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WO2015118726A1 - Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device formed using transparent conductive laminate - Google Patents

Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device formed using transparent conductive laminate Download PDF

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Publication number
WO2015118726A1
WO2015118726A1 PCT/JP2014/077185 JP2014077185W WO2015118726A1 WO 2015118726 A1 WO2015118726 A1 WO 2015118726A1 JP 2014077185 W JP2014077185 W JP 2014077185W WO 2015118726 A1 WO2015118726 A1 WO 2015118726A1
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Prior art keywords
zinc oxide
oxide film
transparent conductive
conductive laminate
film
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French (fr)
Japanese (ja)
Inventor
務 原
智史 永縄
公市 永元
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Lintec Corp
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Lintec Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80517—Multilayers, e.g. transparent multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates

Definitions

  • the present invention relates to a transparent conductive laminate, a method for producing a transparent conductive laminate, and an electronic device using the transparent conductive laminate, and in particular, a transparent conductive laminate and a transparent conductive laminate excellent in wet heat characteristics. And an electronic device using such a transparent conductive laminate.
  • a transparent conductive laminate using tin-doped indium oxide as a material for forming a transparent conductive layer has been widely used.
  • a transparent conductive laminate using zinc oxide with excellent transparency and surface smoothness has been proposed as an alternative to a transparent conductive layer using tin-doped indium oxide containing a large amount of indium, which is an expensive and rare metal.
  • a transparent conductive film is proposed in which an Al 2 O 3 thin film is formed on an organic polymer film substrate, and a GZO thin film of ZnO doped with Ga is formed thereon. (For example, refer to Patent Document 1).
  • a low-resistivity transparent conductor which has a zinc oxide as a main component and a dopant whose concentration can be easily controlled. That is, a transparent conductor made of zinc oxide, indium oxide, and gallium oxide, and a low-resistance transparent conductor in which the element concentrations of indium and gallium are each within a predetermined range has been proposed (for example, Patent Documents). 2).
  • a transparent conductive zinc oxide film doped with a specific element has been proposed for the purpose of obtaining excellent moisture and heat resistance characteristics even at an extremely thin film level. That is, a first element composed of Ga and / or Al and a second element composed of at least one selected from the group consisting of In, Bi, Se, Ce, Cu, Er, and Eu are added to zinc oxide.
  • a conductive zinc oxide film has been proposed (for example, Patent Document 3).
  • the transparent conductive film disclosed in Patent Document 1 requires an Al 2 O 3 thin film as an undercoat layer
  • the zinc oxide film doped only with gallium still has insufficient moisture and heat resistance characteristics.
  • the low resistivity transparent conductor disclosed in Patent Document 2 has improved the resistivity
  • the transparent conductive zinc oxide film disclosed in Patent Document 3 has some wet heat characteristics, the film forming conditions are relatively severe, and the film thickness must be 140 nm or less.
  • the application is relatively narrow and limited.
  • an object of the present invention is to provide a transparent conductive laminate excellent in wet heat characteristics, a method for producing the transparent conductive laminate, and an electronic device using such a transparent conductive laminate.
  • a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is a first zinc oxide along the thickness direction from the base material side.
  • the first zinc oxide film is a zinc oxide film not containing indium
  • the second zinc oxide film is a zinc oxide film containing indium.
  • Another aspect of the present invention is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a substrate, and the transparent conductive layer is formed from the substrate side along the film thickness direction. 2 zinc oxide film and first zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is made of indium.
  • a transparent conductive laminate comprising a zinc oxide film.
  • the first zinc oxide film is preferably a zinc oxide film formed by doping gallium. With this configuration, a zinc oxide film having a particularly low initial specific resistance can be obtained.
  • the second zinc oxide film is preferably a zinc oxide film doped with indium and gallium. By comprising in this way, it can be set as the zinc oxide film
  • the second zinc oxide film has an indium amount of 0 with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. A value within the range of 0.01 to 25 atom% is preferable.
  • the ratio represented by ⁇ 1 / ⁇ 0 is preferably set to a value of 1.3 or less.
  • the base material is at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, cycloolefin polymer, polyethersulfone, and polyimide. preferable.
  • flexibility and transparency can be provided to a transparent conductive laminated body.
  • Another embodiment of the present invention is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode.
  • the long-term stability of an electronic device can be suitably achieved by using the transparent conductive laminated body excellent in wet heat characteristics for a transparent electrode.
  • Still another embodiment of the present invention is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one side of a substrate, and the transparent conductive layer extends in the film thickness direction from the substrate side.
  • Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2) Sputtering method or vapor deposition method on the substrate (1)
  • a step of forming a first zinc oxide film that does not contain indium from the sintered body for the first zinc oxide film (3) Sputtering or vapor deposition is performed on the first zinc oxide film.
  • a transparent conductive laminate having excellent characteristics can be stably produced.
  • step (3) As the step (4), another first zinc oxide having the same composition as the first zinc oxide film is formed on the surface of the second zinc oxide film. It is preferable to include a step of further laminating the film.
  • a transparent conductive layer having at least a three-layer structure a transparent conductive laminate superior in wet heat characteristics can be efficiently produced.
  • Still another embodiment of the present invention is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one side of a substrate, and the transparent conductive layer extends in the film thickness direction from the substrate side.
  • a second zinc oxide film and a first zinc oxide film are sequentially formed, and includes the following steps (1 ′) to (3 ′): It is a manufacturing method.
  • step (4 ′) another second layer having the same composition as the second zinc oxide film is formed on the surface of the first zinc oxide film. It is preferable to include a step of further laminating the zinc oxide film.
  • FIGS. 1 (a) to 1 (d) are views for explaining an embodiment of a transparent conductive laminate including a transparent conductive layer of the present invention.
  • FIG. 2 is a diagram provided for explaining the wet heat characteristics of the transparent conductive laminate of the present invention.
  • the first embodiment is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is first oxidized along the film thickness direction from the base material side.
