WO2015107968A1

WO2015107968A1 - Method for manufacturing transparent conductor and transparent conductor

Info

Publication number: WO2015107968A1
Application number: PCT/JP2015/050319
Authority: WO
Inventors: 一成多田; 仁一粕谷; 健一郎平田
Original assignee: コニカミノルタ株式会社
Priority date: 2014-01-15
Filing date: 2015-01-08
Publication date: 2015-07-23
Also published as: JPWO2015107968A1

Abstract

　The present invention addresses the problem of providing a method for manufacturing a transparent conductor that is highly productive, exhibits excellent flexibility, transparency, and coloring resistance, and exhibits low resistance characteristics, and a transparent conductor obtained using the method for manufacturing a transparent conductor. This method for manufacturing a transparent conductor is characterized in laminating, in the stated order, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer on a transparent substrate, the first high refractive index layer and/or the second high refractive index layer being formed by co-deposition of a mixed film of zinc sulfide and at least one metal compound selected from metal oxides, metal fluorides, and metal nitrides.

Description

Method for producing transparent conductor and transparent conductor

The present invention relates to a method for producing a transparent conductor having a transparent metal layer and a transparent conductor, and more specifically, production of a transparent conductor having excellent productivity, flexibility, transparency, coloration resistance and low resistance characteristics. The present invention relates to a method and a transparent conductor obtained thereby.

Recently, display devices such as touch panel materials, liquid crystal displays and plasma displays, inorganic and organic EL (electroluminescence) displays, and various devices such as solar cells have demanded transparent conductive films having low resistance characteristics.

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

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

In recent years, a capacitive touch panel display device has been developed, and there is a strong demand for setting the surface electrical resistance of the transparent conductive film to be lower, specifically, a resistance value of 50Ω / □ or less. However, the ITO film currently widely used as described above has a resistance value of only about 150Ω / □, which is insufficient for the above-mentioned demand.

Against this background, the development of next-generation transparent conductive films to replace ITO has been actively carried out in recent years.

In response to the above problems, for example, Japanese Patent Application Laid-Open Nos. 2011-138628 and 2011-171292 disclose a method for manufacturing a conductive element to which a silver mesh is applied. However, these methods using silver mesh have a mesh diameter of about 20 μm and can be visually recognized by human eyes, so that it is difficult to apply to touch panel display devices that require light transmission. It is. In addition, silver nanowires that are commercially available from some manufacturers have a microscopic size that is not visible to the naked eye and expresses electrical conductivity in the film, but the surface resistance value is only about 60Ω / □. Therefore, the quality required for the current touch panel display device is insufficient.

In addition, attempts have been made to reduce the resistance by using zinc oxide or the like, but in such a method, the film thickness of the conductive film needs to be laminated to about 200 nm, and it was formed in the manufacturing process. When stress is applied to the conductive film, cracks and the like are likely to occur in the film, resulting in a decrease in yield and a problem in terms of production efficiency. In addition, the conductive film having such characteristics is difficult to apply to flexible touch panels and curved members that are expected to be put to practical use in the near future.

In view of the above problems, a method of applying a silver vapor-deposited film as a transparent conductive film has been actively studied in recent years (see, for example, Patent Document 1). Further, in order to increase the light transmittance of the transparent conductor, a silver film having high conductivity is formed from a metal film having a high refractive index formed by sputtering (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium oxide). A transparent conductive film having a structure sandwiched between zinc oxide), ICO (indium cerium oxide), a-GIO (a film of amorphous oxide made of gallium, indium, and oxygen) has also been proposed (for example, (See Patent Documents 2 to 4 and Non-Patent Document 3.) Furthermore, a method of sandwiching a silver thin film with a zinc sulfide film has also been proposed (see, for example, Non-Patent Documents 1 and 2).

However, as disclosed in Patent Documents 2 to 4 and Non-Patent Documents 1 to 3, for example, ITO / silver thin film / ITO, Nb ₂ O ₅ / silver thin film / IZO, and zinc sulfide / silver thin film / zinc sulfide. The transparent conductor manufactured by the sputtering method having such a configuration has the following problems.

That is,
1) A transparent conductor having a structure in which a silver thin film layer is sandwiched between metal oxide layers such as niobium oxide and IZO has insufficient moisture resistance. As a result, when using a transparent conductor in a humidity environment, the formed silver thin film tends to corrode.
2) In a transparent conductor having a silver thin film sandwiched between zinc sulfide layers, the moisture resistance of the transparent conductor is sufficiently high, but it moves from the adjacent layer when the silver thin film layer is formed or when the zinc sulfide layer is formed. Silver is sulfided easily by the sulfur component, and silver sulfide is easily generated. As a result, the transparent conductor is discolored and the light transmittance is lowered.
3) It is necessary to introduce oxygen at the time of formation, the planarity of the formed silver thin film layer is lowered, and unnecessary absorption is increased.
4) The formed transparent conductor is not flexible and is likely to crack when subjected to bending stress, etc.
5) The formation rate of the metal oxide layer is low, and the manufacturing cost is high (production efficiency is low).
6) It is likely to become high temperature during the production of the transparent conductor, and when applying a plastic base material as a silver thin film layer or a transparent substrate, it is easily damaged by heat, and unnecessary absorption tends to increase
7) The wiring required for the touch panel etc. cannot be formed.
8) Sulfurization increases unnecessary absorption.
9) The compatibility between the component to be sandwiched and silver is poor, and plasmon absorption increases when the silver film is thinned.
10) Since the formation speed of the adjacent layer of the silver thin film layer cannot be increased, the film quality of the silver thin film is deteriorated and illegal absorption increases.
We had various problems such as.

Therefore, there is a demand for the development of a transparent conductor manufacturing method that overcomes the above problems and is excellent in durability, productivity, and quality stability (film quality, absorption stability, etc.).

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-015623 A JP 2008-226581 A

The present invention has been made in view of the above problems, and its solution is a transparent conductor having high productivity, flexibility, excellent transparency and coloring resistance, and low resistance characteristics. And a transparent conductor obtained thereby.

As a result of intensive studies in view of the above problems, the present inventors have laminated at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on a transparent substrate. A method for producing a transparent conductor to be produced, wherein at least one of the first high refractive index layer and the second high refractive index layer is at least selected from zinc sulfide, metal oxide, metal fluoride, and metal nitride. A production method of a transparent conductor characterized by forming a mixed film with a kind of metal compound by a co-evaporation method, has high productivity, has flexibility, excellent transparency and coloring resistance, The inventors have found that a method for producing a transparent conductor having low resistance characteristics can be provided, and have reached the present invention.

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

1. On the transparent substrate, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are laminated in this order to produce a transparent conductor,
At least one layer of the first high-refractive index layer and the second high-refractive index layer is a co-evaporation of a mixed film of zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. A method for producing a transparent conductor, characterized by being formed by a method.

2. 2. The method for producing a transparent conductor according to item 1, wherein the metal oxide is silicon dioxide.

3. 3. The method for producing a transparent conductor according to

item

1 or 2, wherein the transparent metal layer is composed of silver as a main component and is formed under conditions of a formation rate of 0.3 nm / second or more.

4. The first high refractive index layer or the second high refractive index layer has an average zinc sulfide concentration in an interface region adjacent to the transparent metal layer (10% of the total thickness in the thickness direction from the adjacent interface). It forms on the conditions used as 50 volume% or more, The manufacturing method of the transparent conductor as described in any one of 1st term | claim to 3rd term | claim characterized by the above-mentioned.

5. Each of the first high refractive index layer and the second high refractive index layer has an average zinc sulfide concentration of 70 volumes in an interface region adjacent to the transparent metal layer (10% region in the thickness direction from the surface of the total thickness). It forms on the conditions used as% or more, The manufacturing method of the transparent conductor as described in any one of Claim 1 to 3 characterized by the above-mentioned.

6. Items 1 to 5, wherein an antisulfurization layer is formed between the first high refractive index layer and the transparent metal layer, or between the second high refractive index layer and the transparent metal layer. The manufacturing method of the transparent conductor as described in any one of the above.

7. The method for producing a transparent conductor according to item 6, wherein the antisulfurization layer is formed of a material containing a zinc metal element.

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

9. A transparent conductor produced by the method for producing a transparent conductor according to any one of items 1 to 8,
On the transparent substrate, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are provided in this order, and at least of the first high refractive index layer and the second high refractive index layer. One layer is a mixed film of zinc sulfide and at least one metal compound selected from metal oxides, metal fluorides, and metal nitrides.

10. The transparent conductor according to item 9, wherein the metal oxide is silicon dioxide.

11. The first high refractive index layer or the second high refractive index layer has an average zinc sulfide concentration of 50% by volume in an interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the entire layer thickness). The transparent conductor according to Item 9 or 10, which is as described above.

12. Each of the first high refractive index layer and the second high refractive index layer has an average zinc sulfide concentration of 70 volumes in an interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the total thickness). % Or more of the transparent conductor according to item 9 or 10.

13. Item 9 to Item 12 including an antisulfurization layer between the first high refractive index layer and the transparent metal layer, or between the second high refractive index layer and the transparent metal layer. The transparent conductor as described in any one of these.

14. 14. The transparent conductor according to item 13, wherein the sulfidation preventing layer contains a zinc metal element.

15. 15. The transparent conductor according to any one of items 9 to 14, wherein the transparent metal layer is a metal pattern electrode patterned in a predetermined shape.

By the above means of the present invention, there is provided a method for producing a transparent conductor having high productivity, excellent flexibility, transparency, coloring resistance and low resistance characteristics, and a transparent conductor obtained thereby. be able to.

The expression mechanism / action mechanism that has achieved the above-described object effect of the present invention is not clear, but is presumed as follows.

In the method for producing a transparent conductor of the present invention, at least one of the first high-refractive index layer and the second high-refractive index layer is at least one selected from zinc sulfide, metal oxide, metal fluoride, and metal nitride. It is characterized by being formed by a co-evaporation method as a mixed film with the above metal compound. Zinc sulfide has a good barrier property, and can improve the moisture resistance of a transparent metal layer made of, for example, Ag. That is, since zinc sulfide is abundantly present in the vicinity of a transparent metal layer, for example, a silver thin film layer, silver atoms can be gripped and migration of silver atoms can be prevented. As a result, an extremely thin and uniform silver layer of 10 nm or less can be formed. Thereby, silver plasmon absorption can be reduced.

In addition, by providing a sulfide prevention layer with a layer thickness of 10 nm or less between the high refractive index layer containing zinc sulfide and the transparent metal layer composed of silver or the like, the sulfide of the transparent metal layer is prevented, Increase in absorption can be prevented.

Further, in the present invention, since the sulfur sulfide is used for forming the second high refractive index layer provided on the transparent metal layer, the zinc sulfide can be formed without introducing oxygen. Attack (oxidation) to the layer can be reduced. As a result, it is possible to improve the moisture resistance of the transparent metal layer and to suppress the occurrence of plasmon absorption due to the roughening of constituent elements such as silver.

Further, the high refractive index layer containing zinc sulfide can be easily etched with a weak acid, and an arbitrary wiring pattern can be formed using the high refractive index layer. Further, when the high refractive index layer is formed by mixing the second component with zinc sulfide, the crystallinity of the zinc sulfide is impaired, so that etching becomes easier. In addition, by mixing the second component (for example, metal oxide, metal fluoride, metal nitride, etc.) with zinc sulfide, it is possible to prevent crystal growth of the zinc sulfide layer. Amorphous and flexible.

On the other hand, the thin film formation method by the sputtering method has a problem that the film formation speed is slow because the thin film is formed by forming the surface of the thin film and hitting only the atoms on the target surface. Further, in the sputtering method, the target is cracked or heat is generated when the output is increased in order to increase the formation speed of the thin film, so that the resin base material and the thin film metal layer to be formed are damaged. The formation speed also plays an important role from the viewpoint of transmittance. If the silver formation speed is slow, silver absorbs and the transmittance decreases, so the silver formation speed cannot be less than 0.3 nm / second. That is, when film formation is performed roll-to-roll while keeping this condition, the film material formation speed other than silver must be high. Naturally, a high refractive index material having a film thickness larger than that of silver is required to have a formation speed higher than that of silver. However, sputtering has a problem that a high refractive index material cannot be formed at such a speed.

On the other hand, in the manufacturing method of the present invention, the vapor deposition method (for example, resistance heating method or electron beam method) used for forming the high refractive index layer can give energy to a narrow region, and the entire material evaporates. The formation speed of the thin film is dramatically improved as compared with the sputtering method. In particular, in the present invention, zinc sulfide used for forming a high refractive index layer has sublimation properties and can be deposited with low energy and without generating heat. Moreover, even if the melting points of zinc sulfide and the second component are different by using different heating sources for the zinc sulfide and the second component, respectively, the respective proportions can be accurately maintained. However, it can be formed by co-evaporation without slowing down the formation speed of the thin film.

That is, by adopting the configuration defined in the present invention, a high refractive index layer containing zinc sulfide and at least one second component selected from metal oxides, metal fluorides, and metal nitrides is co-evaporated. By forming, the formation speed could be increased without limitation.

In addition, by applying the co-evaporation method, it is possible to avoid damage such as damage to the metal layer and deformation of the transparent substrate due to temperature rise during formation, which is a problem with sputtering, etc. As a result, a high-quality transparent metal layer excellent in homogeneity can be formed. Furthermore, by providing an anti-sulfurization layer between the high refractive index layer and the transparent metal layer, it is possible to obtain a transparent conductor with higher transparency by blocking the adverse effects of sulfide on the transparent metal layer. It was.

