomic film. The underlayer can also be a film in which metal atoms adhere to the transparent substrate 1 with a distance therebetween. When the adhesion amount of the underlayer is 3 nm or less, the underlayer hardly affects the light transmission property and optical admittance of the transparent conductor 100. The presence or absence of the underlayer is confirmed by the ICP-MS method. Further, the thickness of the underlayer is calculated from the product of the film formation speed and the film formation time.

The underlayer can be a layer formed by sputtering or vapor deposition. Examples of the sputtering method include an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, and a bias sputtering method. The sputtering time during the underlayer film formation is appropriately selected according to the desired average thickness of the underlayer and the film formation speed. The sputter deposition rate is preferably from 0.1 to 15 Å / second, more preferably from 0.1 to 7 秒 / second.

On the other hand, examples of the vapor deposition method include vacuum vapor deposition method, electron beam vapor deposition method, ion plating method, ion beam vapor deposition method and the like. The deposition time is appropriately selected according to the desired thickness of the underlayer and the film formation rate. The deposition rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

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

1-8) Low Refractive Index Layer As described above, in the transparent conductor 100 of the present invention, the light transmittance (optical admittance) of the conductive region a of the transparent conductor is adjusted on the second high refractive index layer 4. A low refractive index layer (not shown) may be included. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

In the low refractive index layer, the refractive index of light having a wavelength of 570 nm is more 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 2 and the second high refractive index layer 4. A dielectric material or an oxide semiconductor material having a low rate is included. The refractive index of the light of wavelength 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 material contained in the first high refractive index layer 2 and the second high refractive index layer 4. The refractive index is preferably 0.2 or more lower and more preferably 0.4 or more lower.

The specific 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 preferably less than 1.8, more preferably 1.30 to 1.6, Particularly preferred is 1.35 to 1.5. The refractive index of the low refractive index layer is mainly adjusted by the refractive index of the material included in the low refractive index layer and the density of the material included in the low refractive index layer.

The dielectric material or oxide semiconductor material contained in the low refractive index layer is MgF ₂ , SiO ₂ , AlF ₃ , CaF ₂ , CeF ₃ , CdF ₃ , LaF ₃ , LiF, NaF, Nad, NdF ₃ , YF ₃ , YbF _3. , Ga ₂ O ₃ , LaAlO ₃ , Na ₃ AlF ₆ , Al ₂ O ₃ , MgO, and ThO ₂ . Dielectric material or an oxide semiconductor material is inter _alia, is _{_{_{_{MgF 2, SiO 2, CaF 2}}}} , CeF 3, LaF 3, LiF, NaF, NdF 3, Na 3 AlF 6, Al 2 O 3, MgO or ThO _2, In view of low refractive index, MgF ₂ and SiO ₂ are particularly preferable. Only one of these materials may be included in the low refractive index layer, or two or more of these materials may be included.

The thickness of the low refractive index layer is preferably 10 to 150 nm, more preferably 20 to 100 nm. When the thickness of the low refractive index layer is 10 nm or more, the optical admittance on the surface of the transparent conductor is easily finely adjusted. On the other hand, if the thickness of the low refractive index layer is 150 nm or less, the thickness of the transparent conductor is reduced. The thickness of the low refractive index layer is measured with an ellipsometer.

The low refractive index 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. From the viewpoint of easiness of film formation, the low refractive index layer is preferably a layer formed by electron beam evaporation or sputtering.

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

1-9) Third High Refractive Index Layer As described above, in the transparent conductor 100 of the present invention, the light transmittance (optical admittance) of the conductive region a of the transparent conductor is further adjusted on the low refractive index layer. A third high refractive index layer may be included. The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

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 1 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 100 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 of the material included in the third high refractive index layer and the density of the material included in the third high refractive index layer.

The dielectric material or oxide semiconductor material included in the third high refractive index layer may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material is preferably a metal oxide or ZnS. Examples of the metal oxide include the metal oxide contained in the first high refractive index layer 2 or the second high refractive index layer 4 described above. The third high refractive index layer may contain only one kind of the metal oxide or ZnS, and may contain two or more kinds. Further, a dielectric material such as SiO ₂ may be included together with the metal oxide and ZnS.

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 100 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 2 and the second high refractive index layer 4.

2. About the optical admittance of the transparent conductor The reflectance R of the surface of the conductive area a of the transparent conductor (the surface opposite to the transparent substrate in the transparent conductor) is determined by the optical admittance Y _{env of the} medium on which light is incident and the transparent conductor determined from the equivalent admittance Y _E of the surface of the conductive region a of the body. Here, the medium on which the light is incident refers to a member or environment through which light incident on the transparent conductor passes immediately before the incident; a member or environment made of an organic resin. The relationship between the optical admittance Y _{env of the} medium on which light is incident and the equivalent admittance Y _E of the surface of the transparent conductor is expressed by the following equation.

Based on the above formula, the closer the value | Y _env −Y _E | is to 0, the lower the reflectance R of the surface of the transparent conductor (conduction region a).

The optical admittance Y _{env of the} medium is obtained from the ratio (H / E) of the electric field strength and the magnetic field strength, and is usually the same as the refractive index n _{env of the} medium. On the other hand, the equivalent admittance Y _E of the surface of the conductive region a of the transparent conductor is determined from the optical admittance Y of the layers constituting the conductive region a. For example, when the transparent conductor (conductive region a) is composed of one is equivalent admittance Y _E of the transparent conductor is equal to the of the layer optical admittance Y (refractive index).