  • a zinc film and a second zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is zinc oxide containing indium.
  • the first zinc oxide film is a zinc oxide film that does not contain indium. More specifically, as shown in FIGS. 1A and 1C, the zinc oxide film 16 is formed on at least one surface of the substrate 12 and is a zinc oxide film not containing indium. And
  • the element constituting the first zinc oxide film is not particularly limited as long as it contains zinc oxide as a main component.
  • the first zinc oxide film is preferably a zinc oxide film doped with gallium (hereinafter sometimes referred to as a GZO film).
  • the amount of various additive elements contained is the total amount of zinc, gallium, and oxygen by XPS elemental analysis.
  • the amount of gallium is preferably set to a value in the range of 0.1 to 10 atom% with respect to (100 atom%). This is because the electrical characteristics may be inferior when the amount of gallium falls outside the above range. Therefore, when the first zinc oxide film is a zinc oxide film doped with gallium, the amount of gallium is 0.5 to 8 atoms relative to the total amount of zinc, gallium and oxygen (100 atom%). % Is more preferable, and a value within the range of 1 to 7 atom% is more preferable.
  • the first zinc oxide film does not contain indium.
  • “does not contain indium” specifically refers to the amount of zinc by XPS elemental analysis and gallium in the blending amount of the above-mentioned various additive elements contained in the first zinc oxide film.
  • the amount of indium may be 0 atom% or a value in the range of more than 0 and less than 0.01 atom% with respect to the total amount (100 atom%) of the amount, oxygen amount, and indium amount.
  • each element amount by XPS elemental analysis measurement means the average value of the element amount in each depth measured by the XPS analysis of the depth direction in the whole transparent conductive layer.
  • the film thickness of the first zinc oxide film is preferably in the range of 10 to 300 nm. This is because when the thickness of the first zinc oxide film is less than 10 nm, it may be difficult to stably form the zinc oxide film. On the other hand, when the film thickness of the first zinc oxide film exceeds 300 nm, it takes an excessive amount of time to form the zinc oxide film, resulting in a decrease in productivity and adhesion to the base, resulting in film warpage. This is because there is a case where the problem occurs. Therefore, the thickness of the first zinc oxide film is more preferably in the range of 20 to 250 nm, and still more preferably in the range of 30 to 200 nm.
  • the film thickness (d) of the first zinc oxide film can be measured using a spectroscopic ellipsometer, as will be specifically described in Example 1.
  • the initial specific resistance ( ⁇ 0 ) of the first zinc oxide film 16 is preferably set to a value in the range of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. This is because the film forming conditions may be complicated when the initial specific resistance of the transparent conductive layer is less than 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. On the other hand, when the initial specific resistance of the transparent conductive layer exceeds 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, suitable conductivity may not be obtained.
  • the initial specific resistance of the transparent conductive film layer is more preferably set to a value in the range of 3 ⁇ 10 ⁇ 4 to 8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and 5 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 3. More preferably, the value is within the range of ⁇ ⁇ cm.
  • the specific resistance ( ⁇ ) of the transparent conductive layer should be calculated from the film thickness (d) of the transparent conductive laminate and the measured surface resistivity (R), as specifically described in Example 1. Can do.
  • the second zinc oxide film is a zinc oxide film containing indium. More specifically, as shown in FIGS. 1A and 1C, the zinc oxide film 10 formed on the first zinc oxide film 16 is a zinc oxide film containing indium.
  • the element constituting the second zinc oxide film is not particularly limited as long as it contains zinc oxide as a main component and contains indium. However, in order to improve conductivity, further gallium, aluminum, boron , Silicon, tin, germanium, antimony, iridium, rhenium, cerium, zirconium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, lanthanoid, hafnium It is preferable that at least one selected from tantalum, tungsten, platinum, gold, bismuth, actinoid, scandium and yttrium is contained.
  • the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with indium and gallium (hereinafter sometimes referred to as an In-GZO film) because of its excellent electrical characteristics and wet heat characteristics. It is preferable.
  • the amount of various additive elements contained is determined by the XPS elemental analysis measurement.
  • the zinc content, the gallium content, the oxygen content, and the total content (100 atom%) of the indium content are set to a value in the range of 0.01 to 25 atom%, and the gallium content is 0.1 to 10 atom%. It is preferable to set the value within the range of%. This is because if the amount of indium in the transparent conductive layer is a value within the above range, good wet heat characteristics and electrical characteristics can be obtained. Moreover, it is because an electrical property may be inferior when the amount of gallium becomes a value outside the above range.
  • the amount of indium in the transparent conductive layer is a value within the range of 0.01 to 25 atom%, it is possible to obtain a transparent conductive laminate having a good balance between electrical characteristics and wet heat characteristics and excellent wet heat characteristics. .
  • the amount of indium with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement is preferably in the range of 0.02 to 8 atom%, the gallium content is preferably in the range of 0.5 to 10 atom%, and the indium content is in the range of 0.1 to 7 atom%. More preferably, the gallium content is in the range of 1 to 10 atom%, the indium content is in the range of 0.1 to 6 atom%, and the gallium content is in the range of 1 to 7 atom%. It is particularly preferable to set the value of.
  • the amount of indium is 8 atom% relative to the total amount (100 atom%) of zinc, gallium, oxygen and indium measured by XPS elemental analysis. And a value in the range of 25 atom%, and preferably the gallium content is in the range of 0.5 to 10 atom%, the indium content is in the range of 9 to 22 atom%, and More preferably, the amount of gallium is set to a value within the range of 1 to 10 atom%, the amount of indium is set to a value within the range of 10 to 20 atom%, and the amount of gallium is set to a value within the range of 1 to 7 atom%. Is particularly preferred.
  • the film thickness of the second zinc oxide film is preferably a value within the range of 10 to 300 nm.
  • the reason for this is that when the thickness of the second zinc oxide film is less than 10 nm, stable formation of the zinc oxide film may become difficult, and wet heat characteristics and the like may be significantly reduced. It is.
  • the thickness of the second zinc oxide film exceeds 300 nm, it takes an excessive amount of time to form the zinc oxide film, and the productivity decreases or the adhesion to the base decreases. This is because warping may occur. Therefore, the thickness of the second zinc oxide film is more preferably in the range of 20 to 250 nm, and still more preferably in the range of 30 to 200 nm.