Schematic sectional view showing an example of the configuration of the transparent conductor of the present invention Schematic sectional view showing another example of the configuration of the transparent conductor of the present invention Schematic sectional view showing another example of the configuration of the transparent conductor of the present invention The schematic diagram which shows an example of the pattern which has the conduction | electrical_connection area and insulation area | region of the transparent conductor of this invention Schematic diagram showing an example of a process flow for producing a transparent conductor in an online process The graph which shows an example of the admittance locus | trajectory in wavelength 570nm of a transparent conductor Process drawing showing an example of forming an electrode pattern by a photolithography method on the transparent conductor of the present invention The perspective view which shows an example of a structure of the touchscreen which comprised the transparent conductor of this invention which has an electrode pattern.

The method for producing a transparent conductor according to the present invention includes a transparent conductor produced by laminating at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on a transparent substrate. Wherein at least one of the first high-refractive index layer and the second high-refractive index layer includes zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. The mixed film is formed by a co-evaporation method. This feature is a technical feature common to the inventions according to claims 1 to 15.

As an embodiment of the present invention, the metal oxide contained in the first high-refractive index layer or the second high-refractive index layer is silicon dioxide from the viewpoint that the effect of the present invention can be further expressed. Furthermore, it is preferable from the point which can form the refractive index layer which has high transparency. Furthermore, the formation rate is more preferably in the range of 0.5 to 30 nm / second, and particularly preferably in the range of 1.0 to 15 nm / second.

In addition, it is possible to form the transparent metal layer with silver as a main component under the condition that the formation speed is 0.3 nm / second or more. The conductive layer has low resistance, high uniformity, and no improper absorption. Is preferable in that it can be stably formed.

In addition, the average zinc sulfide concentration in the interface region adjacent to the transparent metal layer (10% region in the thickness direction from the surface of the total layer thickness) of the first high refractive index layer or the second high refractive index layer is 50% by volume. Forming under the above conditions is to form a transparent metal layer formed adjacent to each refractive index layer, particularly when forming a transparent metal layer mainly composed of silver, or a refractive layer on the transparent conductor layer. When forming, the constituent layer coating solution is repelled to prevent the occurrence of sea-striped film surface unevenness, and it is preferable from the viewpoint that a highly uniform coating film can be formed. Both the refractive index layer and the second high refractive index layer have an average zinc sulfide concentration of 70% by volume or more in the interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the total thickness). It is preferable to form under conditions.

In addition, an antisulfurization layer may be formed between the first high refractive index layer and the transparent metal layer or between the second high refractive index layer and the transparent metal layer. High transparency and stability by preventing the discoloration caused by the sulfur component of the zinc sulfide used to form the high refractive index layer being a constituent component of the transparent metal layer, specifically, silver is sulfided and becomes silver sulfide. From the viewpoint of obtaining a transparent metal layer having a desired color tone, a material containing a zinc metal element, for example, zinc oxide or the like is preferably applied.

Also, as a method for producing a transparent conductor of the present invention, it is preferable to form a metal pattern electrode by patterning a transparent metal layer into a predetermined shape.

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

《Basic structure of transparent conductor》
1A to 1C are schematic cross-sectional views showing examples of the configuration of the transparent conductor of the present invention.

In the transparent conductor 1 of the present invention having the configuration shown in FIG. 1A, at least a first high refractive index layer 3A, a transparent metal layer 4, and a second high refractive index layer 3B are laminated in this order on a transparent substrate 2. It has a configuration.

In the transparent conductor 1 having the configuration shown in FIG. 1A, at least one of the first high-refractive index layer 3A or the second high-refractive index layer 3B is zinc oxide (hereinafter also referred to as ZnS), a metal oxide, A mixed film containing at least one metal compound selected from metal fluorides and metal nitrides is formed by a co-evaporation method.

In the transparent conductor of the present invention, as illustrated in FIG. 1A, the first high refractive index layer 3A or the second high refractive index layer 3B is an interface region 0.1 T _A adjacent to the transparent metal layer 4 or 0. _(in the thickness direction from the adjacent surface, 10 percent of the total layer thickness T _a or T _B) 1T B average zinc sulfide concentrations in is preferably formed under the condition that a 50% by volume or more, more preferably , the average zinc sulfide concentration in the interface region 0.1 T _a which is adjacent to the transparent metal layer 4 of the first high refractive index layer 3A, and the second interface region 0.1 T _B which is adjacent to the transparent metal layer 4 of the high refractive index layer 3B It is a preferable aspect that the average zinc sulfide concentration in each is 70% by volume or more. Furthermore, it is preferably 80% by volume or more, particularly preferably 90% by volume or more.

The average zinc sulfide concentration at the interface region adjacent to the transparent metal layer 4 of the high-refractive index layer in the present invention, as shown in FIG. 1A, the high refractive index layer 3A, the total thickness of each T _A of 3B, when the T _B, the average content of each high refractive index layer transparent metal layer 4 and the region 0.1 T a from the adjacent side up to 10% in the depth direction of the layer _thickness, zinc sulfide in 0.1 T _B Each atomic ratio is determined by using a conventionally known method, for example, an analyzer using X-ray photoelectron spectroscopy (XPS) or the like in a predetermined region range of 0.1 T _A and 0.1 T. After randomly measuring 50 or more points for _B , the average value can be calculated.

In addition, the transparent conductor 1 of the present invention preferably has a structure having an antisulfurization layer 5 between at least the first high refractive index layer 3A or the second high refractive index layer 3B and the transparent metal layer 4. It is an aspect.

The transparent conductor 1 shown in FIG. 1B shows a configuration example in which the first sulfidation preventing layer 5A is formed between the first high refractive index layer 3A and the transparent metal layer 4, and FIG. 1C shows the first high refractive index. A configuration example is shown in which a first sulfidation preventing layer 5A is formed between the layer 3A and the transparent metal layer 4, and a second sulfidation preventing layer 5B is formed between the second high refractive index layer 3B and the transparent metal layer 4. .

As described above, by providing the

antisulfurization layer

5A or 5B between the first high refractive index layer 3A or the second high refractive index layer 3B and the transparent metal layer 4, the first high refractive index layer 3A or the second high refractive index layer 3A or second This is a preferred embodiment because the sulfur atoms constituting the zinc sulfide contained in the high refractive index layer 3B can be prevented from moving or mixing into the transparent metal layer 4.

That is, when the transparent metal layer 4 (for example, silver layer) and the first high-refractive index layer 3A or the second high-refractive index layer 3B containing at least ZnS are formed adjacent to each other, an interface region between the transparent metal layer 4 and the transparent metal layer 4 is formed. Further, there is a problem that metal sulfide (for example, silver sulfide) is easily generated, and the light transmittance of the transparent conductor 1 is easily lowered.

In the transparent metal layer 4, it is assumed that the metal sulfide is generated in the following situation.

In the case where the transparent metal layer 4 is formed on the first high refractive index layer 3A containing at least zinc sulfide by a vapor phase film forming method such as a vapor deposition method, the transparent metal layer 4 in the first high refractive index layer 3A containing zinc sulfide is not yet formed. The sulfur component of the reaction is expelled into the forming atmosphere by the material of the transparent metal layer 4 (eg, silver). Then, the ejected sulfur component reacts with a metal, for example, a sulfur atom and a silver atom, and a metal sulfide is deposited on the first high refractive index layer 3A containing zinc sulfide. Further, when forming a transparent conductor by a continuous vapor deposition process, when forming a transparent metal layer by vapor phase film formation such as vapor deposition on the first high refractive index layer 3A containing zinc sulfide, zinc sulfide The sulfur component contained in the formation atmosphere of the first high refractive index layer 3 A containing is left in the transparent metal layer atmosphere. Then, the sulfur component reacts with the metal, and the metal sulfide is deposited on the first high refractive index layer 3A containing zinc sulfide. Alternatively, there are some Zn and unbonded sulfur on the outermost surface of the first high refractive index layer 3A, and then when the transparent metal layer 4 is laminated, the unbonded active sulfur component becomes transparent metal. Combined with the constituent atoms of the layer 4, for example, silver, silver sulfide is produced.

On the other hand, when the second high refractive index layer 3B containing at least zinc sulfide is formed on the transparent metal layer 4, the metal in the transparent metal layer 4 is a material of the second high refractive index layer 3B containing zinc sulfide. Is played in the forming atmosphere. The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer 4. Furthermore, a metal sulfide is also generated on the surface of the transparent metal layer 4 when the surface of the transparent metal layer 4 comes into contact with the sulfur component in the forming atmosphere. Alternatively, when depositing the zinc sulfide constituting the second high refractive index layer 3B, the zinc and sulfur are partly present in the atmosphere, and the released sulfur is a constituent atom of the transparent metal layer. For example, combined with silver.

On the other hand, in the transparent conductor 1 of the present invention, for example, as shown in FIG. 1B, the first sulfidation preventing layer 5A is formed on the first high refractive index layer 3A. Since the first high refractive index layer 3A is protected by the first sulfidation preventing layer 5A by adopting the configuration specified in the present invention, the sulfur component in the first high refractive index layer 3A is not formed when the transparent metal layer 4 is formed. It is difficult to play. Even if the first high refractive index layer 3A and the transparent metal layer 4 are continuously formed, the sulfur component contained in the atmosphere in which the first high refractive index layer 3A is formed is a constituent component of the first antisulfurization layer 5A. Reaction with each other, or adsorption to the constituent components of the first sulfidation preventing layer 5A, the atmosphere in which the transparent metal layer 4 is formed does not easily contain sulfur, and the formation of metal sulfide is suppressed.

Moreover, in the transparent conductor 1 of the present invention, for example, as shown in FIG. 1C, the second sulfidation preventing layer 5B is laminated on the transparent metal layer 4. In this configuration, since the transparent metal layer 4 is protected by the second antisulfurization layer 5B, it is difficult for the metal in the transparent metal layer 4 to be ejected when the second high refractive index layer 3B is formed. Further, the sulfur component in the atmosphere in which the second high refractive index layer 3 B is formed is difficult to come into contact with the surface of the transparent metal layer 4. As a result, a metal sulfide is hardly generated on the surface of the transparent metal layer 4.

In the transparent conductor 1 of the present invention, as illustrated in FIGS. 1A to 1C, the transparent metal layer 4 may be laminated on the entire surface of the transparent substrate 2. As shown in FIG. The transparent electrode unit EU including the refractive index layer 3A, the first antisulfurization layer 5A, the transparent metal layer 4, the second antisulfation layer 5B, and the second high refractive index layer 3B may be patterned into a desired shape. . In the transparent conductor 1 of the present invention, the region a where the transparent electrode unit EU is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, as shown in FIG. 2, the region b that does not have the transparent electrode unit EU is an insulating region.

The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductor 1. Details of the pattern applied to the electrostatic touch panel will be described later.

Further, the transparent conductor 1 of the present invention includes a transparent substrate 2, a first high refractive index layer 3A, a transparent metal layer 4, a second high refractive index layer 3B, a first antisulfurization layer 5A, and a second antisulfurization. In addition to the layer 5B, a known functional layer may be provided as necessary. For example, an underlayer that can be a growth nucleus when the transparent metal layer 4 is formed may be included between the transparent metal layer 4 and the first high refractive index layer 3 A adjacent to the transparent metal layer 4. However, it is preferable that all the layers included in the transparent conductor 1 of the present invention are layers made of an inorganic material except for the transparent substrate 2. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 3B, the laminated body from the transparent substrate 2 to the second high refractive index layer 3B is the transparent conductor 1 of the present invention. Define that there is.

<< Method for producing transparent conductor >>
The method for producing a transparent conductor according to the present invention includes a transparent conductor produced by laminating at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on a transparent substrate. Wherein at least one of the first high-refractive index layer and the second high-refractive index layer includes zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. The mixed film is formed by a co-evaporation method.

In the present invention, from the viewpoint of production efficiency, a method of manufacturing the transparent conductor 1 by a continuous online process is preferable.

FIG. 3 is a schematic diagram showing an example of a process for manufacturing a transparent conductor in an online process that can be applied to the manufacturing method of the present invention and continuously forms each constituent layer while continuously transporting a transparent substrate. .

Hereinafter, on the transparent substrate 2 illustrated in FIG. 1C, the first high refractive index layer 3A, the first antisulfurization layer 5A, the transparent metal layer 4, the second antisulfurization layer 5B, and the second high refractive index layer 3B are formed. The outline of the manufacturing method of the transparent conductor laminated | stacked in order is demonstrated.

In FIG. 3, the first high refractive index layer 3 A is formed by the co-evaporation method in the vacuum vapor deposition chamber 11 in step 1, the first sulfurization prevention layer 5 A is formed in the vacuum vapor deposition chamber in step 2, and the vacuum vapor deposition in step 3. The transparent metal layer 4 is formed in the chamber, the second sulfidation prevention layer 5B is formed in the vacuum deposition chamber in step 4, and finally, the second high refractive index layer 3B is formed in the vacuum deposition chamber in step 5 by co-evaporation. To produce the transparent conductor 1 of the present invention.