On the other hand, when the transparent conductor (conducting region a) is a laminate, the optical admittance Y _x (E _x H _x ) of the laminate from the first layer to the x-th layer is from the first layer to (x−1) It is represented by the product of the optical admittance Y _x-1 (E _x-1 H _x-1 ) of the laminate up to the layer and a specific matrix; specifically, the following formula (1) or formula (2) Is required.

When the x-th layer is a layer made of a dielectric material or an oxide semiconductor material

・ When the xth layer is an ideal metal layer

When the x-th layer is the outermost layer, the optical admittance Y _x (E _x H _x ) of the laminate from the transparent substrate to the outermost layer becomes the equivalent admittance Y _E of the transparent conductor.

FIG. 4A shows a transparent conductor (transparent substrate / first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (ITO) / transparent metal film (Ag) / second high refraction of Example 1 described later. shows the admittance locus of wavelength 570nm conductive region a rate layer (ZnS-SiO ₂₎ a transparent conductor comprising a). The horizontal axis of the graph is the real part when the optical admittance Y of the region is represented by x + iy; that is, x in the equation, and the vertical axis is the imaginary part of the optical admittance; that is, y in the equation. In the transparent conductor of Example 1, the first sulfidation prevention layer (ITO) is sufficiently thin, so that its optical admittance can be ignored.

In Figure 4A, the final coordinates of the admittance locus is equivalent admittance Y _E conductive region a. The distance between the coordinate (x _E , y _E ) of the equivalent admittance Y _E and the admittance coordinate Y _env (n _env , 0) (not shown) of the medium on which the light is incident is determined by the conduction region a of the transparent conductor. It is proportional to the surface reflectance R.

Here, in the transparent conductor of the present invention, the optical admittance at a wavelength of 570 nm on the surface of the transparent metal film on the high refractive index layer side is Y1 (= x ₁ + ii ₁ ), and the wavelength on the surface of the transparent metal film on the intermediate layer side When the optical admittance at 570 nm is Y2 (= x ₂ + iy ₂ ), it is preferable that one or both of x ₁ and x ₂ is 1.6 or more. either one of x ₁ and x ₂ are, it tends enhanced light transmission of the transparent conductor If it is 1.6 or more. The reason will be described below.

The following relational expression is established between the admittance Y at the interface between the layers constituting the transparent conductor and the electric field strength E existing in each layer.

Based on the above relational expression, if the real part (x ₁ and x ₂ ) of the optical admittances Y1 and Y2 on the surface of the transparent metal film increases, the electric field strength E of the transparent metal film decreases and the electric field loss (light absorption). Is suppressed. That is, the light transmittance of the transparent conductor is sufficiently increased.

Accordingly, either one or both of x ₁ and x ₂ are preferably 1.6 or more, more preferably 1.8 or more, and further preferably 2.0 or more. Any one of x ₁ and x ₂ may be 1.6 or more, but x ₁ is particularly preferably 1.6 or more. The _{x 1} and _{x 2} is preferably 7.0 or less, more preferably 5.5 or less. x ₁ is the refractive index of the first high refractive index layer and is adjusted in such a thickness of the first high refractive index layer. x ₂ is the refractive index of the values and the transparent metal film x _1, is adjusted by the thickness or the like of the first transparent metal film. For example, if and refractive index of the first high refractive index layer is high, when the thickness of the first high refractive index layer is somewhat thicker, the value of x ₁ and x ₂ tends to increase. The absolute value (| x ₁ −x ₂ |) of the difference between x ₁ and x ₂ is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.8 or less. is there.

In addition, the admittance locus at a specific wavelength (570 nm in the present invention) is preferably line symmetric with respect to the horizontal axis of the graph. Admittance locus and is centered symmetrically on the horizontal axis of the graph, the coordinates of the equivalent admittance Y _E is at a wavelength other than the specific wavelength (e.g. 450nm or 700 nm), likely to be constant, at any wavelength, reflectance R becomes smaller. Therefore, a coordinate _{y 1} of the imaginary part of the Y1, the coordinate _{y 2} of the imaginary part of the Y2, it is preferable to satisfy the _{y 1} × _{y 2} ≦ 0. Furthermore, | y ₁ + y ₂ | is preferably less than 0.8, more preferably 0.5 or less, and still more preferably 0.3 or less.

Furthermore, it is preferable that the aforementioned y ₁ is sufficiently large. As described above, the optical admittance of the transparent metal film has a large imaginary part value, and the admittance locus greatly moves in the vertical axis (imaginary part) direction. Therefore, if y ₁ is sufficiently large, the absolute value of the imaginary part of the admittance coordinates is likely to be within an appropriate range, and the admittance locus is likely to be line symmetric. y ₁ is preferably 0.2 or more, more preferably 0.3 to 1.5, and still more preferably 0.3 to 1.0. On the other hand, y ₂ described above is preferably −0.3 to −2.0, and more preferably −0.6 to −1.5.

On the other hand, the equivalent admittance coordinates (x _E , y _E ) of light having a wavelength of 570 nm in the conduction region a and the light of wavelength 570 nm in the member or environment (medium) in contact with the surface on the second high refractive index layer side of the transparent conductor. Distance from equivalent admittance coordinates (n _env , 0) ((x _E −n _env ) ² + (y _E ) ² ) ^0.5 is preferably less than 0.5, more preferably 0.3 or less It is. When the distance is less than 0.5, the reflectance Ra of the surface of the conduction region _a is sufficiently small, and the light transmittance of the conduction region a is increased.