  • the film thickness (d) of the second zinc oxide film can be measured using a spectroscopic ellipsometer, as will be specifically described in Example 1.
  • the initial specific resistance ( ⁇ 0 ) of the second zinc oxide film 10 exceeds 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm and is less than 2.1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm. It is preferable to do. This is because, when the initial specific resistance of the second zinc oxide film becomes a value of 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, the film forming conditions may be complicated. On the other hand, if the initial specific resistance of the second zinc oxide film exceeds 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm, suitable conductivity may not be obtained.
  • the initial specific resistance of the second zinc oxide film is more preferably set to a value in the range of 5.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm to 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, more preferably 6 ⁇ 10 ⁇ More preferably, the value is within the range of 4 ⁇ ⁇ cm to 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the specific resistance ( ⁇ ) of the second zinc oxide film is determined from the film thickness (d) of the transparent conductive laminate and the measured surface resistivity (R), as specifically described in Example 1. Can be calculated.
  • the base material 12 illustrated in FIG. 1 is not particularly limited as long as it is excellent in transparency, and examples thereof include glass, ceramics, and resin films.
  • Resin film materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane
  • Examples thereof include olefin copolymers, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like.
  • the substrate is preferably a resin film.
  • these resin films since they are excellent in transparency and have flexibility and versatility, they are at least one selected from the group consisting of polyesters, polycarbonates, polyimides, polyamides, cycloolefin polymers, and polyether sulfones. It is preferable that a polyester or a cycloolefin polymer is more preferable. More specifically, examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate. Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
  • cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • Examples thereof include apell (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), arton (a norbornene polymer manufactured by JSR), zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like.
  • the film thickness of the substrate 12 illustrated in FIG. 1 may be determined according to the purpose of use, etc., but is within the range of 1 to 1000 ⁇ m from the viewpoint of flexibility and easy handling. The value is preferably in the range of 5 to 250 ⁇ m, more preferably in the range of 10 to 200 ⁇ m.
  • the base material may contain various additives such as an antioxidant, a flame retardant, and a lubricant as long as transparency and the like are not impaired.
  • a primer layer is a layer provided in order to improve the adhesiveness of a base material and a transparent conductive layer.
  • a urethane type resin an acrylic resin, a silane coupling agent, an epoxy resin, polyester, for example Known resins such as a resin and an ultraviolet curable resin can be used.
  • the gas barrier layer is preferably provided between the base material and the transparent conductive layer, and the material constituting the gas barrier layer is not particularly limited as long as it prevents the permeation of oxygen and water vapor. It is preferable that the gas barrier property is good. More specifically, examples of the constituent material include metals such as aluminum, magnesium, zirconium, titanium, zinc, and tin; silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, indium oxide, tin oxide, and oxide.
  • the gas barrier layer is more preferably composed of at least one selected from silicon oxide, silicon nitride, silicon oxynitride, and zinc tin oxide (ZTO).
  • the gas barrier layer may contain other compounding components such as various polymer resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.
  • the method for forming the gas barrier layer is not particularly limited.
  • a method for forming the above-described material on a substrate by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, or the like A method in which a solution obtained by dissolving or dispersing the above-described material in an organic solvent is applied onto a substrate by a known application method, and the resulting coating film is appropriately dried to form a coating film. Examples thereof include a method of performing surface modification such as atmospheric pressure plasma, ion implantation, and lamp annealing.
  • the thickness of the gas barrier layer is not particularly limited, and is usually preferably a value within the range of 20 nm to 50 ⁇ m.
  • the film thickness of the gas barrier layer is more preferably set to a value within the range of 30 nm to 1 ⁇ m, and further preferably set to a value within the range of 40 nm to 500 nm.
  • a water vapor permeability as measured in an atmosphere of 90% RH is preferably not more than the value 0.1g / m 2 / day, 0.05g / m 2 / day or less of More preferably, the value is 0.01 g / m 2 / day or less.
  • the reason for this is that by setting such a value of water vapor transmission rate, the transparent conductive layer can be prevented from deteriorating and gas barrier properties excellent in moisture and heat resistance can be obtained.
  • it can measure by a well-known method as a water vapor transmission rate of a gas barrier layer, For example, it can measure using a commercially available water vapor transmission rate measuring apparatus.
  • the transparent conductive laminate 50 illustrated in FIG. 1A is a transparent conductive laminate in which a transparent conductive layer 18 is formed on one side or both sides on a substrate 12.
  • the first zinc oxide film 16 and the second zinc oxide film 10 are sequentially formed from the base material side along the film thickness direction.
  • a zinc oxide film has the above-described configuration.
  • a first zinc oxide film 16 ′ is further laminated on the second zinc oxide film 10.
  • the wet heat characteristic of a transparent conductive laminated body can be adjusted suitably and precisely by combining the 2nd zinc oxide film
  • the light transmittance at a wavelength of 550 nm is preferably 70% or more at a predetermined thickness, for example, any of 20 to 600 nm, and 80% or more. More preferably, the value is 90% or more.
  • the light transmittance at a wavelength of 550 nm is preferably 50% or more at a predetermined thickness, for example, 10 ⁇ m to 1 mm, and is a value of 60% or more. More preferably, the value is more preferably 70% or more.
  • the initial resistivity of the transparent conductive layer 18 in the transparent conductive laminate of the present invention is ⁇ 0, and the ratio after storage for 500 hours at 60 ° C. and 95% relative humidity.
  • the ratio represented by ⁇ 1 / ⁇ 0 is preferably set to a value of 1.3 or less.
  • the transparent conductive layer is formed of a first zinc oxide film not containing indium having excellent electrical characteristics and a second zinc oxide film containing indium having excellent wet heat characteristics. Therefore, by using the second zinc oxide film as a moist heat deterioration suppressing layer, the transparent conductivity having good moist heat characteristics without increasing the initial specific resistance of the transparent conductive laminate by the synergistic effect of the two layers. A laminate can be obtained.
  • the specific resistance ( ⁇ 0 , ⁇ 1 ) of the transparent conductive layer can be measured using a surface resistance measuring device as specifically described in Example 1.