In step 1, the first resistance heating boat T1a is charged with ZnS, and the second resistance heating boat T1b is charged with at least one metal compound selected from metal oxide, metal fluoride, and metal nitride, for example, SiO ₂ . Then, each target is energized and heated under reduced pressure to form a first high refractive index layer 3A composed of ZnS—SiO ₂ on the continuously transported transparent substrate 2 by co-evaporation. At this time, by controlling the heating conditions and vapor deposition rate of the first resistance heating boat T1a and the second resistance heating boat T1b, at least one metal selected from ZnS, metal oxide, metal fluoride, and metal nitride is used. The ratio of the compound and the ratio in the layer can be adjusted.

Next, in step 2, the resistance heating boat T2 is charged with a sulfidation prevention layer forming material, for example, ZnO, energized and heated under predetermined conditions, and on the first high refractive index layer 3A of the transparent substrate 2 being continuously conveyed. Then, the first sulfidation preventing layer 5A is formed.

Next, in step 3, the resistance heating boat T3 is charged with a transparent metal layer forming material, for example, Ag, and is heated by energization under a predetermined condition, on the first sulfidation prevention layer 5A of the transparent substrate 2 being continuously conveyed. The transparent metal layer 4 is formed. At this time, in step 3, it is preferable that the transparent metal layer 4 is formed of silver and the formation rate of the silver layer is 0.3 nm / second or more.

From the viewpoint of realizing higher productivity, the formation rate is more preferably in the range of 0.5 to 30 nm / second, and particularly preferably in the range of 1.0 to 15 nm / second. The vapor deposition method applied in the present invention is characterized by extremely high production efficiency compared to the sputtering method.

The formation speed S (nm / second) referred to in the present invention means that, in Step 3 shown in FIG. 3, a transparent metal layer forming material is loaded on the resistance heating boat T3 as an evaporation source, and a monitor glass is directly above the evaporation source. The transparent metal layer 4 is formed on the monitor glass in a state where the monitor glass is placed so as not to move, and the formation time (seconds) required for forming the transparent metal layer 4 is formed on the monitor glass. The layer thickness of the transparent metal layer 4 is measured, and the formation speed S (nm / second) is calculated from the layer thickness (nm) of the transparent metal layer / formation time (seconds).

Next, in step 4, the resistance heating boat T4 is charged with a sulfidation prevention layer forming material, for example, ZnO, energized and heated under predetermined conditions, and on the transparent metal layer 4 of the transparent substrate 2 being continuously conveyed, A disulfide prevention layer 5B is formed.

Finally, in step 5, the first resistance heating boat T5a is made of ZnS, and the second resistance heating boat T5b is at least one metal compound selected from metal oxide, metal fluoride and metal nitride, for example, was charged with SiO _2, by energizing heating each target under reduced pressure, the second refractive index configured on the transparent metal layer 4 of the transparent substrate 2 which is continuously conveyed, by a co-evaporation method with ZnS-SiO ₂ Layer 3B is formed. At this time, by controlling the heating conditions and vapor deposition rate of the first resistance heating boat T5a and the second resistance heating boat T5b, at least one metal selected from ZnS, metal oxide, metal fluoride, and metal nitride. The ratio of the compound and the ratio in the layer can be adjusted.

In addition, although the vapor deposition method using a resistance heating boat was demonstrated as an example in the above, you may apply the other vapor deposition method using an electron beam etc., for example.

The transparent conductor 1 of this invention can be manufactured through the above processes.

In the step shown in FIG. 3, the pressure P ₃ in the vacuum deposition chamber 11 of the step 3 of forming a transparent metal layer 4, and the pressure P ₁ of the vacuum deposition chamber 11 of the step 1 of forming a first high refractive index layer 3A, be set higher than the pressure P ₅ in the vacuum deposition chamber 11 of the step 5 of forming a second high refractive index layer 3B, prevents the inflow of the sulfur component from step 1 to step 3 of forming a transparent metal layer 4 From the viewpoint of being able to do so. Furthermore, the pressure P ₂ of the first pressure P ₁ in the vacuum deposition chamber 11 of the step 1 of forming a high-refractive index layer _3A, the vacuum deposition chamber 11 of the step 2 of forming a first anti-sulfuration layer _5A, the transparent metal layer 4 vacuum deposition chamber 11 the pressure P ₃ of the step 3 of forming the _pressure P ₄ in the vacuum deposition chamber 11 of the step 4 of forming a second anti-sulfuration layer _5B, the vacuum step 5 of forming a second high refractive index layer 3B as the pressure _{P 5} of the deposition chamber 11,
Pressure P ₁ <Pressure P ₂ <Pressure P ₃ > Pressure P ₄ > Pressure P ₅
Maintaining this pressure relationship is a preferred embodiment from the viewpoint of more efficiently preventing the inflow of the sulfur component into Step 3 which is the formation of the transparent metal layer 4.

In the manufacturing process of the transparent conductor, it is preferable to provide a cooling system that can suppress the temperature rise of the transparent substrate during formation and can control the temperature in the range of −20 to 65 ° C.

The pressure in each vacuum deposition chamber is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻³ Pa. In each step, it is preferable to monitor online with a layer thickness monitor so as to obtain a desired layer thickness.

<< Each component of transparent conductor >>
The transparent conductor of the present invention has a configuration in which at least the first high refractive index layer 3A, the transparent metal layer 4, and the second high refractive index layer 3B are laminated in this order on the transparent substrate 2. Furthermore, it has

antisulfurization layers

5A and 5B between the first high refractive index layer 3A and the transparent metal layer 4, or between the second high refractive index layer 3B and the transparent metal layer 4. It is a preferable aspect.

[Transparent substrate]
Examples of the transparent substrate 2 applicable to the transparent conductor 1 of the present invention include materials used for transparent substrates of various display devices.

As the transparent substrate 2, a glass substrate, a cellulose ester resin (for example, triacetyl cellulose (abbreviation: TAC), diacetyl cellulose, acetylpropionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (above, manufactured by Teijin Ltd.)) ), Cycloolefin resin (for example, ZEONOR (manufactured by ZEON), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resin (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon)), Sumipex (manufactured by Sumitomo Chemical Co., Ltd.)), polyimide, phenol resin, epoxy resin, polyphenylene ether (abbreviation: PPE) resin, polyester resin (for example, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN)), poly -Tersulfone resin, acrylonitrile / butadiene / styrene resin (abbreviation: ABS resin) / acrylonitrile / styrene resin (abbreviation: AS resin), methyl methacrylate / butadiene / styrene resin (abbreviation: MBS resin), polystyrene, methacrylic resin, polyvinyl alcohol / ethylene The transparent resin film etc. which consist of vinyl alcohol resin (abbreviation: EVOH), a styrene-type block copolymer resin, etc. can be mentioned. When the transparent substrate 2 is a transparent resin film, the film may contain two or more kinds of resins.

From the viewpoint of achieving high transparency, the transparent substrate 2 applied to the present invention includes a glass substrate, a cellulose ester resin, a polycarbonate resin, a polyester resin (particularly polyethylene terephthalate), a triacetyl cellulose, a cycloolefin resin, Resin components such as phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyether sulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin It is preferable that it is a film comprised from these.

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

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate 2. On the other hand, the average absorptance is measured by measuring the average reflectance of the transparent substrate 2 by making light incident from the same angle as the average transmittance.
Average absorptivity = 100− (average transmittance + average reflectance)
Calculate as The average transmittance and the average reflectance can be measured using a spectrophotometer.

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

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

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

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

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

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

The first high refractive index layer 3A includes a dielectric material or metal oxide semiconductor material having a refractive index higher than that of the transparent substrate 2 described above. The refractive index of light with a wavelength of 570 nm of the dielectric material or metal oxide semiconductor material is preferably about 0.1 to 1.1 higher than the refractive index of light with a wavelength of 570 nm of the transparent substrate 1, and 0.4 to 1 More preferably, it is about 0.0 larger. The refractive index as used in the present invention is a refractive index value measured in an environment of 25 ° C. The refractive index can be determined by measuring using a commercially available ellipsometer.

On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or metal oxide semiconductor material contained in the first high refractive index layer 3A is preferably greater than 1.5, and is preferably 1.7 to 2.5. More preferably, it is within the range, and more preferably within the range of 1.8 to 2.5. When the refractive index of the dielectric material or the metal oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 1 is sufficiently adjusted by the first high refractive index layer 3A. The refractive index of the first high refractive index layer 3A is adjusted by the refractive index of the material included in the first high refractive index layer 3A and the density of the material included in the first high refractive index layer 3A.

In the present invention, at least one of the first high-refractive index layer and the second high-refractive index layer described later is composed of zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. The mixed film is formed by a co-evaporation method.

Examples of the metal oxide that can be used with zinc sulfide include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ATO (Sb-doped SnO) ), ICO (indium cerium oxide), Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , A-GIO (amorphous oxide composed of gallium, indium, and oxygen). Among the metal oxides, silicon dioxide (SiO ₂ ) is particularly preferable.

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

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

The first high-refractive index layer 3A or the second high-refractive index layer 3B according to the present invention is characterized by containing at least ZnS as a dielectric material. By making ZnS coexist in the rate layer 3B, it becomes difficult for water to permeate from the transparent substrate 2 side, and corrosion of the transparent metal layer 4 is suppressed.

In the present invention, the first high refractive index layer 3A is formed by co-evaporating at least one metal compound selected from metal oxide, metal fluoride and metal nitride together with zinc sulfide. Tends to be amorphous, and the flexibility of the transparent conductor is likely to increase.

In the first high refractive index layer 3A, the average content of zinc sulfide is in the range of 0.5 to 99% by mass with respect to the total number of moles of the material constituting the first high refractive index layer 3A. Preferably, it is in the range of 50 to 95% by mass, and more preferably in the range of 60 to 85% by mass. When the ratio of ZnS is high, the co-evaporation rate is increased, and the formation rate of the first high refractive index layer 3A is increased. Further, when the ratio of zinc sulfide is high, the refractive index is increased, and the absorption of Ag can be reduced. On the other hand, when many components other than ZnS are contained, the amorphousness of the first high refractive index layer 3A is increased, and the occurrence of cracks in the first high refractive index layer 3A is suppressed.

In the transparent conductor of the present invention, as described above, the first high refractive index layer 3A or the second high refractive index layer 3B further includes an interface region 0.1T (adjacent interface) adjacent to the transparent metal layer 4. To the thickness direction, and the average zinc sulfide concentration in the region of 10% of the total layer thickness) is preferably 50% by volume or more, more preferably the transparent metal of the first high refractive index layer 3A. mean zinc sulfide concentration, and the average zinc sulfide concentration in the interface region 0.1 T _B which is adjacent to the transparent metal layer 5 of the second high refractive index layer 3B are both 70 volume in the interface region 0.1 T _a and the adjacent layer 5 % Is a preferred embodiment. Furthermore, it is preferably 80% by volume or more, particularly preferably 90% by volume or more.

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

The first high refractive index layer 3A is formed by a co-evaporation method. Deposition methods applicable to the present invention include resistance heating vapor deposition, electron beam vapor deposition, ion plating, and ion beam vapor deposition. As the vapor deposition apparatus, for example, a BMC-800T vapor deposition machine manufactured by SYNCHRON Co., Ltd. can be used.

Further, when the first high refractive index layer 3A is a layer patterned into a desired shape, the patterning method is not particularly limited. The first high refractive index layer 3A may be, for example, a layer formed in a pattern by a vapor phase forming method by placing a mask having a desired pattern on the surface to be formed, and may be a known etching method, For example, it may be a layer patterned by photolithography.

[First sulfurization prevention layer]
The first high refractive index layer 3A or the second high refractive index layer 3B according to the present invention is characterized by containing zinc sulfide. For example, when the first high-refractive index layer 3A is a layer containing zinc sulfide, as shown in FIGS. 1B and 1C, the first anti-sulfurization layer is provided between the first high-refractive index layer 3A and the transparent metal layer 4. It is a preferred embodiment to form the layer 5A. Although the first sulfidation preventing layer 5A may be formed also in the insulating region b of the transparent conductor 1, as shown in FIG. 2 from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b. Preferably, it is formed only in the conduction region a.

The first antisulfurization layer 5A according to the present invention can be configured as a metal oxide, metal nitride, metal fluoride, or the like, or a layer containing Zn. The first sulfidation preventing layer 5A may contain only one kind, or two or more kinds, but preferably contains a compound containing a zinc metal element. However, when the first high refractive index layer 3A, the first sulfidation preventing layer 5A, and the transparent metal layer 4 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. A compound is preferred. In the case where the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Examples of the metal oxide, metal nitride, and metal fluoride applicable to the first sulfidation preventing layer 5A according to the present invention include the metal oxide, metal nitride, and metal described in the description of the first high refractive index layer 3A. The metal compound similar to a fluoride can be mentioned. In the present invention, Zn, ZnO, IZO (indium oxide / zinc oxide) and GZO (gallium-doped zinc oxide) are particularly preferable.

Here, the thickness of the first antisulfurization layer 5A is preferably a thickness capable of protecting the surface of the first high refractive index layer 3A from an impact when forming the transparent metal layer 4 described later. On the other hand, ZnS that can be included in the first high refractive index layer 3 A has a high affinity with the metal included in the transparent metal layer 4. Therefore, if the thickness of the first anti-sulfurization layer 5A is very thin and a part of the first high refractive index layer 3A is slightly exposed, a transparent metal layer grows around the exposed part, and the transparent metal Layer 4 tends to be dense. In other words, the first antisulfurization layer 5A is preferably relatively thin, preferably in the range of 0.1 to 15 nm, more preferably in the range of 0.5 to 10 nm, and still more preferably 1 to 5 nm. Is within the range. The thickness of the first sulfurization preventing layer 5A can be measured using an ellipsometer.