Further, when the transparent metal film 3 is patterned, an equivalent admittance coordinate (x _E , y _E ) of light with a wavelength of 570 nm in the conduction region a and an equivalent admittance coordinate (( x ( _b , y _b )), ((x _E −x _b ) ² + (y _E −y _b ) ² ) ^0.5 is preferably less than 0.5, more preferably 0 .3 or less. The coordinates of the equivalent admittance Y _E conductive region a, the coordinate of the equivalent admittance Y _b of the insulating region b is sufficiently close, so these patterns are hardly visually recognized. Furthermore, it is preferable that | (x _env −x _b ) ² + (y _env −y _b ) ² − (x _env −x _E ) ² + (y _env −y _E ) ² | . If the said value is satisfy | filled, both the conduction | electrical_connection area | region a and the insulation area | region b will become difficult to visually recognize.

3. Regarding the physical properties of the transparent conductor The average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductor of the present invention is preferably 83% or more, more preferably 85% in both the conduction region a and the insulation region b. Or more, more preferably 88% or more. When the average transmittance in the above wavelength range is 83% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor is preferably 80% or more in both the conduction region a and the insulation region b, more preferably 83% or more, and still more preferably 85%. That's it. When the average transmittance of light having a wavelength of 400 to 1000 nm is 80% or more, the transparent conductor is also applied to applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. can do.

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

The average transmittance, average reflectance, and average reflectance are preferably the average transmittance, average reflectance, and average reflectance under the usage environment of the transparent conductor. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to measure the average transmittance and the average 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 transmittance and the average reflectance in the air. The transmittance and the 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 absorptance is calculated from a calculation formula of 100− (transmittance + reflectance).

In addition, when the conductive region a and the insulating region b are included in the transparent conductor 100, 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).

In addition, when the transparent conductor 100 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 electric resistance of the conductive region a of the transparent conductor is preferably 50Ω / □ or less, 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 electric resistance value of the conduction region a is adjusted by the thickness of the transparent metal film. 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.

4). Applications of transparent conductors The above-mentioned transparent conductors include various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescent dimming elements, etc. It can be preferably used for a substrate of an optoelectronic device.

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, as described above, it is preferable that the equivalent admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the adhesive layer approximate each other. Thereby, reflection at the interface between the transparent conductor and the adhesive layer is suppressed.

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.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this.

[Example 1]
On a film made of cycloolefin polymer, the following method is used to form a first high refractive index layer (ZnS-SiO ₂ ) / first antisulfurization layer (ITO) / transparent metal film (Ag) / second high refractive index layer ( ITO) was sequentially laminated by the following method. Thereafter, the laminate was patterned by the following method. The thickness of each layer is described in J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer. However, the average thickness of the underlayer was calculated from the film formation rate at the nominal value of the manufacturer of the sputtering apparatus. FIG. 4A shows the admittance locus of the obtained transparent conductor at a wavelength of 570 nm, and FIG. 4B shows the spectral characteristics of the conduction region of the transparent conductor.

(First high refractive index layer (ZnS—SiO ₂ ))
On the transparent substrate, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS—SiO ₂ at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 3.0 Å / s. Was RF sputtered. The target-substrate distance was 90 mm.
The ratio (molar ratio) between ZnS and SiO ₂ was 80:20, and the refractive index of the first high refractive index layer was 2.14.

(First anti-sulfurization layer (ITO))
On the first high refractive index layer, L-430S-FHS manufactured by Anelva Co., Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 150 W, film formation rate 2.0 レート / s The ITO was DC sputtered. The target-substrate distance was 86 mm.

(Transparent metal film (Ag))
Using a counter sputtering machine manufactured by FTS Corporation, Ag was counter sputtered at an Ar of 20 sccm, a sputtering pressure of 0.5 Pa, a room temperature, a target power of 150 W, and a film formation rate of 14 K / s. The target-substrate distance was 90 mm.

(Second high refractive index layer (ITO))
On the transparent metal film, L-430S-FHS manufactured by Anerva Co., Ltd. was used. Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 150 W, film formation rate 2.0 Å / s. DC sputtered. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of ITO was 2.12, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.12.

(Layer patterning)
A resist layer is formed into a pattern on the obtained laminate, and the first high-refractive index layer, the first antisulfurization layer, the transparent metal film, and the second high-refractive index layer are formed as shown in FIG. The pattern was formed with an ITO etching solution (manufactured by Hayashi Junyaku Co., Ltd.) in a shape including a conductive region a and a line-shaped insulating region b separating the conductive region a. Only the transparent substrate was included in the insulating region. The width of the line-shaped insulating region b was 16 μm.

[Example 2]
On the Konica Minolta TAC film, the first high refractive index layer (ZnS-SiO ₂ ) / first antisulfuration layer (IGZO) / transparent metal film (Ag-Bi) / second high refractive index layer (IGZO) in this order. Laminated.
The first high refractive index layer (ZnS—SiO ₂ ) was formed in the same manner as in Example 1.
The first sulfurization prevention layer and the second high refractive index layer (IGZO) were formed by the following method.
The transparent metal film (Ag—Bi) was formed in the same manner as in Example 1 except that the target at the time of film formation was an Ag alloy (manufactured by Kobelco).
The obtained laminate was patterned in the same manner as in Example 1. FIG. 5 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

(First antisulfurization layer and second high refractive index layer (IGZO))
Using Anelva L-430S-FHS, IGZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of IGZO was 2.09, and the refractive index of light with a wavelength of 570 nm of the first antisulfurization layer and the second high refractive index layer was also 2.09.