  • the relationship between the film thickness of the 2nd transparent conductive film in a transparent conductive laminated body, and the change of the specific resistance before and behind an environmental test is demonstrated. That is, the horizontal axis of FIG. 2 shows the thickness of the second zinc oxide film, and the vertical axis shows the elapsed storage time under conditions of 60 ° C. and relative humidity 95%. On the vertical axis, the ratio represented by ⁇ 1 / ⁇ 0 is taken. From this characteristic curve, it is understood that the wet heat characteristics of the transparent conductive laminate are remarkably improved by providing the first zinc oxide film with the second zinc oxide film as the wet heat deterioration suppressing layer.
  • the transparent conductive laminated body formed into a film in each film thickness using a sintered body having a weight ratio of 0% by weight is used.
  • the surface resistivity (R) of the transparent conductive laminated body of this invention is a value of 1000 ohms / square or less. More specifically, when the surface resistivity of the transparent conductive laminate is a value exceeding 1000 ⁇ / ⁇ , conductivity suitable for the transparent conductive laminate may not be obtained. Therefore, the surface resistivity of the transparent conductive laminate is more preferably a value of 500 ⁇ / ⁇ or less, and further preferably a value of 200 ⁇ / ⁇ or less. In addition, about the measuring method of surface resistivity, it can measure using a surface resistance measuring apparatus so that it may demonstrate concretely in an Example.
  • the second embodiment is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is second oxidized along the film thickness direction from the base material side.
  • a zinc film and a first zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is zinc oxide containing indium.
  • the transparent conductive laminate 50 ′ illustrated in FIG. 1B is a transparent conductive laminate in which a transparent conductive layer is formed on one side or both sides of the substrate 12, In the transparent conductive layer, the second zinc oxide film 10 and the first zinc oxide film 16 are sequentially formed along the film thickness direction from the substrate side. Further, as shown in FIG. 1D, it is also a preferable aspect that a second zinc oxide film 10 ′ is further laminated on the first zinc oxide film 16.
  • the wet heat characteristic of a transparent conductive laminated body can be adjusted suitably and precisely by combining the 2nd zinc oxide film
  • the first and second zinc oxide films have the same structure as described above, and the characteristics as the transparent conductive laminate are the same as those described above, and thus the details are omitted.
  • 3rd Embodiment is a manufacturing method of the transparent conductive laminated body formed by forming a transparent conductive layer in the at least single side
  • Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2) Sputtering method or vapor deposition method on the substrate (1)
  • a step of forming a first zinc oxide film that does not contain indium from the sintered body for the first zinc oxide film (3) Sputtering or vapor deposition is performed on the first zinc oxide film.
  • Step of forming a second zinc oxide film containing indium from a sintered body for the second zinc oxide film will be described in detail. Explained.
  • Step (1) is a step of preparing the base material and the sintered body. That is, the first zinc oxide film 16 illustrated in FIGS. 1A and 1C is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide.
  • the second zinc oxide film 10 is formed from a sintered body containing zinc oxide as a main component and at least indium oxide. The details of the base material are the same as described above, and will be omitted.
  • the first zinc oxide film is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide but containing gallium oxide.
  • the blending amount of zinc oxide is set to a value within the range of 90 to 99.9% by weight with respect to the total amount of the sintered body, and gallium oxide
  • the blending amount is preferably set to a value within the range of 0.1 to 10% by weight. The reason for this is that when the amount of gallium oxide is less than 0.1% by weight relative to the total amount of the sintered body, the amount of gallium contained in the first zinc oxide film after film formation is significantly reduced.
  • the blending amount of zinc oxide is set to a value in the range of 92 to 99% by weight and the blending amount of gallium oxide is set to a value in the range of 1 to 8% by weight with respect to the total amount of the sintered body. More preferred.
  • the blending amount of zinc oxide is set to a value within the range of 93 to 99% by weight, and the blending amount of gallium oxide is set to a value within the range of 1 to 7% by weight. Further preferred.
  • the second zinc oxide film is formed from a sintered body containing zinc oxide as a main component and further containing indium oxide and gallium oxide.
  • the blending amount of zinc oxide is set to a value within the range of 15 to 99.98% by weight with respect to the total amount of the sintered body, The blending amount is preferably set to a value within the range of 0.01 to 15% by weight, and the indium oxide content is preferably set to a value within the range of 0.01 to 70% by weight.
  • the reason for this is that by using a ternary sintered body of zinc oxide-gallium oxide-indium oxide whose amount is controlled, a second zinc oxide film having excellent wet heat characteristics can be efficiently formed. This is because production efficiency can be improved. More specifically, when the blending amount of indium oxide is less than 0.01% by weight with respect to the total amount of the sintered body, the amount of indium contained in the second zinc oxide film after film formation is remarkably large. This is because there may be a case where sufficient wet heat characteristics are not obtained. On the other hand, when the amount of indium oxide exceeds 70% by weight, the amount of indium contained in the second zinc oxide film after film formation may increase remarkably.
  • the zinc oxide content is within the range of 27 to 99.4% by weight and the gallium oxide content is within the range of 0.5 to 8% by weight relative to the total amount of the sintered body.
  • the blending amount of indium oxide is set to a value within the range of 0.1 to 65 weight.
  • the blending amount of zinc oxide is set to a value within the range of 33 to 98.7% by weight
  • the blending amount of gallium oxide is set to a value within the range of 1 to 7% by weight with respect to the total amount of the sintered body.
  • the blending amount of indium oxide is a value within the range of 0.3 to 60% by weight.
  • Step (2) is a method of forming the first zinc oxide film 16 on at least one surface of the substrate 12 as shown in FIG. .
  • a method for forming the first zinc oxide film for example, a physical manufacturing method typified by a sputtering method or a vapor deposition method and a chemical manufacturing method typified by a chemical vapor deposition method can be given.
  • a sputtering method or a vapor deposition method is preferable because a zinc oxide film can be easily formed. That is, since the composition of the first zinc oxide film to be formed can be easily controlled by forming by sputtering or vapor deposition, the first zinc oxide film can be formed efficiently.
  • More specific sputtering methods include DC sputtering method, DC magnetron sputtering method, RF sputtering method, RF magnetron sputtering method, DC + RF superposition sputtering method, DC + RF superposition magnetron sputtering method, counter target sputtering method, ECR sputtering method, dual magnetron sputtering method.