The first sulfurization preventing layer 5A can be 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, etc. It is preferable to do.

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

(Transparent metal layer)
The transparent metal layer 4 is a film for conducting electricity in the transparent conductor 1. The transparent metal layer 4 may be formed on the entire surface of the transparent substrate 2 as shown in FIGS. 1A to 1C, or may be patterned into a desired shape as shown in FIG.

The metal contained in the transparent metal layer 4 is not particularly limited as long as it is a highly conductive metal, and examples thereof include silver, copper, gold, platinum group, titanium, and chromium. The transparent metal layer 4 may contain only one kind of these metals or two or more kinds.

From the viewpoint of high conductivity, the metal element constituting the transparent metal layer 4 is preferably made of silver or an alloy containing 90 atomic% or more of silver. Examples of the metal combined with silver include zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, and molybdenum. For example, when silver and zinc are combined, the sulfide resistance of the transparent metal layer is increased. When silver and gold are combined, salt resistance (NaCl) resistance increases. Furthermore, when silver and copper are combined, the oxidation resistance increases.

The plasmon absorption rate of the transparent metal layer 4 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region a of the transparent conductor 1 is likely to be colored.

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

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

(Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal film, and the 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 layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, the transmittance | permeability and a reflectance are measured similarly. 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 layer 4 is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm. In the transparent conductor 1 of the present invention, since the thickness of the transparent metal layer 4 is 10 nm or less, the metal inherent reflection hardly occurs in the transparent metal layer 4. Furthermore, when the thickness of the transparent metal layer 4 is 10 nm or less, the optical admittance of the transparent conductor 1 can be easily adjusted by the first high refractive index layer 3A and the second high refractive index layer 3B, and the surface of the conductive region a can be adjusted. Light reflection is easily suppressed. The thickness of the transparent metal layer 4 can be determined by measurement using an ellipsometer.

The transparent metal layer 4 may be a layer formed by any formation method, but is preferably a layer formed by a vacuum deposition method.

If it is a vacuum evaporation method, a transparent substrate will not be exposed to a high temperature environment, but a transparent metal layer with high flatness can be formed at a very high formation rate.

On the other hand, when the transparent metal layer 4 is formed on an underlayer described later, since the underlayer becomes a growth nucleus when the transparent metal layer 4 is formed, the transparent metal layer 4 tends to be a smooth film. As a result, even if the transparent metal layer 4 is thin, plasmon absorption hardly occurs.

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

[Second anti-sulfurization layer]
The second high refractive index layer 3B is a layer containing at least zinc sulfide. As illustrated in FIG. 1C, the second antisulfuric layer 5B is formed between the transparent metal layer 4 and the second high refractive index layer 3B. It is preferable that it is the structure comprised.

The second sulfidation preventing layer 5B may be formed also in the insulating region b of the transparent conductor 1, 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 sulfidation preventing layer 5B can be formed by the same material and method as the first sulfidation preventing layer.

The thickness of the second antisulfurization layer 5B is preferably a thickness capable of protecting the surface of the transparent metal layer 4 from an impact during film formation of the second high refractive index layer 3B described later. On the other hand, since the metal contained in the transparent metal layer 4 and ZnS contained in the second high refractive index layer 3B have high affinity, the thickness of the second antisulfurization layer 5B is very thin. If a part of the layer is slightly exposed, the adhesion between the transparent metal layer 4 or the second antisulfurization layer 5B and the second high refractive index layer 3B is likely to increase. Therefore, the specific thickness of the second antisulfurization layer 5B is preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.5 to 5 nm, and still more preferably in the range of 1 to 3 nm. Within range. The thickness of the second sulfidation preventive layer 5B is measured with an ellipsometer.

[Second high refractive index layer]
The second high refractive index layer 3B is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor 1, that is, the region where the transparent metal layer 4 is formed, and at least the transparent conductor 1 conductive region a. The second high-refractive index layer 3B may be formed in the insulating region b of the transparent conductor 1, but is formed only in the conductive region a from the viewpoint of making it difficult to visually recognize the pattern including the conductive region a and the insulating region b. It is preferable that

When the first high refractive index layer 3A is a layer not containing zinc sulfide, the second high refractive index layer 3B is at least selected from zinc sulfide, metal oxide, metal fluoride, and metal nitride. The high refractive index layer according to the present invention is formed by co-evaporation with a kind of metal compound. Further, both the first high refractive index layer 3A and the second high refractive index layer 3B are prepared by co-evaporation of zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. It may be a formed layer.

The second high-refractive index layer 3B according to the present invention can be formed by using the same constituent material as that of the first high-refractive index layer 3A described above, under the same method and conditions, and detailed description thereof is omitted. .

[Other component layers]
(Underlayer)
In the transparent conductor 1 of this invention, you may provide the base layer used as a growth nucleus at the time of formation of the transparent metal layer 4 as needed. The underlayer is a layer disposed on the transparent substrate 1 side with respect to the transparent metal layer 4 and at a position adjacent to the transparent metal layer 4, and between the first high refractive index layer 3A and the transparent metal layer 4, or the first 1 It is preferable to form between the sulfidation prevention layer 5A and the transparent metal layer 4. The underlayer is preferably formed at least in the conductive region a of the transparent conductor 1, and may be formed in the insulating region b of the transparent conductor 1.

By providing the base layer on the transparent conductor 1, even when the transparent metal layer 4 is thin, the smoothness of the surface of the transparent metal layer 4 can be improved. The reason is as follows.

When the material of the transparent metal layer 4 is vapor-deposited on the first high refractive index layer 3A by a general vacuum vapor deposition method, for example, at the initial stage of formation, atoms attached on the first high refractive index layer 3A, for example, Silver atoms migrate (move), and atoms gather together to form a mass (sea-island structure). And a film grows clinging to this lump. Therefore, in the film at the initial stage of formation, there is a gap between the lumps, and the film 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 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 3A, the transparent metal layer 4 grows using the base layer as a growth nucleus. That is, the material of the transparent metal layer 4 is difficult to migrate, and the film grows without forming the island-like structure described above. As a result, a smooth transparent metal layer 4 can be easily obtained even if the thickness is small.

The underlayer preferably contains palladium, molybdenum, zinc, germanium, niobium or indium, an alloy of these metals with other metals, or an oxide or sulfide of these metals (for example, ZnS). . 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 layer 4 increases, and the adhesion between the base layer and the transparent metal layer 4 tends to increase. 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, and examples thereof include platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, and chromium.

The layer thickness of the underlayer is preferably 3 nm or less, more preferably 0.5 nm or less, and particularly preferably a monoatomic film. The underlayer can also be a film in which metal atoms are deposited on the transparent substrate 2 so as to be separated from each other. When the adhesion amount of the underlayer is 3 nm or less, the underlayer hardly affects the light transmittance and optical admittance of the transparent conductor 1. The presence or absence of the underlayer is confirmed by the ICP-MS method. The layer thickness of the underlayer is calculated from the product of the formation speed and the formation time.

The underlayer is preferably a layer formed by a vapor deposition method. The vapor deposition method includes a vacuum vapor deposition method, an electron beam vapor deposition method, an ion plating method, an ion beam vapor deposition method and the like. The deposition time is appropriately selected according to the desired thickness of the underlying layer and the formation speed. The deposition rate is preferably 0.01 to 1.5 nm / second, more preferably 0.01 to 0.7 nm / 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 phase forming method by placing a mask having a desired pattern on the surface to be formed; a layer patterned by a known etching method There may be.

(Low refractive index layer)
In the transparent conductor 1 of the present invention, a low refractive index layer (not shown) is provided on the second high refractive index layer 3B for the purpose of adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor. You may have. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 1 or may be formed in both the conductive region a and the insulating region b of the transparent conductor 1.

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

[Physical properties of 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% or more, and even more preferably in both the conduction region a and the insulation region b. Is 88% or more. When the average transmittance in the above wavelength range is 83% or more, the transparent conductor can be applied to applications that require high transparency to visible light, such as touch panels.

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 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and even more preferably in both the conduction region a and the insulation region b. 7% or less. In addition, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 to 800 nm is preferably 15% or less, more preferably 10% or less, both in the conduction region a and the insulation region b. Preferably it is 9% or less. On the other hand, the average reflectance of light having a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, 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 absorptance, and average reflectance are preferably the average transmittance, average absorptivity, and average reflectance measured in the environment where the transparent conductor is used. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to measure the average 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).

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

When the transparent conductor 1 includes the conduction region a and the insulation region b, the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are preferably within ± 30 in any region. More preferably, it is within ± 5.0, 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 commercially available 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 electrical resistance value of the conduction region a is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the conduction region a is measured in accordance with, for example, JIS K7194, ASTM D257, and the like. It is also measured by a commercially available surface electrical resistivity meter.

[Optical admittance of transparent conductor]
The reflectance R of the surface of the transparent conductor transmission region a (the surface of the transparent conductor opposite to the transparent substrate) is determined by the optical admittance Y _{env of the} medium on which light is incident and the surface of the transparent conductor transmission region a. determined from the equivalent admittance _{Y E.} Here, the medium on which 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.

In the above formula, R is the reflectance of the surface. Based on the above formula, the closer the value of | Y _env −Y _E | is to 0, the lower the reflectance R of the surface of the transparent conductor (transmission 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 transparent region a of the transparent conductor is determined from the optical admittance Y of the layers constituting the transparent region a. For example, when the transparent conductor (transmission 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 (transmission region a) is composed of 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)

In the above formula (1), δ = 2πnd / λ, y = n (admittance of the x-th layer film), and d is the thickness of the x-th layer film.

(When the x-th layer is an ideal metal layer)

In the above formula (2), γ = 2π / λ · kd, d is the thickness of the x-th layer film, and k is the refractive index (imaginary part) of the film.

When the x-th layer is the outermost layer, the optical admittance Yx (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.

In FIG. 4, as an example of the transparent conductor, transparent substrate 2 / first high refractive index layer 3A (ZnS—SiO ₂ ) / first antisulfurization layer 5A (ITO) / transparent metal layer 4 (Ag) / second high Refractive index layer 3B (the admittance locus of wavelength 570 nm of the conductive region a of the transparent conductor 1 composed of ZnS—SiO ₂ is shown. The horizontal axis of the graph represents the optical admittance Y of the region expressed as x + ii. The vertical part is the imaginary part of the optical admittance, that is, y in the formula (1) In the illustrated transparent conductor 1, the first antisulfurization layer Since 5A (ITO) is sufficiently thin, its optical admittance is negligible.

4, the last coordinate in 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 of the surface of the transparent metal layer 4 on the high refractive index layer side is Y1 (= x ₁ + iy ₁ ), and the surface of the transparent metal layer 4 on the intermediate layer side When the optical admittance at a wavelength of 570 nm is Y2 (= x ₂ + iy ₂ ), it is preferable that either 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 holds between the admittance Y at the interface between 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 layer 4 is increased, the electric field strength E of the transparent metal layer 4 is decreased 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 and the first high refractive index layer 3A, is adjusted by the thickness of the first high refractive index layer 3A and the like. x ₂ is the refractive index of x ₁ values and the transparent metal layer 4 is adjusted by the thickness and the like of the first transparent metal layer 3A. For example, if a high refractive index and the first high refractive index layer 3A, when the thickness of the first high refractive index layer 3A 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 layer 4 has a large imaginary part value, and the admittance locus greatly moves in the direction of the vertical axis (imaginary part). 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, an equivalent admittance coordinate (x _E , y _E ) of light having a wavelength of 570 nm in the conduction region a and light having a wavelength of 570 nm of a member or environment (medium) in contact with the surface on the second high refractive index layer 3B side of the transparent conductor. The equivalent admittance coordinates (n _env , 0) of the distance ((x _E −n _env ) ² + (y _E ) ² ) ^0.5 ) is preferably less than 0.5, more preferably 0. 3 or less. 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 layer 4 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.

[Method for forming transparent conductor having electrode pattern]
A method for forming a pattern comprising a conductive region and an insulating region as shown in FIG. 2 using the transparent conductor of the present invention will be described.

In the transparent conductor of the present invention, at least the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are laminated in this order on the transparent substrate 1 by the method described above. After the production, it is preferable to pattern the transparent metal layer into a predetermined shape to form a metal pattern electrode. Specifically, for example, as shown in FIG. It is preferable to form an electrode pattern. The line width (conducting region a) of the electrode to be formed is preferably 50 μm or less, and particularly preferably 20 μm or less.

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

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

In the present invention, a conventionally known general photolithography method can be used as appropriate. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally active energy rays such as ultraviolet rays and electron beams may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used. After the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pretreated or post-baked as necessary, and then is etched with an etching solution containing an organic solvent to dissolve each constituent layer in a region not protected by the resist and to form a transparent metal. The layer (silver thin film electrode) is removed. After etching, the remaining resist is removed to obtain a transparent electrode having an intended pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.

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

FIG. 5 is a process diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by a photolithography method.

As a first step, as shown in FIG. 5A, on the transparent substrate 2, the first high refractive index layer 3A, the first antisulfuration layer 5A, the transparent metal layer 4, the second antisulfurization layer 5B, the second high The transparent conductor 1 in which the refractive index layer 3B is laminated in this order is produced.