[Example 3]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), a first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (Ga ₂ O ₃ ) / transparent metal film (Ag—Nd—) Bi—Au) / second high refractive index layer (Ga ₂ O ₃ ) was laminated in this order.
The first high refractive index layer (ZnS—SiO ₂ ) was formed in the same manner as in Example 1.
The first sulfurization prevention layer and the second high refractive index layer (Ga ₂ O ₃ ) were formed by the following method.
The transparent metal film (Ag—Nd—Bi—Au) was formed in the same manner as in Example 1 except that the target during film formation was an Ag alloy (manufactured by Kobelco).
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First sulfurization prevention layer and second high refractive index layer (Ga ₂ O ₃ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ga ₂ O ₃ was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of Ga ₂ O ₃ was 1.95, and the refractive index of light with a wavelength of 570 nm of the first antisulfurization layer and the second high refractive index layer was also 1.95.

[Example 4]
A first high refractive index layer (ZnS) / first antisulfurization layer (ZnO) / transparent metal film (APC-TR alloy) / second high refractive index layer (ITO) were laminated in this order on a transparent substrate made of polycarbonate. .
The first high refractive index layer (ZnS) was formed by the following method.
The first sulfurization prevention layer (ZnO) was formed by the following method.
The transparent metal film (APC-TR alloy) was formed by the same method as in Example 1 except that the target at the time of film formation was an Ag alloy (manufactured by Furuya Metal Co., Ltd.).
The second high refractive index layer (ITO) was formed in the same manner as the second high refractive index layer of Example 1.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 7 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

(First high refractive index layer (ZnS))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS was RF-sputtered at Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of ZnS was 2.37, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.37.

(First antisulfurization layer (ZnO))
Using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnO was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / s. The target-substrate distance was 90 mm.

[Example 5]
On the TAC film (transparent substrate) manufactured by Konica Minolta, the first high refractive index layer (ZnS) / first antisulfuration layer (Nb ₂ O ₅ ) / underlayer (Pd) / transparent metal film (Ag) / second high A refractive index layer (Nb ₂ O ₅ ) was laminated in order.
The first high refractive index layer (ZnS) was formed in the same manner as in Example 4.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The first sulfurization prevention layer and the second high refractive index layer (Nb ₂ O ₅ ) were formed by the following method.
The underlayer (Pd) was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First sulfurization prevention layer and second high refractive index layer (Nb ₂ O ₅ ))
Nb ₂ O ₅ was DC sputtered at 20 sccm Ar, 1 sccm O ₂ , sputtering pressure 0.5 Pa, room temperature, target side power 150 W, deposition rate 1.2 Å / s using L-430S-FHS manufactured by Anerva. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of Nb ₂ O ₅ was 2.31, and the refractive indexes of light with a wavelength of 570 nm of the first antisulfurization layer and the second high refractive index layer were also 2.31.

(Underlayer (Pd))
Using a magnetron sputtering apparatus (MSP-1S) manufactured by Vacuum Device Inc., palladium was deposited for 0.2 seconds to form an underlayer with an average thickness of 0.1 nm.

[Example 6]
A first high refractive index layer (ZnS) / first antisulfurization layer (SnO ₂ ) / transparent metal film (Ag) / second high refractive index layer (SnO ₂ ) are laminated in this order on a transparent substrate made of a cycloolefin polymer. did.
The first high refractive index layer (ZnS) was formed in the same manner as the first high refractive index layer of Example 4.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The first sulfurization prevention layer and the second high refractive index layer (SnO ₂ ) were formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First antisulfurization layer and second high refractive index layer (SnO ₂ ))
Using Anelva L-430S-FHS, SnO ₂ was RF-sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of SnO ₂ was 2.0, and the refractive index of light with a wavelength of 570 nm of the first antisulfurization layer and the second high refractive index layer was also 2.0.

[Example 7]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), a first high refractive index layer (ZnS) / first antisulfuration layer (ZnO) / transparent metal film (Ag) / second high refractive index layer ( TiO ₂ ) was laminated in order.
The first high refractive index layer (ZnS) and the first antisulfurization layer (ZnO) were formed in the same manner as the first high refractive index layer and the first antisulfurization layer of Example 4, respectively.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The second high refractive index layer (TiO ₂ ) was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(Second high refractive index layer (TiO ₂ ))
The Optorun's Gener 1300, 320 mA, the TiO ₂ at a deposition rate of 3 Å / s, and electron beam (EB) vapor deposition with ion assist. The ion beam was irradiated at a current of 500 mA, a voltage of 500 V, and an acceleration voltage of 400 V. In the ion beam apparatus, O ₂ gas: 50 sccm and Ar gas: 8 sccm were introduced. The refractive index of light with a wavelength of 570 nm of TiO ₂ was 2.35, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.35.