  • More specific vapor deposition methods include a resistance heating method, an electron beam heating method, a laser heating method, an arc vapor deposition method, and an induction heating method.
  • the conditions for sputtering or vapor deposition are not particularly limited, but the back pressure is preferably 1 ⁇ 10 ⁇ 2 Pa or less, and more preferably 1 ⁇ 10 ⁇ 3 Pa or less.
  • the internal pressure is preferably set to a value in the range of 0.1 to 5 Pa, more preferably 0.2 to 1 Pa.
  • argon (Ar) or a mixed gas of argon (Ar) and oxygen (O 2 ) is used as a gas species to be introduced into the system by sputtering or vapor deposition, but rare gases other than Ar are used. Gas, nitrogen (N 2 ), or the like may be used.
  • the mixing ratio (O 2 / (Ar + O 2 )) is preferably set to a value within the range of 0.01 to 20, and more preferably set to a value within the range of 0.1 to 10. preferable. This is because when the mixing ratio of argon and oxygen is in the above range, a conductive layer having a low specific resistance and a low reflectance can be formed.
  • the temperature of the substrate when forming the transparent conductive layer on the substrate is preferably set to a value within the range of 10 to 150 ° C. This is because, if the temperature of the substrate is a value within the range of 10 to 150 ° C., the transparent conductive layer can be suitably formed even with a substrate having a relatively low softening point.
  • Step (3) is a step of forming second zinc oxide film 10 on first zinc oxide film 16 as shown in FIG. It is. Note that the method for forming the second zinc oxide film is the same as the method for forming the first zinc oxide film, and thus the details thereof are omitted.
  • Step (4) Step of Forming First Zinc Oxide Film Step (4) is the same as the first zinc oxide film described above on the second zinc oxide film 10 as shown in FIG. This is a step of forming another first zinc oxide film 16 'having the above composition. Since this process is the same as described above, the details are omitted.
  • [Fourth Embodiment] 4th Embodiment is a manufacturing method of the transparent conductive laminated body formed by forming a transparent conductive layer in the at least single side
  • a method for producing a transparent conductive laminate comprising the steps of (1 ′) to (3 ′) below, wherein a zinc oxide film of 2 and a first zinc oxide film are sequentially formed. .
  • the fourth embodiment is a method for manufacturing the transparent conductive laminate illustrated in FIGS. 1B and 1D described in the second embodiment.
  • the transparent conductive laminates 50 ′ and 50 ′′ ′′ include the steps of forming the zinc oxide film 10 and then forming the first zinc oxide film 16.
  • step (4 ′) as shown in FIG. 1D, another second zinc oxide film having the same composition as that of the second zinc oxide film is formed on the first zinc oxide film 16.
  • a step of forming 10 ' may be included. Note that the details of each step are the same as those described in the first to third embodiments, and will be omitted.
  • Embodiment is an electronic device characterized by using any one of the transparent conductive laminated bodies mentioned above for a transparent electrode. More specifically, a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, an organic transistor, an organic EL illumination, and an inorganic EL illumination each having a transparent electrode provided with a predetermined transparent conductive laminate. , Thermoelectric conversion devices, gas sensors and the like.
  • the electronic device of the present invention includes the transparent conductive laminate described in the first embodiment, it is excellent in wet heat characteristics and transparency, and can exhibit good electrical characteristics.
  • alkali-free glass manufactured by Corning, Eagle XG, thickness: 700 ⁇ m
  • ZnO: Ga 2 O 3 94.3% by weight: 5.7% by weight
  • the following sputtering is performed on the alkali-free glass as a base material by the DC magnetron sputtering method using the above-described ternary sintered body.
  • a second zinc oxide film (In-GZO film, film thickness: 100 nm) was formed.
  • the obtained second zinc oxide film is subjected to DC magnetron sputtering, using the above-described binary sintered body, A first zinc oxide film (GZO film, film thickness: 100 nm) was formed under the same sputtering conditions as described above.
  • Elemental analysis measurement in XPS analysis Elemental analysis of zinc, gallium, indium and oxygen in the transparent conductive layer in the transparent conductive laminate obtained using an XPS measurement analyzer (manufactured by ULVAC-PHI, Quantum 2000) It was.
  • the amount of each element by XPS measurement of the obtained first zinc oxide film (GZO film) was 4.47 atom% of gallium and 52.1 atom% of zinc.
  • the amount of each element obtained by XPS measurement of the obtained second zinc oxide film (In-GZO film) is an indium amount of 0.3 atom%, a gallium amount of 4.27 atom%, and a zinc amount of 51.4 atom%. Met.
  • the initial surface resistivity (R 0 ) in the transparent conductive layer of the obtained transparent conductive laminate was used as a surface resistance measuring device as a LOCESTA-GP MCP-T600 ( Using PROBE TYPE ASP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) as a probe and a probe (Mitsubishi Chemical Co., Ltd.), the measurement was performed under environmental conditions of a temperature of 23 ° C. and 50% RH. Next, the obtained transparent conductive film was placed in an environment of 60 ° C. and 95% RH for 500 hours, taken out, then subjected to temperature control and humidity control in a 23 ° C. and 50% RH environment for 1 day.
  • the surface resistivity (R 1 ) was measured. That is, the initial surface resistivity (R 0 ) and the surface resistivity (R 1 ) after the wet heat test in the transparent conductive layer, and the film thickness (d) of the transparent conductive laminate were measured. From 1) and (2), the specific resistance ( ⁇ 0 ) and the specific resistance after the wet heat test ( ⁇ 1 ) were calculated to obtain a ratio of ⁇ 1 / ⁇ 0 . The obtained results are shown in Table 1.
  • R 0 ⁇ 0 / d (1)
  • R 1 ⁇ 1 / d (2)
  • Example 2 In Example 2, a first zinc oxide film (GZO film, film thickness: 100 nm) is formed on a substrate, and then a second zinc oxide film (In-GZO film, film thickness: 100 nm) is formed. A transparent conductive film was produced and evaluated in the same manner as in Example 1 except that. The obtained results are shown in Table 1.
  • Example 3 In Example 3, a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 20 nm. The obtained results are shown in Table 1.
  • Example 4 a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 200 nm. The obtained results are shown in Table 1.
  • Comparative Example 1 In Comparative Example 1, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 200 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.
  • Comparative Example 2 In Comparative Example 2, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 100 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.
  • the transparent conductive laminate of the present invention is a transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate, and the transparent conductive layer is a predetermined layer.
  • the transparent conductive laminate of the present invention can be used in electrical products, electronic components, image display devices (organic electroluminescent elements, inorganic electroluminescent elements, liquid crystal display devices, electronic paper, etc.), thermoelectrics that require predetermined wet heat characteristics. It is expected to be used effectively as a transparent electrode in various applications such as conversion devices and solar cells.