Next, it is preferable to subject the transparent conductor 1 to an ultrasonic cleaning treatment before forming a resist film in the next step. As ultrasonic cleaning, for example, ultrasonic cleaning and washing with pure water are performed several times using a detergent clean-through 3030 manufactured by Kao Corporation, and then water is blown off with a spin coater and dried in an oven.

Next, in the resist film forming step shown by B in FIG. 5, a resist film 6 composed of a photosensitive resin composition or the like is uniformly coated on the transparent conductor 1. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used. FIG. 5 shows an example of a positive type. As the resist, for example, OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.

As a coating method, it is applied on the transparent conductor 1 by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and heated by a hot plate, oven or the like. It can be pre-baked in the apparatus. Pre-baking can be performed, for example, using a hot plate or the like in a temperature range of 50 to 150 ° C. for 30 seconds to 30 minutes.

Next, in the exposure process shown in FIG. 5C, the exposure apparatus 8 such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner or the like is used through a mask 7 made with a predetermined electrode pattern. The resist film 6A to be removed in the next step is irradiated with light of about 4000 J / m ² (wavelength 365 nm exposure amount conversion). The exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

Next, in the developing step shown in FIG. 5D, when a positive photosensitive resin composition is used by immersing the exposed transparent conductor in a developer, the solubility in the developer by irradiation with light. The resist film 6A in the region where the improvement is made is dissolved. As the developer, for example, when a positive photosensitive resin composition is used as a resist, a developer for positive photoresist “Tokuso SD” series (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation should be used. Can do.
As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed at a temperature range of 50 to 150 ° C.

Next, as shown in FIG. 5E, an etching process using an etching solution 9 is performed.

As the etching solution applicable to the present invention, a solution containing an inorganic acid or an organic acid is preferable, and oxalic acid, hydrochloric acid, acetic acid, and phosphoric acid can be mentioned, and oxalic acid, acetic acid, and phosphoric acid are particularly preferable. Commercially available products can also be used as the etchant, for example, Pure Etch DE100 (oxalic acid) manufactured by Hayashi Junyaku Kogyo Co., Ltd., and “Mixed liquid SEA-5” manufactured by Kanto Chemical Co. (phosphoric acid: 55% by mass, Acetic acid: 30% by mass, water and other components: 15% by mass) and the like can be used.

Specifically, for example, the transparent conductor 1 having the resist film 6 is immersed in an etching solution containing an organic acid or the like, and the transparent electrode unit EU in the insulating region b not protected by the resist film 6 is dissolved. The transparent electrode unit EU in the conductive region a protected by the film 6 is formed as a predetermined electrode pattern. The etching time varies depending on the type of acid to be applied, but is preferably adjusted within a range of 30 to 120 seconds.

Finally, as shown in FIG. 5F, the transparent conductive film is etched using, for example, acetone, sodium hydroxide solution as a resist film remover, or N-300 manufactured by Nagase ChemteX as a commercial product. A transparent conductor having an electrode pattern can be produced by immersing the body and removing the resist film 6.

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

At this time, the surface of the transparent conductor 1 (for example, the surface opposite to the transparent substrate 2) 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, an example in which the transparent conductor of the present invention is applied to a touch panel will be shown.

FIG. 6 is a perspective view showing an example of a configuration of a touch panel including a transparent conductor having an electrode pattern.

A touch panel 21 shown in FIG. 6 is a projected capacitive touch panel. The touch panel 21 includes a transparent conductor 1-1 having a first transparent electrode unit EU-1 on the main surface of the transparent substrate 2-1, and a second transparent on the main surface of the transparent substrate 2-2. The transparent conductor 1-2 having the electrode unit EU-2 is arranged in this order, and the upper part is covered with the front plate 13.

The first transparent electrode unit EU-1 and the second transparent electrode unit EU-2 are each a conductive region a of a transparent conductor on which the electrode pattern described with reference to FIGS. 2 and 5 is formed. Therefore, the first transparent electrode unit EU-1 includes the first high refractive index layer 3A, the first sulfidation preventing layer 5A, the transparent metal layer 4, the second sulfidation preventing layer 5B, the second on the transparent substrate 2-1. The high refractive index layer 3B is laminated in this order. Similarly, the second transparent electrode unit EU-2 has the same configuration.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented. Moreover, in the following description, the numerical value and code | symbol described in the parenthesis after each structural element represent the code | symbol shown in each figure.

<< Production of transparent conductor >>
[Preparation of transparent conductor 1]
Using a cycloolefin polymer (abbreviation: COP) film as a transparent substrate, the first high refractive index layer 3A (ZnS—TiO ₂ ) / transparent metal layer 4 (Ag) / The second high refractive index layer 3B (ZnS—TiO ₂ ) was laminated in this order to form a laminate. Next, the laminate was patterned by the following method, and transparent conductors 1 (1-1, 1-2) having wiring shown in FIG. 6 were produced by a batch method. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of first high refractive index layer (ZnS—TiO ₂ ))
As a vacuum deposition apparatus, a BMC-800T deposition apparatus manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded on the first molybdenum resistance heating boat, TiO ₂ was loaded on the _second resistance heating boat made of molybdenum, and the vacuum chamber was 1 × 10 × 10. After depressurizing to ⁻⁴ Pa, the first resistance heating boat and the second resistance heating boat were energized and heated, and the energization heating conditions of both resistance heating boats were adjusted as appropriate, so that the volume ratio of ZnS and TiO ₂ was 80: The first high refractive index layer having a layer thickness of 36 nm was formed by co-evaporation on the COP film under the conditions of 20 at a formation rate of 0.3 nm / second and a formation time of 120 seconds.

The volume ratio of ZnS to TiO ₂ in the first high refractive index layer was measured using X-ray photoelectron spectroscopy (XPS). As a result, the volume ratio of ZnS to TiO ₂ was 80:20. It was confirmed that.

(Formation of transparent metal layer (Ag))
Next, the COP film on which the first high refractive index layer is formed is fixed to a vacuum vapor deposition apparatus similar to the above, Ag is loaded into a resistance heating boat T3 made of molybdenum, and the vacuum chamber is decompressed to 1 × 10 ⁻⁴ Pa. did. Subsequently, the resistance heating boat was energized and heated, and was vacuum-deposited on the first high refractive index layer of the COP film under the condition that the formation time was 6 seconds, thereby forming a transparent metal layer having a layer thickness of 7.7 nm. The formation speed at this time was 2.7 nm / second as a result of measurement by the following method.

In step 3 shown in FIG. 3, Ag is loaded in a resistance heating boat T3 as an evaporation source in the step 3 shown in FIG. 3, and a monitor glass is disposed immediately above the evaporation source, and the monitor glass is fixed and not moved. A transparent metal layer was formed. The formation time required for forming the thin film was 2.85 seconds, and the thickness of the transparent metal layer formed on the monitor crow was 7.7 nm. From the above measurement results, the formation rate S (nm / second) is 2.7 (layer thickness (nm) / formation time (seconds) = 7.7 (nm) /2.85 (seconds) of the transparent metal layer. nm / second).

(Formation of Second High Refractive Index Layer (ZnS—TiO ₂ ))
Next, the COP film on which the transparent metal layer is formed is fixed to a vacuum vapor deposition apparatus similar to the above, and the first molybdenum resistance heating boat is charged with ZnS, and the second molybdenum resistance heating boat is charged with TiO ₂ . After depressurizing the vacuum tank to 1 × 10 ⁻⁴ Pa, the first resistance heating boat and the second resistance heating boat were energized and heated, and the energization heating conditions of both resistance heating boats were adjusted as appropriate, so that ZnS and TiO ₂ The second high refractive index layer having a layer thickness of 44 nm was formed by co-evaporation on the COP film under the conditions of a volume ratio of 80:20 and a formation speed of 0.37 nm / second and a formation time of 120 seconds. Thus, a transparent conductor 1 was produced.

(Patterning of transparent conductor)
Next, a pattern having the conductive region a and the insulating region b shown in FIG. 2 was formed on the produced transparent conductor 1 according to the patterning method shown in FIG.

Before forming the resist layer (6), the produced transparent conductor 1 was subjected to ultrasonic cleaning treatment. As a cleaning solution, an ultrasonic cleaning process was performed at 25 ° C. for 4 minutes using a detergent “Clean Through 3030 (10%)” manufactured by Kao Corporation. Subsequently, after washing 5 times with pure water at 25 ° C., ultrasonic washing was performed twice with pure water at 25 ° C. for 4 minutes. Finally, water was scattered with a spin coater and then dried in an oven.

Next, on the cleaned transparent conductor 1, OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied as a resist by spin coating and dried at 2000 rpm for 30 seconds to form a resist layer (6) having a thickness of 1 μm. Formed.

Next, ultraviolet rays were irradiated through the mask 7 under conditions of 60 mJ, and developed using a developer for positive photoresist “Tokuso SD-1” (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation as a developer. .

Next, as the etching solution, “mixed liquid SEA-5” (phosphoric acid: 55% by mass, acetic acid: 30% by mass, water and other components: 15% by mass) manufactured by Kanto Chemical Co., Ltd. was used, as shown in FIG. An electrode pattern comprising an insulating region b having only the transparent substrate (2) and an energizing region a having the transparent electrode unit EU was formed. The width of the line-shaped insulating region b was 16 μm.

Finally, the remaining resist layer (6) was peeled off using acetone to form an electrode pattern having wiring.

[Preparation of transparent conductor 2 and transparent conductor 3]
Table 1 shows the types of the transparent substrate, the types and thicknesses of the constituent materials of the first high refractive index layer and the second high refractive index layer, and the formation speed and thickness of the transparent metal layer in the production of the transparent conductor 1. A transparent conductor 2 and a transparent conductor 3 were produced in the same manner except that the conditions were changed.

[Preparation of transparent conductor 4]
A long polycarbonate (abbreviation: PC) film is used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / transparent metal layer (Ag) / second high is formed on the PC film according to the following method. A refractive index layer (ZnS—SiO ₂ ) was successively laminated in this order by a roll-to-roll method using a vacuum deposition method. Next, this laminate was patterned by the same method as used for the transparent conductor 1 to produce a transparent conductor 4 having wiring. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

The production of the transparent conductor 4 was performed using a roll-to-roll type transparent conductor manufacturing apparatus having Steps 1 to 5 shown in FIG. 3 in which five vacuum deposition chambers are continuously arranged.

In the production of the transparent conductor 4, the first high refractive index layer (ZnS—SiO ₂ ) is formed in Step 1, the transparent metal layer (Ag) is formed in Step 3, and the second high refractive index layer is formed. (ZnS—SiO ₂ ) was formed in Step 5.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
A first high refractive index layer was formed by a co-evaporation method while continuously transporting the PC film as the transparent substrate (2) into the vacuum deposition chamber (11) of Step 1 shown in FIG.

Vacuum deposition chamber a first ZnS to molybdenum resistance heating boat (T1a) of (11), the SiO ₂ was loaded into a second resistive heating molybdenum boat (T1b), the pressure _{P 1} in the vacuum deposition chamber 1 × After depressurizing to 10 ⁻⁴ Pa, the first resistance heating boat (T1a) and the second resistance heating boat (T1b) are energized and heated. The first high refractive index layer having a layer thickness of 43 nm is formed by co-evaporation on a PC film with a formation rate of 4.3 nm / second and a formation time of 10 seconds under the condition that the volume ratio of ₂ is 99: 1. did.

(Formation of transparent metal layer (Ag))
Next, the PC film on which the first high refractive index layer was formed was continuously conveyed to Step 3, and a transparent metal layer was formed according to the following method.

In Step 3, the PC film having the first high refractive index layer formed in Step 1 is conveyed, Ag is loaded into the molybdenum resistance heating boat (T3) in the vacuum deposition chamber (11), and the pressure P in the vacuum deposition chamber is set. ₃ was depressurized to 1 × 10 ⁻³ Pa. Next, the resistance heating boat (T3) was heated by energization, and was vacuum-deposited on the first high refractive index layer of the PC film under the conditions of a formation speed of 1.8 nm / second and a formation time of 4.4 seconds. A transparent electrode layer of 8.0 nm was formed.

(Formation of Second High Refractive Index Layer (ZnS—SiO ₂ ))
Next, the PC film on which the transparent metal layer was formed in Step 3 was conveyed to the vacuum vapor deposition chamber in Step 5, and a second high refractive index layer was formed according to the following method to produce a transparent conductor 4.

Vacuum deposition chamber of step 5 the first ZnS to molybdenum resistance heating boat (T5a) of (11), the SiO ₂ was loaded into a second resistive heating molybdenum boat (T5b), the pressure _{P 5} in the vacuum deposition chamber After the pressure is reduced to 1 × 10 ⁻⁴ Pa, the first resistance heating boat (T5a) and the second resistance heating boat (T5b) are energized and heated, and the energization heating conditions of both resistance heating boats are appropriately adjusted, A second high refractive index layer having a layer thickness of 42 nm is formed by co-evaporation on a PC film at a formation rate of 4.2 nm / second and a formation time of 10 seconds under the condition that the volume ratio of ZnS and SiO ₂ is 99: 1. Then, a transparent conductor 4 was produced.