[Example 8]
On Konica Minolta TAC film (transparent substrate), first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (ITO) / transparent metal film (Ag—Nd—Bi—Au alloy) / second An antisulfurization layer (ITO) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order.
The first high refractive index layer and the second high refractive index layer (ZnS—SiO ₂ ) were formed in the same manner as the first high refractive index layer of Example 1.
The first sulfidation prevention layer and the second sulfidation prevention layer (ITO) were formed in the same manner as the first sulfidation prevention layer of Example 1.
A transparent metal film (Ag—Nd—Bi—Au alloy) was formed in the same manner as in Example 3.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 11 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

[Example 9]
On a Konica Minolta TAC film (transparent substrate), a first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (ZnO) / underlayer (Pd) / transparent metal film (Ag—Nd—Bi—) Au alloy) / second anti-sulfurization layer (ZnO) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order.
The first high refractive index layer and the second high refractive index layer (ZnS—SiO ₂ ) were formed in the same manner as the first high refractive index layer of Example 1.
The first sulfidation prevention layer and the second sulfidation prevention layer (ZnO) were formed in the same manner as the first sulfidation prevention layer of Example 4.
The underlayer (Pd) was formed in the same manner as the underlayer of Example 5.
A transparent metal film (Ag—Nd—Bi—Au alloy) was formed in the same manner as in Example 3.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

[Example 10]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (IGZO) / transparent metal film (Ag) / second antisulfurization Layer (IGZO) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order.
The first high refractive index layer, the second high refractive index layer (ZnS—SiO ₂ ), and the transparent metal film (Ag) were formed in the same manner as the first high refractive index layer and the transparent metal film in Example 1, respectively.
The first sulfidation prevention layer and the second sulfidation prevention layer (IGZO) were formed in the same manner as the first sulfidation prevention layer of Example 2.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

[Example 11]
On a transparent substrate made of glass, a first high refractive index layer (ZnS) / first antisulfurization layer (ZnO) / transparent metal film (Ag) / second antisulfuration layer (IZO) / second high refractive index layer ( ZnS) were stacked in order.
The first high refractive index layer and the second high refractive index layer (ZnS) were formed in the same manner as the first high refractive index layer of Example 4.
The first antisulfurization layer (ZnO) was formed in the same manner as the first antisulfurization layer of Example 4.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The second antisulfurization layer (IZO) was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 14 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

(Second anti-sulfurization layer (IZO))
Using an Anelva L-430S-FHS, IZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm.

[Example 12]
On the transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), the first high refractive index layer (ZnS) / first antisulfuration layer (ZnO) / transparent metal film (Ag) / second antisulfuration layer (ZnO) ) / Second high refractive index layer (ZnS) / low refractive index layer (SiO ₂ ) / third high refractive index layer (ZnS).
The first high refractive index layer, the second high refractive index layer, the third high refractive index layer (ZnS), the first antisulfurization layer, and the second antisulfation layer (ZnO) The rate layer and the first antisulfurization layer were formed in the same manner.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The low refractive index layer (SiO ₂ ) was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(Low refractive index layer (SiO ₂ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., SiO ₂ was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 300 W, and deposition rate 1.6 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of SiO ₂ was 1.46, and the refractive index of light with a wavelength of 570 nm of the low refractive index layer was also 1.46.

[Example 13]
On a transparent substrate made of glass, a first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / second antisulfurization layer (ITO) / second high refractive index layer (ZnS—SiO 2) ₂ ) were laminated in order.
The first high refractive index layer and the second high refractive index layer (ZnS—SiO ₂ ) were formed in the same manner as the first high refractive index layer of Example 1.
A transparent metal film (APC-TR alloy) was formed in the same manner as in Example 4.
The second antisulfation layer (ITO) was formed in the same manner as the first antisulfation layer of Example 1.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 16 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

[Example 14]
On a Konica Minolta TAC film (transparent substrate), a first high refractive index layer (ZnS-SiO ₂ ) / transparent metal film (APC alloy) / second antisulfuration layer (ZnO) / second high refractive index layer (ZnS -SiO ₂ ) were sequentially laminated.
The first high refractive index layer and the second high refractive index layer (ZnS—SiO ₂ ) were formed in the same manner as in Example 1.
The transparent metal film (APC alloy) was formed by the same method as in Example 1 except that the target at the time of film formation was an Ag alloy (manufactured by Furuya Metal Co., Ltd.).
The second antisulfurization layer (ZnO) was formed in the same manner as the first antisulfurization layer of Example 4.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 17 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

[Example 15]
On a transparent substrate made of glass, a first high refractive index layer (ZnS) / transparent metal film (Ag) / second antisulfurization layer (GZO) / second high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer and the second high refractive index layer (ZnS) were formed in the same manner as the first high refractive index layer of Example 4.
The transparent metal film (Ag) was formed in the same manner as in Example 1.
The second antisulfurization layer (GZO) was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 18 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

(Second anti-sulfurization layer (GZO))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., GZO was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 Å / s. The target-substrate distance was 90 mm.
The refractive index of light with a wavelength of 570 nm of GZO was 2.04, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.04.

[Example 16]
On the transparent substrate made of cycloolefin polymer, the first high refractive index layer (Nb ₂ O ₅ ) / underlayer (Pd) / transparent metal film (Ag) / second antisulfuration layer (ZnO) / second high refractive index Layers (ZnS—SiO ₂ ) were sequentially stacked.
The first high refractive index layer (Nb ₂ O ₅ ) was formed in the same manner as the second high refractive index layer of Example 5.
The underlayer (Pd) was formed in the same manner as the underlayer of Example 5.
The transparent metal film (Ag) and the second high refractive index layer (ZnS—SiO ₂ ) were formed in the same manner as the transparent metal film and the first high refractive index layer in Example 1, respectively.
The second antisulfurization layer (ZnO) was formed in the same manner as the first antisulfurization layer of Example 4.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 19 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