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Abstract

The present invention provides a transparent conductive laminate having excellent moist heat characteristics, a method for producing said transparent conductive laminate, and an electronic device formed using such a transparent conductive laminate. Provided is a transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate, said transparent conductive layer being formed by sequentially forming, from the substrate side along the film thickness direction, a first zinc oxide film and a second zinc oxide film, wherein the first zinc oxide film is a zinc oxide film that does not include indium, and the second zinc oxide film is a zinc oxide film that includes indium.

Description

透明導電性積層体、透明導電性積層体の製造方法、および透明導電性積層体を用いてなる電子デバイスTransparent conductive laminate, method for producing transparent conductive laminate, and electronic device using transparent conductive laminate

　本発明は、透明導電性積層体、透明導電性積層体の製造方法、および透明導電性積層体を用いてなる電子デバイスに関し、特に、湿熱特性に優れる透明導電性積層体、透明導電性積層体の製造方法、およびそのような透明導電性積層体を用いてなる電子デバイスに関する。 The present invention relates to a transparent conductive laminate, a method for producing a transparent conductive laminate, and an electronic device using the transparent conductive laminate, and in particular, a transparent conductive laminate and a transparent conductive laminate excellent in wet heat characteristics. And an electronic device using such a transparent conductive laminate.

　従来、液晶デバイスや有機エレクトロルミネッセンスデバイス（有機ＥＬ素子）を備えた画像表示装置において、錫ドープ酸化インジウムを透明導電層の形成材料として用いた透明導電性積層体が広く用いられている。
　一方、高価で希少金属であるインジウムを多量に含む錫ドープ酸化インジウムを用いた透明導電層の代替として、透明性や表面平滑性に優れた酸化亜鉛を用いた透明導電性積層体が提案されている。
　より具体的には、有機高分子フィルム基材上にＡｌ2Ｏ3薄膜が形成されており、その上にＧａをドープしたＺｎＯであるＧＺＯ薄膜が形成されている透明導電フィルムが提案されている（例えば、特許文献１参照）。 Conventionally, in an image display device provided with a liquid crystal device or an organic electroluminescence device (organic EL element), a transparent conductive laminate using tin-doped indium oxide as a material for forming a transparent conductive layer has been widely used.
On the other hand, a transparent conductive laminate using zinc oxide with excellent transparency and surface smoothness has been proposed as an alternative to a transparent conductive layer using tin-doped indium oxide containing a large amount of indium, which is an expensive and rare metal. Yes.
More specifically, a transparent conductive film is proposed in which an Al 2 O 3 thin film is formed on an organic polymer film substrate, and a GZO thin film of ZnO doped with Ga is formed thereon. (For example, refer to Patent Document 1).

　また、酸化亜鉛を主成分とし、濃度制御容易なドーパントによって、抵抗率の低下を目的とした低抵抗率透明導電体が提案されている。
　すなわち、酸化亜鉛、酸化インジウムおよび酸化ガリウムからなる透明導電体であって、インジウムおよびガリウムの元素濃度をそれぞれ所定範囲内の値とした低抵抗率透明導電体が提案されている（例えば、特許文献２）。 In addition, a low-resistivity transparent conductor has been proposed which has a zinc oxide as a main component and a dopant whose concentration can be easily controlled.
That is, a transparent conductor made of zinc oxide, indium oxide, and gallium oxide, and a low-resistance transparent conductor in which the element concentrations of indium and gallium are each within a predetermined range has been proposed (for example, Patent Documents). 2).

　一方で、極薄膜レベルであっても優れた耐湿熱特性を得ることを目的として、特定の元素をドープした透明導電性酸化亜鉛膜が提案されている。
　すなわち、酸化亜鉛に、Ｇａ及び／又はＡｌからなる第１元素と、Ｉｎ、Ｂｉ、Ｓｅ、Ｃｅ、Ｃｕ、Ｅｒ及びＥｕからなる群から選択される少なくとも１つからなる第２元素が添加された透明導電性酸化亜鉛膜であって、所定の湿熱試験前後における比抵抗が所定範囲内の値であり、亜鉛と第２元素の原子数量比および膜厚を所定の範囲内の値に規定した透明導電性酸化亜鉛膜が提案されている（例えば、特許文献３）。 On the other hand, a transparent conductive zinc oxide film doped with a specific element has been proposed for the purpose of obtaining excellent moisture and heat resistance characteristics even at an extremely thin film level.
That is, a first element composed of Ga and / or Al and a second element composed of at least one selected from the group consisting of In, Bi, Se, Ce, Cu, Er, and Eu are added to zinc oxide. A transparent conductive zinc oxide film having a specific resistance value within a predetermined range before and after a predetermined wet heat test, and a transparent value in which the atomic quantity ratio and film thickness of zinc and the second element are specified within the predetermined range. A conductive zinc oxide film has been proposed (for example, Patent Document 3).

特許第４９１７８９７号公報（特許請求の範囲等）Japanese Patent No. 4917897 (Claims etc.) 特開２００６－１４７３２５号公報（特許請求の範囲等）JP 2006-147325 A (Claims etc.) 特開２０１３－１４７７２７号公報（特許請求の範囲等）JP 2013-147727 A (Claims etc.)