[Production of transparent conductors 5 to 7, 26 and 27]
In the production of the transparent conductor 4, the type of transparent substrate, the types of constituent materials of the first high refractive index layer and the second high refractive index layer, the constituent ratio and the layer thickness to be formed, the formation speed and the layer thickness of the transparent metal layer Transparent conductors 5 to 7, 26 and 27 were produced in the same manner except that the conditions were changed to those described in Tables 1 and 2. However, no wiring was formed in the transmissive conductors 26 and 27.

[Preparation of transparent conductor 8]
A long triacetyl cellulose (abbreviation: TAC) film is used as the transparent substrate, and the first high refractive index layer (ZnS-AZO) / transparent metal layer (Ag) / second is formed on the TAC film according to the following method. An anti-sulfurization layer (TiO ₂ ) / second high refractive index layer (ZnS-AZO) were successively laminated in this order by a roll-to-roll method using a vacuum deposition method. Subsequently, the laminated body was patterned by the same method as that used for the transparent conductor 1 to produce a transparent conductor 8 having wiring. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer. AZO described in the above abbreviations is ZnO doped with Al.

The production of the transparent conductor 8 was performed using a roll-to-roll type transparent conductor manufacturing apparatus provided with five vacuum deposition chambers of Step 1 to Step 5 shown in FIG.

In the production of the transparent conductor 8, the first high refractive index layer (ZnS-AZO) is formed in Step 1, the transparent metal layer (Ag) is formed in Step 3, and the second antisulfurization layer (TiO 2) is formed. ₂ ) was formed in Step 4, and the second high refractive index layer (ZnS-AZO) was formed in Step 5.

(Formation of first high refractive index layer (ZnS-AZO))
A first high refractive index layer was formed by a co-evaporation method while continuously transporting the TAC film as the transparent substrate (2) to the vacuum deposition chamber (11) of Step 1 shown in FIG.

The ZnS to first resistive heating molybdenum boat vacuum deposition chamber (11) (T1a), loaded with AZO to a second resistive heating molybdenum boat (T1b), a 1 × 10 pressure _{P 1} in the vacuum deposition chamber After depressurizing to ^-4 Pa, the first resistance heating boat (T1a) and the second resistance heating boat (T1b) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, and ZnS and AZO A first high refractive index layer having a layer thickness of 42 nm was formed by co-evaporation on the TAC film at a formation rate of 2.1 nm / second and a formation time of 20 seconds under the condition that the volume ratio was 80:20.

(Formation of transparent metal layer (Ag))
Next, the TAC film on which the first high refractive index layer was formed was continuously conveyed to Step 3, and a transparent metal layer was formed according to the following method.

The TAC film on which the first high refractive index layer is formed in Step 1 is conveyed to Step 3, and Ag is loaded into the molybdenum resistance heating boat (T3) in the vacuum deposition chamber (11), and the pressure P ₃ in the vacuum deposition chamber is set. The pressure was reduced to 1 × 10 ⁻³ Pa. Next, the resistance heating boat (T3) was heated by energization, and was vacuum-deposited on the first high refractive index layer of the TAC film under the conditions that the formation speed was 1.4 nm / second and the formation time was 5.3 seconds, and the layer thickness was Formed a transparent metal layer of 7.4 nm.

(Formation of second sulfidation preventive layer (TiO ₂ ))
Next, the TAC film on which the transparent metal layer was formed was conveyed to step 4 and a second sulfidation preventive layer was formed according to the following method.

In Step 4, the TAC film on which the transparent metal layer has been formed in Step 3 is transported, and in the vacuum deposition chamber (11), TiO ₂ is loaded into the molybdenum resistance heating boat (T4), and the pressure P ₄ in the vacuum deposition chamber is set. The pressure was reduced to 5 × 10 ⁻⁴ Pa. Next, the resistance heating boat (T4) was heated by energization, and was vacuum-deposited on the transparent metal layer of the TAC film under the conditions of a formation rate of 0.50 nm / second and a formation time of 20 seconds. A disulfide prevention layer was formed.

(Formation of Second High Refractive Index Layer (ZnS-AZO))
Next, the TAC film on which the second sulfidation-preventing layer was formed in Step 4 was conveyed to the vacuum deposition chamber in Step 5, and a second high refractive index layer was formed according to the following method to produce a transparent conductor 8.

The ZnS to first resistive heating molybdenum boat vacuum deposition chamber (11) (T5a), loaded with AZO to a second resistive heating molybdenum boat (T5b), the pressure _{P 5} to 1 × 10 vacuum deposition chamber After depressurizing to ^-4 Pa, the first resistance heating boat (T5a) and the second resistance heating boat (T5b) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, so that ZnS and AZO A second high refractive index layer having a layer thickness of 44 nm was formed by co-evaporation on the TAC film under the conditions of a volume ratio of 80:20 and a formation speed of 2.1 nm / second and a formation time of 20 seconds.

[Production of transparent conductors 9 to 12, 16, 21 to 25, 28]
In the production of the transparent conductor 8, the type of the transparent substrate, the type of constituent material of the first high refractive index layer and the second high refractive index layer, the constituent ratio and layer thickness, the constituent material of the transparent metal layer, the forming speed and the layer Transparent conductors 9 to 12, 16, 21 to 25, and 28 were produced in the same manner except that the thickness, the constituent material and the film thickness of the second sulfurization prevention layer were changed to the conditions described in Tables 1 and 2. . In the transparent conductor 28, no wiring was formed.

[Preparation of transparent conductor 13]
A long thin glass is used as the transparent substrate, and the first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (ZnO) / transparent metal layer (Ag) is formed on the thin glass according to the following method. / Second anti-sulfurization layer (ZnO) / second high refractive index layer (ZnS—SiO ₂ ) were successively laminated in this order by a roll-to-roll method using a vacuum deposition method. Next, the laminate was patterned by the same method as that used for the transparent conductor 1 to produce a transparent conductor 13 having wiring. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

For production of the transparent conductor 13, a roll-to-roll type transparent conductor manufacturing apparatus including the five vacuum deposition chambers, which includes the steps 1 to 5 shown in FIG. 3, was used.

In the production of the transparent conductor 13, the first high refractive index layer (ZnS—SiO ₂ ) is formed in Step 1, the first antisulfurization layer (ZnO) is formed in Step 2, and the transparent metal layer (Ag ) Was formed in Step 3, the second anti-sulfurization layer (ZnO) was formed in Step 4, and the second high refractive index layer (ZnS—SiO ₂ ) was formed in Step 5.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
The first high refractive index layer was formed by a co-evaporation method while continuously transporting the thin glass as the transparent substrate (2) into the vacuum deposition chamber (11) of Step 1 shown in FIG.

Vacuum deposition chamber a first ZnS to molybdenum resistance heating boat (T1a) of (11), the SiO ₂ was loaded into a second resistive heating molybdenum boat (T1b), the pressure _{P 1} in the vacuum deposition chamber 1 × After depressurizing to 10 ⁻⁴ Pa, the first resistance heating boat (T1a) and the second resistance heating boat (T1b) are energized and heated. The first high refractive index layer having a layer thickness of 42 nm was formed by co-evaporation on the thin glass under the condition that the volume ratio of ₂ was 90:10 and the formation rate was 42 nm / second and the formation time was 1 second.

(Formation of first antisulfurization layer (ZnO))
Next, the thin glass on which the first high refractive index layer was formed in Step 1 was conveyed to Step 2, and a first sulfurization prevention layer was formed according to the following method.

In Step 2, the thin glass on which the first high refractive index layer is formed in Step 1 is transported, and in the vacuum deposition chamber (11), the molybdenum resistance heating boat (T2) is loaded with ZnO, and the pressure P in the vacuum deposition chamber is increased. ₂ was depressurized to 5 × 10 ⁻⁴ Pa. Next, the resistance heating boat (T2) was heated by energization, and was vacuum-deposited on the first high refractive index layer of thin glass under the conditions of a formation rate of 0.3 nm / second and a formation time of 1 second, and the layer thickness was 0. A first anti-sulfurization layer having a thickness of 3 nm was formed.

(Formation of transparent metal layer (Ag))
Subsequently, the thin glass in which the 1st sulfurization prevention layer was formed in process 2 was conveyed to process 3, and the transparent metal layer was formed according to the following method.

In Step 3, the thin glass on which the first sulfidation-preventing layer is formed in Step 2 is conveyed, Ag is loaded into the molybdenum resistance heating boat (T3) in the vacuum deposition chamber (11), and the pressure P ₃ in the vacuum deposition chamber is set. The pressure was reduced to 1 × 10 ⁻³ Pa. Next, the resistance heating boat (T3) was heated by energization, and was vacuum-deposited on the first sulfidation prevention layer of thin glass under the conditions of a formation speed of 7.7 nm / second and a formation time of 0.87 second. A transparent metal layer of 6.7 nm was formed.

(Formation of second anti-sulfurization layer (ZnO))
Next, the thin glass on which the transparent metal layer was formed in Step 3 was continuously conveyed to Step 4, and a second antisulfurization layer was formed according to the following method.

In Step 4, the thin glass on which the transparent metal layer is formed in Step 3 is transported, and in the vacuum deposition chamber (11), ZnO is loaded into the molybdenum resistance heating boat (T4), and the pressure P ₄ in the vacuum deposition chamber is 5 The pressure was reduced to ^10-4 Pa. Next, the resistance heating boat (T4) was heated by energization, and was vacuum-deposited on the transparent metal layer of thin glass under the conditions that the formation rate was 1.0 nm / second and the formation time was 1 second, and the layer thickness was 1.0 nm. A second antisulfurization layer was formed.

(Formation of Second High Refractive Index Layer (ZnS—SiO ₂ ))
Next, the thin glass on which the second sulfidation-preventing layer was formed in Step 4 was transferred to the vacuum vapor deposition chamber in Step 5, and a second high refractive index layer was formed according to the following method to produce a transparent conductor 13.

Vacuum deposition chamber a first ZnS to molybdenum resistance heating boat (T5a) of (11), the SiO ₂ was loaded into a second resistive heating molybdenum boat (T5b), the pressure _{P 5} in the vacuum deposition chamber 1 × After depressurizing to 10 ⁻⁴ Pa, the first resistance heating boat (T5a) and the second resistance heating boat (T5b) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, so that ZnS and SiO _{2 under} the condition that the volume ratio of ₂ is 90:10, a second high refractive index layer having a layer thickness of 47 nm is formed by co-evaporation on a thin glass with a formation rate of 47 nm / second and a formation time of 1 second, and transparent conductive A body 13 was produced.

[Preparation of transparent conductor 14 and transparent conductor 29]
In the production of the transparent conductor 13, the type of transparent substrate, the types of constituent materials of the first high refractive index layer and the second high refractive index layer, the constituent ratio and the layer thickness to be formed, the formation speed and the layer thickness of the transparent metal layer The transparent conductor 14 and the transparent conductor 29 were produced in the same manner except that the film thicknesses of the first sulfidation prevention layer and the second sulfidation prevention layer were changed to the conditions shown in Tables 1 and 2. In the transparent conductor 29, no wiring was formed.

[Preparation of transparent conductor 15]
A long polycarbonate (abbreviation: PC) film is used as a transparent substrate, and the first high refractive index layer (TiO ₂ ) / first antisulfuration layer (Ge) / transparent metal layer is formed on the PC film according to the following method. The (Ag) / second high refractive index layer (ZnS—SiO ₂ ) was successively laminated in this order by a roll-to-roll method using a vacuum deposition method. Subsequently, the laminated body was patterned by the same patterning method as that used for the transparent conductor 1 to produce a transparent conductor 15 having wiring. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

For production of the transparent conductor 15, a roll-to-roll type transparent conductor manufacturing apparatus provided with five vacuum deposition chambers of Step 1 to Step 5 shown in FIG. 3 was used.

In the production of the transparent conductor 15, the first high refractive index layer (TiO ₂ ) is formed in Step 1, the first antisulfurization layer (Ge) is formed in Step 2, and the transparent metal layer (Ag) is formed. The formation was performed in Step 3, and the formation of the second high refractive index layer (ZnS—SiO ₂ ) was performed using Step 5.

(Formation of first high refractive index layer (TiO ₂ ))
The first high-refractive-index layer was formed by a vapor deposition method while continuously conveying the PC film as the transparent substrate (2) to the vacuum vapor deposition chamber (11) in Step 1 shown in FIG.

The first resistance heating boat (T1a) made of molybdenum in the vacuum deposition chamber (11) is charged with TiO ₂ and the pressure P ₁ in the vacuum deposition chamber is reduced to 1 × 10 ⁻⁴ Pa, and then the first resistance heating boat (T1a) is energized and heated, and vapor-deposited on a PC film under conditions of a formation speed of 4.6 nm / second and a formation time of 10 seconds to form a first high refractive index layer composed of TiO ₂ having a layer thickness of 46 nm. did.

(Formation of first antisulfurization layer (Ge))
Next, the PC film on which the first high refractive index layer was formed was conveyed to step 2, and a first sulfidation prevention layer was formed according to the following method.

In Step 2, the PC film on which the first high refractive index layer is formed in Step 1 is transported, and in the vacuum deposition chamber (11), the molybdenum simple heating boat (T2) is loaded with Ge alone, and the pressure in the vacuum deposition chamber is increased. P ₂ was depressurized to 5 × 10 ⁻⁴ Pa. Next, the resistance heating boat (T2) was heated by energization, and was vacuum-deposited on the first high refractive index layer of the PC film under the conditions that the formation speed was 0.01 nm / second and the formation time was 10 seconds. A 1 nm first antisulfurization layer was formed.