[Example 17]
On a transparent substrate made of a cycloolefin polymer, a first high refractive index layer (ZrO ₂ ) / underlayer (Pd) / transparent metal film (Ag) / second antisulfuration layer (ZnO) / second high refractive index layer ( ZnS) were stacked in order.
The first high refractive index layer (ZrO ₂ ) was formed by the following method.
The underlayer (Pd) was formed in the same manner as the underlayer of Example 5.
A transparent metal film (Ag) was formed in the same manner as the transparent metal film of Example 1.
The second antisulfurization layer (ZnO) and the second high refractive index layer (ZnS) were formed in the same manner as the first antisulfurization layer and the first high refractive index layer of Example 4, respectively.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First high refractive index layer (ZrO ₂ ))
Using Arnelva L-430S-FHS, ZrO ₂ was RF sputtered at Ar 20 sccm, O ₂ 1 sccm, sputtering pressure 0.5 Pa, room temperature, target-side power 150 W, and deposition rate 0.5 Å / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of ZrO ₂ was 2.05.

[Example 18]
On a transparent substrate made of glass, a first high refractive index layer (ITO) / underlayer (Pd) / transparent metal film (Ag) / second antisulfuration layer (ZnO) / second high refractive index layer (ZnS) Laminated in order.
The first high refractive index layer (ITO) and the transparent metal film (Ag) were formed in the same manner as the second high refractive index layer and the transparent metal film in Example 1, respectively.
The underlayer (Pd) was formed in the same manner as the underlayer of Example 5.
The second antisulfurization layer (ZnO) and the second high refractive index layer (ZnS) were formed in the same manner as the first antisulfurization layer and the first high refractive index layer of Example 4, respectively.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 21 shows the spectral characteristics of the conductive region of the obtained transparent conductor.

[Example 19]
On a transparent substrate made of PET / CHC (PET film with clear hard coat layer), first high refractive index layer (ZnS) / first antisulfurization layer (GZO) / transparent metal film (Ag) / second high refractive index Layer (IGZO) / third high refractive index layer (ITO) were laminated in order.
The first high refractive index layer (ZnS) was formed in the same manner as the first high refractive index layer of Example 4.
The first antisulfurization layer (GZO) was formed in the same manner as the first antisulfurization layer of Example 1 except that the target was GZO.
The transparent metal film (Ag) was formed in the same manner as the transparent metal film of Example 1.
The second high refractive index layer (IGZO) was formed in the same manner as the second high refractive index layer of Example 2.
The third high refractive index layer (ITO) was formed in the same manner as the second high refractive index layer of Example 1.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG. The surface electrical resistance of the conductive region of the transparent conductor was measured and found to be 5Ω / □. The surface electrical resistance was measured with a resistivity meter “Loresta EP MCP-T360” manufactured by Mitsubishi Chemical Analytech Co., Ltd. in accordance with JIS K7194, ASTM D257 and the like.

[Example 20]
On a transparent substrate made of PET / CHC (PET film with clear hard coat layer), first high refractive index layer (ZnS) / first antisulfurization layer (IGZO) / transparent metal film (Ag) / second high refractive index Layer (IGZO) / third high refractive index layer (ITO) were laminated in order.
A laminate was obtained in the same manner as in Example 19 except that the first sulfurization prevention layer was changed to IGZO. The obtained laminate was patterned in the same manner as in Example 1. The surface electrical resistance of the conductive region of the transparent conductor was measured and found to be 5Ω / □. The surface electrical resistance was measured with a resistivity meter “Loresta EP MCP-T360” manufactured by Mitsubishi Chemical Analytech Co., Ltd. in accordance with JIS K7194, ASTM D257 and the like.

[Comparative Example 1]
On a transparent substrate made of quartz, a first high refractive index layer (ZnS) / transparent metal film (Ag) / second high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer (ZnS), the transparent metal film (Ag), and the second high refractive index layer (ZnS) were formed by the following methods, respectively.
FIG. 23 shows the spectral characteristics of the conduction region of the obtained transparent conductor.

(First high refractive index layer and second high refractive index layer (ZnS))
A film made of ZnS was formed by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the film formation rate was 5 Å / s.

(Transparent metal film (Ag))
On the first high refractive index layer, a silver film having a thickness of 12 nm was formed by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the film formation rate was 5 Å / s.

[Comparative Example 2]
On a transparent substrate made of EAGLE Glass, a first high refractive index layer (ZnS) / transparent metal film (Ag) / second high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer and the second high refractive index layer were formed by the same method as the first high refractive index layer of Example 4.
The transparent metal film was formed in the same manner as in Comparative Example 1.

[Comparative Example 3]
A first high refractive index layer (Nb ₂ O ₅ ) / transparent metal film (Ag) / second high refractive index layer (IZO) were laminated in this order on a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm). .
Each layer was formed by the following method.
The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First high refractive index layer (Nb ₂ O ₅ ))
Nb ₂ O ₅ was RF-sputtered using Arnelva L-430S-FHS at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 0.74 Å / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of Nb ₂ O ₅ is 2.31, but the refractive index of light with a wavelength of 570 nm of the high refractive index layer is 2.35.

(Transparent metal film (Ag))
DC sputtering was performed with a small sputtering apparatus (BC4279) manufactured by Nippon Vacuum Technology Co., Ltd. At this time, the target side power was set to 200 W.

(Second high refractive index layer (IZO))
Using an Anelva L-430S-FHS, IZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of IZO is 2.05, but the refractive index of light with a wavelength of 570 nm of the second high refractive index layer is 1.98.