　しかしながら、特許文献１に開示された透明導電フィルムは、アンダーコート層としてＡｌ2Ｏ3薄膜を必須としているにも関わらず、ガリウムのみをドープした酸化亜鉛膜は、未だ耐湿熱特性が不十分であるという問題が見られた。
　また、特許文献２に開示された低抵抗率透明導電体は、抵抗率の改善は図れたものの、湿熱特性については、何ら考慮されていないという問題が見られた。
　また、特許文献３に開示された透明導電性酸化亜鉛膜は、ある程度の湿熱特性は得られているものの、成膜条件が比較的過酷であり、また膜厚が１４０ｎｍ以下であることを必須としており、用途が比較的狭く限定されるという問題が見られた。 However, although the transparent conductive film disclosed in Patent Document 1 requires an Al 2 O 3 thin film as an undercoat layer, the zinc oxide film doped only with gallium still has insufficient moisture and heat resistance characteristics. There was a problem.
Moreover, although the low resistivity transparent conductor disclosed in Patent Document 2 has improved the resistivity, there has been a problem that no consideration has been given to the wet heat characteristics.
Moreover, although the transparent conductive zinc oxide film disclosed in Patent Document 3 has some wet heat characteristics, the film forming conditions are relatively severe, and the film thickness must be 140 nm or less. However, there has been a problem that the application is relatively narrow and limited.

　そこで、本発明者らは、このような問題を鋭意検討した結果、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とから形成されてなり、第１の酸化亜鉛膜および第２の酸化亜鉛膜がそれぞれ特定の構造を有する透明導電性積層体を構成することにより、湿熱特性に優れることを見出し、本発明を完成させたものである。
　すなわち、本発明は、湿熱特性に優れる透明導電性積層体、透明導電性積層体の製造方法、およびそのような透明導電性積層体を用いてなる電子デバイスを提供することを目的とする。 Therefore, as a result of intensive studies on such a problem, the inventors of the present invention are transparent conductive laminates in which a transparent conductive layer is formed on at least one side of a substrate, and the transparent conductive layer is a first oxidation layer. By forming a transparent conductive laminate comprising a zinc film and a second zinc oxide film, each of the first zinc oxide film and the second zinc oxide film having a specific structure, wet heat characteristics And the present invention has been completed.
That is, an object of the present invention is to provide a transparent conductive laminate excellent in wet heat characteristics, a method for producing the transparent conductive laminate, and an electronic device using such a transparent conductive laminate.

　本発明によれば、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体が提供され、上述した問題を解決することができる。
　すなわち、本発明の透明導電層が、特定の構造を有する第１の酸化亜鉛膜と、特定の構造を有する第２の酸化亜鉛膜とを順に積層していることから、透明導電層の湿熱特性を向上させることができる。 According to the present invention, there is provided a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is a first zinc oxide along the thickness direction from the base material side. The first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is a zinc oxide film containing indium. A transparent conductive laminate is provided that can solve the above-described problems.
That is, since the transparent conductive layer of the present invention is formed by sequentially laminating a first zinc oxide film having a specific structure and a second zinc oxide film having a specific structure, the wet heat characteristics of the transparent conductive layer Can be improved.

　また、本発明の別の態様は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体である。
　このように構成することにより、本発明の透明導電層が、特定の構造を有する第２の酸化亜鉛膜と、特定の構造を有する第１の酸化亜鉛膜とを順に積層していることから、透明導電層の湿熱特性を向上させることができる。 Another aspect of the present invention is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a substrate, and the transparent conductive layer is formed from the substrate side along the film thickness direction. 2 zinc oxide film and first zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is made of indium. A transparent conductive laminate comprising a zinc oxide film.
By comprising in this way, since the transparent conductive layer of this invention has laminated | stacked in order the 2nd zinc oxide film | membrane which has a specific structure, and the 1st zinc oxide film | membrane which has a specific structure, The wet heat characteristics of the transparent conductive layer can be improved.

　また、本発明を構成するにあたり、第１の酸化亜鉛膜が、ガリウムをドープしてなる酸化亜鉛膜であることが好ましい。
　このように構成することにより、特に、初期の比抵抗が低い酸化亜鉛膜とすることができる。 In configuring the present invention, the first zinc oxide film is preferably a zinc oxide film formed by doping gallium.
With this configuration, a zinc oxide film having a particularly low initial specific resistance can be obtained.

　また、本発明を構成するにあたり、第２の酸化亜鉛膜が、インジウムおよびガリウムをドープしてなる酸化亜鉛膜であることが好ましい。
　このように構成することにより、湿熱特性に優れた酸化亜鉛膜とすることができる。 In configuring the present invention, the second zinc oxide film is preferably a zinc oxide film doped with indium and gallium.
By comprising in this way, it can be set as the zinc oxide film | membrane excellent in the wet heat characteristic.

　また、本発明を構成するにあたり、第２の酸化亜鉛膜は、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を０．０１～２５ａｔｏｍ％の範囲内の値とすることが好ましい。
　このように構成することにより、比抵抗が低く、湿熱特性に優れた酸化亜鉛膜を得ることができる。 Further, in constituting the present invention, the second zinc oxide film has an indium amount of 0 with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement. A value within the range of 0.01 to 25 atom% is preferable.
By comprising in this way, the zinc oxide film | membrane with a low specific resistance and excellent in the heat-and-moisture characteristic can be obtained.

　また、本発明を構成するにあたり、透明導電膜層における初期の比抵抗をρ0とし、６０℃、相対湿度９５％の条件下で、５００時間、保管した後の比抵抗をρ1としたとき、ρ1/ρ0で表わされる比率を１．３以下の値とすることが好ましい。
　このように構成することにより、長時間にわたって湿熱特性に優れる透明導電性積層体を得ることができる。 Further, in configuring the present invention, when the initial specific resistance in the transparent conductive film layer is ρ 0 and the specific resistance after storage for 500 hours at 60 ° C. and a relative humidity of 95% is ρ 1 The ratio represented by ρ 1 / ρ 0 is preferably set to a value of 1.3 or less.
By comprising in this way, the transparent conductive laminated body which is excellent in wet heat characteristics over a long time can be obtained.

　また、本発明を構成するにあたり、基材が、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、シクロオレフィン系コポリマ、シクロオレフィン系ポリマ、ポリエーテルスルフォン、ポリイミドからなる群から選ばれる少なくとも１種であることが好ましい。
　このように構成することにより、透明導電性積層体に柔軟性および透明性を付与することができる。 In constructing the present invention, the base material is at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, cycloolefin polymer, polyethersulfone, and polyimide. preferable.
By comprising in this way, a softness | flexibility and transparency can be provided to a transparent conductive laminated body.