(Formation of transparent metal layer (Ag))
Next, the PC film on which the first sulfidation-preventing layer was formed in Step 2 was conveyed to Step 3, and a transparent metal layer was formed according to the following method.

In Step 3, the PC film on which the first sulfidation-preventing layer is formed in Step 2 is conveyed, Ag is loaded into the molybdenum resistance heating boat (T3) in the vacuum deposition chamber (11), and the pressure P ₃ in the vacuum deposition chamber is set. The pressure was reduced to 1 × 10 ⁻³ Pa. Next, the resistance heating boat (T3) was heated by energization, and was vacuum-deposited on the first antisulfurization layer of the PC film under the conditions of a formation rate of 1.6 nm / second and a formation time of 3.56 seconds. A 5.7 nm transparent metal layer was formed.

(Formation of Second High Refractive Index Layer (ZnS—SiO ₂ ))
Next, the PC film on which the transparent metal layer was formed in Step 3 was conveyed to the vacuum vapor deposition chamber in Step 5, and a second high refractive index layer was formed according to the following method to produce a transparent conductor 15.

Vacuum deposition chamber a first ZnS to molybdenum resistance heating boat (T5a) of (11), the SiO ₂ was loaded into a second resistive heating molybdenum boat (T5b), the pressure _{P 5} in the vacuum deposition chamber 1 × After depressurizing to 10 ⁻⁴ Pa, the first resistance heating boat (T5a) and the second resistance heating boat (T5b) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, so that ZnS and SiO The second high refractive index layer having a layer thickness of 45 nm is formed by co-evaporation on a thin glass under the conditions that the volume ratio of ₂ is 80:20 and the formation speed is 4.5 nm / second and the formation time is 10 seconds. did.

[Preparation of transparent conductor 17]
The production of the transparent conductor 17 is carried out by using two roll-to-roll type transparent conductor manufacturing apparatuses equipped with five vacuum deposition chambers of Step 1 to Step 5 shown in FIG. The vapor deposition chambers (vacuum vapor deposition chambers 1A and 1B, vacuum

vapor deposition chambers

5A and 5B) are configured, and the formation of the first high refractive index layer (ZnS—TiO ₂ ) having two regions is performed in the vacuum vapor deposition chamber 1A and the vacuum vapor deposition chamber 1B. The transparent metal layer (Ag) is formed in Step 3, the second antisulfurization layer (ZnO) is formed in Step 4, and the second high refractive index layer (ZnS—TiO ₂ ) having two regions is formed. Was formed in the vacuum deposition chamber 5A and the vacuum deposition chamber 5B.

(Formation of first high refractive index layer (ZnS—TiO ₂ ))
3 is divided into a process 1A (vacuum deposition chamber 1A) and a process 1B (vacuum deposition chamber 1B), and a polyethylene terephthalate (substantially equipped: PET) film as a transparent substrate (2) is continuously conveyed. The first high refractive index layer having two regions having different composition ratios was formed by a co-evaporation method.

The first molybdenum resistance heating boat (T1Aa) in the vacuum deposition chamber 1A is charged with ZnS, the second molybdenum resistance heating boat (T1Ab) is charged with TiO _2, and the pressure P ₁ in the vacuum deposition chamber is set to 1 × 10 ^{−. The} pressure was reduced to ⁴ Pa.

In addition, ZnS is loaded into the first molybdenum resistance heating boat (T1Ba) in step 1B (vacuum deposition chamber 1B), TiO ₂ is loaded into the second molybdenum resistance heating boat (T1Bb), and the pressure P in the vacuum deposition chamber is increased. ₁ was depressurized to 1 × 10 ⁻⁴ Pa.

As a first step, the region 1 of the first high refractive index layer was formed by co-evaporation while continuously transporting the PET film as the transparent substrate (2) to the process 1A (vacuum deposition chamber 1A). Specifically, the first resistance heating boat (T1Aa) and the second resistance heating boat (T1Ab) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, and the volume ratio of ZnS and TiO ₂ is adjusted. Was 50:50, and the region 1 was formed under the condition that the layer thickness was 32 nm.

Next, as a second step, the PET film which is the transparent substrate (2) in which the region 1 is formed is transported to the process 1B (vacuum deposition chamber 1B), and the first resistance heating boat (T1Ba) and the second resistance heating are performed. The boat (T1Bb) is energized and heated, and the energization and heating conditions of both resistance heating boats are adjusted as appropriate to form region 2 under the condition that the volume ratio of ZnS and TiO ₂ is 80:20 and the layer thickness is 10 nm. A first high refractive index layer having a layer thickness of 42 nm was formed.

The region 1 formed in the step 1A (vacuum deposition chamber 1A) is a region constituting the transparent substrate side of the first high refractive index layer, and the details are shown in the upper part of the “first high refractive index layer” column in Table 2. Described. In addition, the region 2 formed in the step 1B (vacuum deposition chamber 1B) is a region constituting the transparent metal layer side, and details are described in the lower part of the “first high refractive index layer” column in Table 2.

The volume ratio of ZnS and TiO ₂ in each layer in the first high refractive index layer was confirmed to be the above-described ratio using X-ray photoelectron spectroscopy (XPS).

(Formation of transparent metal layer (Ag))
Subsequently, the PET film on which the first high refractive index layer composed of two regions was formed was continuously conveyed to Step 3, and a transparent metal layer was formed according to the following method.

The PET film on which the first high refractive index layer is formed in step 1 is conveyed to step 3, and Ag is loaded into the molybdenum resistance heating boat (T3) in the vacuum deposition chamber (11), and the pressure P ₃ in the vacuum deposition chamber is set. The pressure was reduced to 1 × 10 ⁻³ Pa. Next, the resistance heating boat (T3) was heated by energization, and was vacuum-deposited on the first high refractive index layer of the PET film under the conditions that the formation speed was 0.7 nm / second and the formation time was 10.6 seconds, and the layer thickness was Formed a transparent metal layer of 7.4 nm.

(Formation of second anti-sulfurization layer (ZnO))
Subsequently, the PET film on which the transparent metal layer was formed was conveyed to Step 4 and a second sulfidation preventive layer was formed according to the following method.

In Step 4, the PET film on which the transparent metal layer is formed in Step 3 is transported, and in the vacuum vapor deposition chamber (11), ZnO is loaded into the molybdenum resistance heating boat (T4), and the pressure P ₄ in the vacuum vapor deposition chamber is 5 The pressure was reduced to ^10-4 Pa. Next, the resistance heating boat (T4) was heated by energization, and was vacuum-deposited on the transparent metal layer of the PET film under the conditions of a formation rate of 1.0 nm / second and a formation time of 1 second. A disulfide prevention layer was formed.

(Formation of Second High Refractive Index Layer (ZnS—TiO ₂ ))
Step 5 shown in FIG. 3 is divided into step 5A (vacuum deposition chamber 5A) and step 5B (vacuum deposition chamber 5B), and the first high refractive index layer, the transparent electrode layer, and the second sulfurization prevention by the above method. While continuously transporting the transparent substrate (2) (PET film) on which the layer was formed, a second high refractive index layer having regions having two different composition ratios was formed by a co-evaporation method.

ZnS was charged in the first molybdenum resistance heating boat (T5Aa) in the vacuum evaporation chamber 5A, TiO ₂ was charged in the second molybdenum resistance heating boat (T5Ab), and the pressure P ₁ in the vacuum evaporation chamber was set to 1 × 10 ^{−. The} pressure was reduced to ⁴ Pa.

In addition, ZnS is loaded into the first molybdenum resistance heating boat (T5Ba) in step 5B (vacuum deposition chamber 5B), TiO ₂ is loaded into the second molybdenum resistance heating boat (T5Bb), and the pressure P in the vacuum deposition chamber is increased. ₁ was depressurized to 1 × 10 ⁻⁴ Pa.

As a first step, the region 1 of the second high-refractive-index layer is formed by co-evaporation while continuously transporting the PET film having the second anti-sulfurization layer (ZnO) formed in the process 5A (vacuum deposition chamber 5A). Formed. Specifically, the first resistance heating boat (T5Aa) and the second resistance heating boat (T5Ab) are energized and heated, and the energization heating conditions of both resistance heating boats are adjusted as appropriate, and the volume ratio of ZnS and TiO ₂ is adjusted. Was 80:20, and the region 1 was formed under the condition that the layer thickness was 10 nm.

As a second step, the PET film in which the region 1 is formed is transported to the process 5B (vacuum deposition chamber 5B), and the first resistance heating boat (T5Ba) and the second resistance heating boat (T5Bb) are energized and heated. A second high refraction with a total layer thickness of 44 nm is formed by appropriately adjusting the current heating conditions of both resistance heating boats, forming region 2 under the condition that the volume ratio of ZnS and TiO ₂ is 50:50, and the layer thickness is 34 nm. A rate layer was formed.

Region 1 formed in step 5A (vacuum deposition chamber 5A) is a region constituting the transparent metal layer side of the second high refractive index layer, and the details are shown in the upper part of the “second high refractive index layer” column in Table 2. Was described. Further, the region 2 formed in the step 5B (vacuum deposition chamber 5B) is a region constituting the surface side of the second high refractive index layer, and the details are shown in the lower part of the “second high refractive index layer” column in Table 2. Was described.

It should be noted that the volume ratio of ZnS and TiO ₂ in each layer in the second high refractive index layer was confirmed to be the above-described ratio using X-ray photoelectron spectroscopy (XPS).

[Preparation of transparent conductors 18 to 20]
In the production of the transparent conductor 17, the types and constituent ratios of the constituent materials in the respective regions having different constituent ratios of the first high refractive index layer and the second high refractive index layer were changed to the conditions described in Table 2. Transparent conductors 18 to 20 were produced in the same manner except for the above.

[Preparation of transparent conductor 30]
Using quartz as the transparent substrate, the following high-refractive index layer (ZnS) / transparent metal layer (Ag) / second high-refractive index layer (ZnS) are sequentially deposited on the quartz by the following method. Laminated by the method. Next, the laminate was patterned by the following method, and the transparent conductor 30 having the wiring shown in FIG. 6 was produced by a batch method. The thickness of each layer is J. A. Woollam
Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

In the transparent conductor 30, the first high refractive index layer and the second high refractive index layer are each made of ZnS alone.

(Formation of first high refractive index layer (ZnS))
As a vacuum deposition device, a BMC-800T deposition device manufactured by SYNCHRON Co., Ltd. was used, ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. A first high refractive index layer having a layer thickness of 40 nm was formed.

(Formation of transparent metal layer (Ag))
Next, the quartz on which the first high refractive index layer was formed was fixed to a vacuum vapor deposition apparatus similar to the above, and Ag was loaded into a molybdenum resistance heating boat, and the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa. Subsequently, the resistance heating boat was energized and heated, and a transparent metal layer having a layer thickness of 12 nm was formed under the condition that the formation speed was 0.2 nm / second.

(Formation of Second High Refractive Index Layer (ZnS))
Next, the quartz on which the transparent metal layer was formed was fixed to a vacuum vapor deposition apparatus similar to the above, ZnS was loaded into a molybdenum resistance heating boat, and the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat Was heated by electric current to form a second high refractive index layer having a layer thickness of 40 nm, and a transparent conductor 30 was produced.

[Preparation of transparent conductor 31]
A PET film is used as a transparent substrate, and a first high refractive index layer (Nb ₂ O ₅ ) / transparent metal layer (Ag) / second high refractive index layer (IZO) are sequentially formed on the PET film by the following sputtering method. The transparent conductor 31 was prepared by laminating by the sputtering method.

(Formation of the first high refractive index layer (Nb ₂ O ₅ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, formation rate 0.3. Nb ₂ O ₅ was RF sputtered at nm / second. A target-substrate distance was 90 mm, and a first high refractive index layer having a layer thickness of 28 nm was formed.

(Formation of transparent metal layer (Ag))
Using an opposing sputtering machine manufactured by FTS Corporation, facing sputtering with Ar 20 sccm, sputtering pressure 0.5 Pa, room temperature, target side power 150 W, formation rate 1.4 nm / s, and Ag layer thickness of 7.3 nm did. The target-substrate distance was 90 mm.

(Second high refractive index layer (IZO))
On the transparent metal 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, formation rate 0.2 nm / s, IZO, DC sputtering was performed under the condition that the layer thickness was 36 nm. The target-substrate distance was 86 mm.

[Production of Transparent Conductor 32]
A transparent substrate (TAC) / first high refractive index layer (ICO: 27 nm, Cr: 0.8 nm) is formed by sputtering using a TAC film as the transparent substrate and according to the method described in Examples of Japanese Patent Application Laid-Open No. 2006-184849. / Transparent metal layer (Ag / Au: 9 nm) / Second anti-sulfurization layer (Cr: 0.8 nm) / Second high refractive index layer (ICO: 20 nm, SiO2: 40 nm, KP801M: 8 nm) are laminated in this order Thus, a transparent conductor 32 was produced.

KP501M is a fluorine-based silane compound (fluoroalkylsilazane, manufactured by Shin-Etsu Chemical Co., Ltd.).

[Preparation of transparent conductor 33]
A PET film is used as a transparent substrate, and according to the method described in Examples of Japanese Patent Application Laid-Open No. 2002-15623, a transparent substrate (TAC) / first high refractive index layer (ITO: 40 nm) / transparent metal layer (APC) is formed by sputtering. : 9 nm) / second high refractive index layer (ITO: 40 nm) was laminated in this order to produce a transparent conductor 33.