[Comparative Example 4]
On Konica Minolta TAC film (transparent substrate), first high refractive index layer (ICO) / underlayer (NiCr) / transparent metal film (AgAu) / adhesion layer (NiCr) / second high refractive index layer (ICO) / Low refractive index layer (SiO ₂ ) / Fluorine-based material layer (KP801M) were laminated in this order.
The low refractive index layer (SiO ₂ ) was formed in the same manner as the low refractive index layer of Example 12. The other layers were formed by the following methods.

(First high refractive index layer and second high refractive index layer (ICO))
The target was formed in the same manner as the second high refractive index layer of Comparative Example 3 except that the target was made of a material (ICO) containing 10 atomic% of cerium in indium. The refractive index of light with a wavelength of 570 nm of ICO was 2.2, and the refractive indexes of light with a wavelength of 570 nm of the first high refractive index layer and the second high refractive index layer were also 2.2.

(Underlayer and adhesion layer (NiCr))
A film was formed in the same manner as the base layer (Pd) of Example 5 except that the target was NiCr.

(Transparent metal film (AgAu))
An alloy alloy L-430S-FHS, Ar 20 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 100 W, film formation rate 2.5 kg / s, Ag alloy (1.5 atomic% of Au in Ag) An alloy containing 0.5 atomic% of Cu) was RF sputtered. The target-substrate distance was 86 mm.

(Fluorine material layer (KP801M))
Fluorine-based material (manufactured by Shin-Etsu Chemical Co., Ltd .: KP801M) was vapor-deposited by resistance heating with a Gener 1300 manufactured by Optorun at 190 mA and a film formation rate of 10 kg / s.

[Comparative Example 5]
A first high refractive index layer (ITO) / transparent metal film (APC alloy) / second high refractive index layer (ITO) were laminated in this order on a transparent substrate made of Toyobo PET (Cosmo Shine A4300, thickness 50 μm).
The first high refractive index layer and the second high refractive index layer (ITO) were formed in the same manner as the first high refractive index layer of Example 17, respectively.
The transparent metal film was formed by the following method.

(Transparent metal film (APC alloy))
An alloy of L-430S-FHS manufactured by Anelva, an alloy of Ag, Pd, and Cu (Ag: Pd :) at Ar 20 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 100 W, and deposition rate 2.5 Å / s. RF sputtering was performed on Cu = 99: 1: 1 (mass ratio). The target-substrate distance was 86 mm.

[Comparative Example 6]
On a transparent substrate made of Corning glass substrate (# 7059, thickness 1.1 mm), first high refractive index layer (a-GIO) / transparent metal film (Ag) / second high refractive index layer (a-GIO) ) In order.
Each layer was formed by the following method.

(First high refractive index layer and second high refractive index layer (a-GIO))
An oxide sintered body of Ga and In was DC sputtered at an electric power density of 2.2 W / cm ^{2 in} an atmosphere of 0.6 Pa of Ar gas mixed with O ₂ gas. The ratio of O ₂ gas to be introduced was 8 to 12% by volume.

(Transparent metal film (Ag))
In an atmosphere of Ar gas 0.6 Pa, a 4N purity Ag target was DC sputtered at a power density of 0.55 W / cm ² .

[Evaluation]
(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 65 ° C. and 95% Rh for 100 hours. Evaluation was based on the following criteria.
○: In the area of 30 mm × 30 mm, 0 corrosion sites with a size of 20 μm or more Δ: In the region of 30 mm × 30 mm, 1 or more and less than 10 corrosion sites with a size of 20 μm or more ×: Size in the region of 30 mm × 30 mm 10 or more corrosion spots of 20μm or more

(Measurement of light transmittance, reflectance and absorptance)
For the transparent conductors of Examples 1 to 5, 8 to 11, 13, 14, and 16 to 20, the light transmittance, reflectance, and absorptance were measured as follows.
Matching oil (refractive index = 1.515 manufactured by Nikon Corporation) was applied to the surface of the transparent conductor obtained in each example on the second high refractive index layer side. Then, the transparent conductor and a non-alkali glass substrate (EAGLE XG (thickness 7 mm × length 30 mm × width 30 mm)) manufactured by Corning were bonded together. And the transmittance | permeability and reflectance of the transparent conductor were measured from the alkali free glass substrate side. At this time, measurement light (for example, light having a wavelength of 450 nm to 800 nm) is incident on the conduction region from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate. The light transmittance and reflectance were measured at U4100. The absorptance was calculated from a formula of 100− (transmittance + reflectance).

The value obtained by subtracting the reflection at the interface between the alkali-free glass substrate and the atmosphere (4%) and the reflection at the interface between the transparent substrate and the atmosphere (4%) from the measured value of the reflectance The reflectance of the transparent conductor was used. Also, the transmittance was added to the measured value of transmittance by 8% in consideration of the reflection at the interface between the alkali-free glass substrate and the atmosphere and the reflection of the transparent conductor at the interface between the transparent substrate and the atmosphere. The value was the transmittance of the transparent conductor.

On the other hand, the transparent conductors of Examples 6, 7, 12, 15, Comparative Example 1 and Comparative Example 3 were used in contact with air. Therefore, measurement light (for example, light having a wavelength of 450 nm to 800 nm) is incident on the conductive region without bonding an alkali-free glass substrate on the transparent conductor, and light is emitted by Hitachi, Ltd .: spectrophotometer U4100. The transmittance and reflectance were measured. The absorptance was calculated from a formula of 100− (transmittance + reflectance). The measurement light was incident from the second high refractive index layer side.