In addition, as APC, the alloy which consists of Ag (40 atomic%) * Pd (40 atomic%) * Cu (20 atomic%) was used.
[Preparation of transparent conductor 34]
Glass is used as the transparent substrate, and a transparent substrate (glass substrate) / first high-refractive index layer (a-GIO: 50 nm) / transparent metal layer is formed by sputtering according to the method described in the examples of JP-A-2008-226581 (Ag: 10 nm) / second high refractive index layer (a-GIO: 50 nm) were laminated in this order to produce a transparent conductor 34.

Note that a-GIO is an amorphous oxide film made of gallium, indium and oxygen.
[Preparation of transparent conductor 35]
Glass is used as the transparent substrate, and the transparent substrate (glass substrate) / first high refractive index layer (ZnO.SiO ₂ : 45 nm) / transparent is formed by sputtering according to the method described in the example of CN1026777012A, which is a Chinese patent. A metal layer (Ag: 11 nm) / second high refractive index layer (ZnO.SiO ₂ : 45 nm) was laminated in this order to produce a transparent conductor 35.

Tables 1 and 2 show the structures of the transparent conductors 1 to 35 produced as described above.

The details of the constituent elements described in Table 1 and Table 2 with abbreviations or symbols are as follows.

(Transparent substrate)
COP: cycloolefin polymer TAC: triacetyl cellulose PET: polyethylene terephthalate PC: polycarbonate (constituent material of high refractive index layer)
* 1: ZnS-TiO ₂
* 2: ZnS-SiO ₂
* 3: ZnS—Nb ₂ O ₅
* 4: CeO ₂
* 5: ZnS-CeO ₂
* 6: ZnS-AZO (Al-doped ZnO)
* 7: ZnS—HfO ₂
* 8: ZnS—Al ₂ O ₃
* 9: ZnS—Y ₂ O ₃
* 10: ZnS-AlF ₃
* 11: ZnS-LiF
* 12: ZnS-SiN
* 13: ZnS-TiN
* 14: ZnS—Ta ₂ O ₃
* 15: ICO-Cr = 27/1 (nm)
* 16: ICO-SiO ₂ -KP801M = 20/40/6 (nm)
ITO: Indium tin oxide ICO: Indium cerium oxide IZO: Indium zinc oxide ATO: Sb-doped SnO
AZO: Al-doped ZnO
TNO: Nb-doped TiO ₂
a-GIO: amorphous oxide composed of gallium, indium and oxygen KP801M: fluorinated silane compound (fluoroalkylsilazane, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Constituent material of transparent metal layer)
APC: Alloy made of Ag (40 atomic%), Pd (40 atomic%), Cu (20 atomic%) << Evaluation of Transparent Conductor >>
About each produced said transparent conductor, the following characteristic value was measured and evaluated.

[Evaluation of corrosion resistance]
The area range of each of the produced transparent conductors 30 mm × 30 mm was observed using a 100-fold magnifier, the number of corrosions having a size of 20 μm or more was measured, and corrosion resistance was evaluated according to the following criteria.

○: Corrosion is not observed over the entire area (corrosion number: 0)
Δ: The number of occurrences of corrosion is 1 or more and less than 5 over the entire area range ×: The number of occurrences of corrosion is 5 or more over the entire area range [Evaluation of flexibility]
About each produced said transparent conductor, after winding and open | release 1000 times to a metal rod of (phi) 5mm so that a transparent electrode unit surface may become an outer side, the area range of 30 mm x 30 mm of a transparent conductor is 100 times. Observation was made using a magnifying glass, the number of corrosions having a size of 20 μm or more was measured, and flexibility was evaluated according to the following criteria.

○: Corrosion is not observed over the entire area (corrosion number: 0)
Δ: The number of corrosion occurrences is 1 or more and less than 50 in the entire area range ×: The number of corrosion occurrences is 50 or more in the entire area range [Average transmittance, average reflectance and average absorption rate Measurement)
(Measurement of transparent conductor with wiring)
For the transparent conductors 1 to 25, the average transmittance, average reflectance, and average absorptance were measured according to the following method.

Matching oil (refractive index = 1.515 manufactured by Nikon Corporation) was applied to the surface of the transparent conductors 1 to 25 on the second high refractive index layer side. Then, a 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 from the alkali-free glass substrate side, the transparent conductor 450 to 800 nm The average transmittance (%) in the wavelength range, the average transmittance (%) in the wavelength range of 400 to 1000 nm, and the average reflectance were measured and tilted by 5 ° with respect to the normal of the surface of the alkali-free glass substrate. Measurement light (for example, light having a wavelength of 450 nm to 800 nm) was made incident on the conduction region from the measured angle, and light transmittance and reflectance were measured with a spectrophotometer U4100 manufactured by Hitachi, Ltd.

The average absorptance was calculated from a calculation 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 average reflectance. Was defined as the average reflectance of the transparent conductor. Also, regarding the average transmittance, the reflection at the interface between the non-alkali glass substrate and the atmosphere and the reflection at the interface between the transparent substrate and the atmosphere of the transparent conductor are taken into account by 8%. The obtained value was defined as each average transmittance of the transparent conductor.

(Measurement of transparent conductor without wiring)
On the other hand, the transparent conductors 26 to 35 having no wiring are used in contact with air, and the measurement light (for example, wavelength) is applied to the conduction region without bonding an alkali-free glass substrate on the transparent conductor. 450 nm to 800 nm light), and Hitachi Co., Ltd .: spectrophotometer U4100, transparent conductor average transmittance (%) in the wavelength range of 450 to 800 nm, average transmittance in the wavelength range of 400 to 1000 nm (%) And average reflectance were measured.
The average absorptance was calculated from a calculation formula of 100− (average transmittance + average reflectance). The measurement light was incident from the second high refractive index layer side.

Also, a value obtained by subtracting the reflection (4%) at the interface between the transparent substrate and the atmosphere of the transparent conductor from the measured value of the average reflectance was defined as the average reflectance of the transparent conductor. Further, regarding the average transmittance, the reflection of the transparent conductor at the interface between the transparent substrate and the atmosphere is taken into consideration, and the value obtained by adding 4% to the measured value of the average transmittance is defined as the transmittance of the transparent conductor.

[Evaluation of b ^* value of conduction region]
The b ^* value in the L ^* a ^* b ^* color system of each transparent conductor was measured with a spectrophotometer U4100 manufactured by Hitachi, Ltd. Then, based on the measured b ^* value, ranking was performed according to the following criteria.

A: b ^* value is in a range of −1.0 or more and less than +1.0 ○: b ^* value is −2.0 or more and less than −1.0 X: b ^* value is less than −2.0 or more than +2.0 [Measurement of sheet resistance value]
Measure the sheet resistance value (Ω / □) of the conductive region (a) by bringing a resistivity meter “Loresta EP MCP-T360” made by Mitsubishi Chemical Analytech into contact with the conductive region (a) of each transparent conductor. did.

[Evaluation of production efficiency]
The production rate (m / min) per unit time (min) in the method for producing each transparent conductor was measured to determine the production rate (m / min), and the production efficiency was evaluated according to the following criteria.

A: Production speed is 10 m / min or more. O: Production speed is 5 m / min or more and less than 10 m / min. Δ: Production speed is 3 m / min or more and less than 5 m / min. X: Production speed Table 3 shows the results obtained as described above.

As is clear from the results shown in Table 3, the first high refractive index layer has the first high refractive index layer, the transparent metal layer, and the second high refractive index layer on the transparent substrate defined in the present invention. And at least one layer of the second high refractive index layer was produced by forming a mixed film of zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride and metal nitride by a co-evaporation method. It turns out that the transparent conductor of this invention is excellent in corrosion resistance and flexibility with respect to a comparative example, is excellent in the average transmittance | permeability, average reflectance, and average absorptivity as a transparent conductor, and b ^* value is also favorable. . Moreover, the low sheet resistance value as a transparent conductor was able to be obtained.

Further, the above characteristics are that the metal oxide constituting the first high-refractive index layer or the second high-refractive index layer is silicon dioxide, the transparent metal layer is mainly composed of silver, and the formation rate is 0.8. Forming a silver film under the condition of 3 nm / second or more, as confirmed by the transparent conductors 17 to 20, the first high refractive index layer and the second high refractive index layer are adjacent to the transparent metal layer (adjacent region). Forming an average zinc sulfide concentration in the thickness direction from the interface to 10% of the total layer thickness) under the condition of 70% by volume or more, between the first high refractive index layer and the transparent metal layer, Alternatively, by forming a sulfidation prevention layer between the second high refractive index layer and the transparent metal layer, and forming the sulfidation prevention layer from a material containing a zinc metal element, the above characteristics are further improved. It can be seen that this is a more preferable condition.

In addition, in the transparent conductors 1 to 29 of the present invention produced by the vapor deposition method, the production rate (m / min) represented by the production amount (m) per unit time (min) is 3 m / min or more, and the sputtering is performed. In the transparent conductors 31 to 35 produced by the method, the production rate is less than 3 m / min, the production rate is extremely low, and the transparent conductor production method (evaporation method) of the present invention is a comparative example (sputtering method). On the other hand, it can be seen that the production efficiency is extremely superior.

The transparent conductor produced by the method for producing a transparent conductor of the present invention has flexibility, excellent transparency and resistance to coloring, and has low resistance characteristics, such as a liquid crystal method, a plasma method, an organic electroluminescence method, a field emission. It can be suitably used for various optoelectronic device substrates such as various types of displays, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescence light control elements, and the like.

1, 1-1, 1-2 Transparent conductor 2, 2-1, 2-2 Transparent substrate 3A First high refractive index layer 3B Second high refractive index layer 4 Transparent metal layer 5 Antisulfuration layer 5A First antisulfuration Layer 5B Second sulfidation prevention layer 6 Resist film 6A Resist film to be removed 7 Mask 8 Exposure machine 9 Etching solution 10 Bulkhead 11 Vacuum deposition chamber 13 Front plate 21 Touch panel a Conduction area b Insulation area EU, EU-1, EU-2 Transparent Electrode unit L formation range (m)
T1aM, T1b, T2, T3, T4, T5a, T5b Target (resistance heating boat)
P ₁ , P ₂ , P ₃ , P ₄ , P ₅ Pressure in the vacuum deposition chamber

Claims

On the transparent substrate, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are laminated in this order to produce a transparent conductor,
At least one layer of the first high-refractive index layer and the second high-refractive index layer is a co-evaporation of a mixed film of zinc sulfide and at least one metal compound selected from metal oxide, metal fluoride, and metal nitride. A method for producing a transparent conductor, characterized by being formed by a method.
The method for producing a transparent conductor according to claim 1, wherein the metal oxide is silicon dioxide.
3. The method for producing a transparent conductor according to claim 1, wherein the transparent metal layer is composed of silver as a main component and is formed under a condition of a formation rate of 0.3 nm / second or more.
The first high refractive index layer or the second high refractive index layer has an average zinc sulfide concentration of 50% by volume in an interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the entire layer thickness). It forms on the conditions used as the above, The manufacturing method of the transparent conductor as described in any one of Claim 1- Claim 3 characterized by the above-mentioned.
Each of the first high refractive index layer and the second high refractive index layer has an average zinc sulfide concentration of 70 volumes in an interface region adjacent to the transparent metal layer (10% region in the thickness direction from the surface of the total thickness). The method for producing a transparent conductor according to any one of claims 1 to 3, wherein the transparent conductor is formed under a condition of% or more.
6. An antisulfurization layer is formed between the first high refractive index layer and the transparent metal layer, or between the second high refractive index layer and the transparent metal layer. The manufacturing method of the transparent conductor as described in any one of the above.
The method for producing a transparent conductor according to claim 6, wherein the anti-sulfurization layer is formed of a material containing a zinc metal element.
The method for producing a transparent conductor according to any one of claims 1 to 7, wherein the transparent metal layer is patterned into a predetermined shape to form a metal pattern electrode.
A transparent conductor produced by the method for producing a transparent conductor according to any one of claims 1 to 8,
On the transparent substrate, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are provided in this order, and at least of the first high refractive index layer and the second high refractive index layer. One layer is a mixed film of zinc sulfide and at least one metal compound selected from metal oxides, metal fluorides, and metal nitrides.
The transparent conductor according to claim 9, wherein the metal oxide is silicon dioxide.
The first high refractive index layer or the second high refractive index layer has an average zinc sulfide concentration of 50% by volume in an interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the entire layer thickness). It is the above, The transparent conductor of Claim 9 or Claim 10 characterized by the above-mentioned.
Each of the first high refractive index layer and the second high refractive index layer has an average zinc sulfide concentration of 70 volumes in an interface region adjacent to the transparent metal layer (10% in the thickness direction from the surface of the total thickness). The transparent conductor according to claim 9 or 10, wherein the transparent conductor is at least%.
13. A sulfidation preventing layer is provided between the first high refractive index layer and the transparent metal layer, or between the second high refractive index layer and the transparent metal layer. The transparent conductor as described in any one of these.
The transparent conductor according to claim 13, wherein the antisulfurization layer contains a zinc metal element.
The transparent conductor according to any one of claims 9 to 14, wherein the transparent metal layer is a metal pattern electrode patterned in a predetermined shape.