The value obtained by subtracting the reflection (4%) at the interface between the transparent substrate of the transparent conductor and the atmosphere from the measured value of the reflectance was taken as the reflectance of the transparent conductor. Also, the transmittance of the transparent conductor was determined by adding 4% to the measured value of the transmittance in consideration of the reflection of the transparent conductor at the interface between the transparent substrate and the atmosphere.

(Measuring method of luminous reflectance)
The luminous reflectance of each transparent conductor was measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation). ΔR in Tables 1 and 2 represents the absolute value of the difference between the luminous efficiency of the conductive area and the luminous efficiency of the insulating area.

(Measurement method of a * value and b * value of conduction region)
The a * value and b * value in the L * a * b * color system of each transparent conductor were measured with a spectrophotometer U4100 manufactured by Hitachi, Ltd.

(Optical admittance)
The optical admittance of the transparent conductor obtained by the Example and the comparative example was specified. The optical admittance of wavelength 570nm of the first high refractive index layer side of the surface of the transparent metal Y1 ₌ x ₁ + iy 1, the optical admittance of wavelength 570nm of the second high refractive index layer side of the surface of the transparent metal film Y2 = x Tables 3 and 4 show the values of (x ₁ , y ₁ ) and (x ₂ , y ₂ ) when ₂ + iy ₂ is set.
For the transparent conductor obtained by patterning the first high-refractive index layer, the transparent metal film, and the second high-refractive index layer, the equivalent admittance of light having a wavelength of 570 nm on the surface of the laminate (conduction region) including the transparent metal film Is expressed as Y _E = x _E + iy _E , and the equivalent admittance of light with a wavelength of 570 nm on the surface of the laminate (insulating region) that does not include the transparent metal film; that is, Y _sub = x _sub + iy _sub The values of (x _sub , y _sub ) are shown in Table 3 and Table 4, respectively. Furthermore, the values of (x _env , y _env ) when the equivalent admittance of light having a wavelength of 570 nm of the medium in which light enters the transparent conductor is expressed by Y _env = x _env + iy _env are also shown in Table 3 and Table 4, respectively. . The values of | (x _env −x _sub ) ² + (y _env −y _sub ) ² − (x _env −x _E ) ² + (y _env −y _E ) ² | are shown in Table 3 and Table 4, respectively. .

The optical admittance of the layer contained in the transparent conductor was calculated by the thin film design software Essential Macleod Ver.9.4.375. Note that the thickness d, refractive index n, and absorption coefficient k of each layer necessary for the calculation are as follows. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

As shown in Tables 1 and 2, in the transparent conductors (Examples 1 to 20) each having an anti-sulfurization layer between the zinc sulfide-containing layer and the transparent metal film, the average transmittance is 450 to 800 nm. Was 86.4% or more. Here, both the first high-refractive index layer and the second high-refractive index layer are zinc sulfide-containing layers, and only between one of the zinc sulfide-containing layers and the transparent metal film is sulfided. In the case of having the prevention layer (Examples 13 to 15), the average transmittance at a wavelength of 450 to 800 nm was 88.6% or less. However, between both the zinc sulfide-containing layers and the transparent metal film, In the case of having a prevention layer (Examples 8 to 12), the average transmittance at a wavelength of 450 to 800 nm was 89.3% or more.

On the other hand, as shown in Table 2, the transparent conductor (Comparative Example 1) having no anti-sulfurization layer between the zinc sulfide-containing layer and the transparent metal film has an average transmittance of 450 to 800 nm. It was 85.3%.

In addition, as shown in Tables 1 and 2, when one or both of the transparent metal films has a zinc sulfide-containing layer (Examples 1 to 20 and Comparative Examples 1 and 2), the wet heat environment No corrosion occurred even underneath. On the other hand, when the transparent conductor did not contain a zinc sulfide-containing layer (Comparative Examples 3 to 6), corrosion was likely to occur in a humid heat environment.

In Comparative Example 2 in which a transparent metal film having a thickness of 7.3 nm was prepared by vapor deposition, a continuous film was not obtained and electricity was not conducted.

This application claims priority based on Japanese Patent Application No. 2013-211185 filed on Oct. 9, 2013. The contents described in the application specification and the drawings are all incorporated herein.

The transparent conductor obtained by the present invention hardly corrodes the transparent metal film even in a humid heat environment, and has high light transmittance. Therefore, it is preferably used in various optoelectronic devices such as various types of displays, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescence light control elements, and the like.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer 3 Transparent metal film 4 2nd high

refractive index layer

5a, 5b Antisulfuration layer 100 Transparent conductor

Claims

A transparent substrate;
A first high refractive index layer including a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate;
A transparent metal film,
A transparent conductor including a second high-refractive-index layer including a dielectric material or an oxide semiconductor material in which the refractive index of light having a wavelength of 570 nm is higher than the refractive index of light having a wavelength of 570 nm of the transparent substrate in this order. ,
Of the first high refractive index layer or the second high refractive index layer, at least one layer is a zinc sulfide-containing layer containing ZnS,
A transparent conductor further comprising a sulfide prevention layer containing metal oxide, metal fluoride, metal nitride, or Zn between the zinc sulfide-containing layer and the transparent metal film.
The transparent conductor according to claim 1, wherein the anti-sulfurization layer contains ZnO.
The transparent conductor according to claim 1, wherein the zinc sulfide-containing layer further contains SiO 2 .
The transparent conductor according to claim 1, wherein the transparent metal film is a metal pattern patterned into a predetermined shape.