　また、本発明の別の態様は、上述したいずれかの透明導電性積層体を透明電極に用いてなることを特徴とする電子デバイスである。
　このように、湿熱特性に優れる透明導電性積層体を透明電極に用いることにより、電子デバイスの長期安定性を好適に図ることができる。 Another embodiment of the present invention is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode.
Thus, the long-term stability of an electronic device can be suitably achieved by using the transparent conductive laminated body excellent in wet heat characteristics for a transparent electrode.

　また、本発明のさらに別の態様は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、透明導電層が、基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、下記工程（１）～（３）を含むことを特徴とする透明導電性積層体の製造方法である。
（１）基材と、第１の酸化亜鉛膜用の焼結体と、第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２）基材上に、スパッタリング法または蒸着法を用いて、第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、第１の酸化亜鉛膜を形成する工程
（３）第１の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、第２の酸化亜鉛膜用の焼結体から、インジウムを含む、第２の酸化亜鉛膜を形成する工程
　すなわち、少なくとも２層構造の透明導電層を形成することによって、電気特性および湿熱特性に優れた透明導電性積層体を安定的に製造することができる。 Still another embodiment of the present invention is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one side of a substrate, and the transparent conductive layer extends in the film thickness direction from the substrate side. A method for producing a transparent conductive laminate, wherein a first zinc oxide film and a second zinc oxide film are sequentially formed, and include the following steps (1) to (3): It is.
(1) Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2) Sputtering method or vapor deposition method on the substrate (1) A step of forming a first zinc oxide film that does not contain indium from the sintered body for the first zinc oxide film (3) Sputtering or vapor deposition is performed on the first zinc oxide film. A step of forming a second zinc oxide film containing indium from the sintered body for the second zinc oxide film, that is, by forming a transparent conductive layer having at least a two-layer structure, thereby providing electrical characteristics and wet heat A transparent conductive laminate having excellent characteristics can be stably produced.

　また、本発明を実施するにあたり、工程（３）の後に、工程（４）として、第２の酸化亜鉛膜の表面に、第１の酸化亜鉛膜と同一の組成の別の第１の酸化亜鉛膜を、さらに積層する工程を含むことが好ましい。
　このように、少なくとも３層構造の透明導電層を形成することによって、湿熱特性により優れた透明導電性積層体を効率的に製造することができる。 In carrying out the present invention, after the step (3), as the step (4), another first zinc oxide having the same composition as the first zinc oxide film is formed on the surface of the second zinc oxide film. It is preferable to include a step of further laminating the film.
Thus, by forming a transparent conductive layer having at least a three-layer structure, a transparent conductive laminate superior in wet heat characteristics can be efficiently produced.

　また、本発明のさらに別の態様は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、透明導電層が、基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、下記工程（１´）～（３´）を含むことを特徴とする透明導電性積層体の製造方法である。
（１´）基材と、第１の酸化亜鉛膜用の焼結体と、第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２´）基材上に、スパッタリング法または蒸着法を用いて、第２の酸化亜鉛膜用の焼結体から、インジウムを含む、第２の酸化亜鉛膜を形成する工程
（３´）第２の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、第１の酸化亜鉛膜を形成する工程
　すなわち、このように、少なくとも２層構造の透明導電層を形成することによって、電気特性および湿熱特性に優れた透明導電性積層体を安定的に製造することができる。 Still another embodiment of the present invention is a method for producing a transparent conductive laminate in which a transparent conductive layer is formed on at least one side of a substrate, and the transparent conductive layer extends in the film thickness direction from the substrate side. A second zinc oxide film and a first zinc oxide film are sequentially formed, and includes the following steps (1 ′) to (3 ′): It is a manufacturing method.
(1 ′) Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2 ′) On the substrate, a sputtering method or Step of forming a second zinc oxide film containing indium from the sintered body for the second zinc oxide film by using a vapor deposition method (3 ′) Sputtering or vapor deposition on the second zinc oxide film Step of forming a first zinc oxide film that does not contain indium from the sintered body for the first zinc oxide film using the method, that is, forming a transparent conductive layer having at least a two-layer structure in this way Thus, a transparent conductive laminate excellent in electrical characteristics and wet heat characteristics can be stably produced.

　また、本発明を実施するにあたり、工程（３´）の後に、工程（４´）として、第１の酸化亜鉛膜の表面に、第２の酸化亜鉛膜と同一の組成の別の第２の酸化亜鉛膜を、さらに積層する工程を含むことが好ましい。
　このように、少なくとも３層構造の透明導電層を形成することによって、湿熱特性により優れた透明導電性積層体を効率的に製造することができる。 In carrying out the present invention, after the step (3 ′), as the step (4 ′), another second layer having the same composition as the second zinc oxide film is formed on the surface of the first zinc oxide film. It is preferable to include a step of further laminating the zinc oxide film.
Thus, by forming a transparent conductive layer having at least a three-layer structure, a transparent conductive laminate superior in wet heat characteristics can be efficiently produced.

図１（ａ）～（ｄ）は、本発明の透明導電層を含む透明導電性積層体の態様を説明するために供する図である。FIGS. 1 (a) to 1 (d) are views for explaining an embodiment of a transparent conductive laminate including a transparent conductive layer of the present invention. 図２は、本発明の透明導電性積層体の湿熱特性を説明するために供する図である。FIG. 2 is a diagram provided for explaining the wet heat characteristics of the transparent conductive laminate of the present invention.

［第１の実施形態］
　第１の実施形態は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体である。
　以下、第１の実施形態の透明導電性積層体につき、適宜図面を参照して具体的に説明する。 [First Embodiment]
The first embodiment is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is first oxidized along the film thickness direction from the base material side. A zinc film and a second zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is zinc oxide containing indium. A transparent conductive laminate characterized by being a film.
Hereinafter, the transparent conductive laminate of the first embodiment will be specifically described with reference to the drawings as appropriate.

１．透明導電層
１－１．第１の酸化亜鉛膜
　第１の酸化亜鉛膜は、インジウムを含まない酸化亜鉛膜であることを特徴とする。
　より具体的には、図１(ａ)、（ｃ）に示すように、基材１２の少なくとも片面に形成される酸化亜鉛膜１６であって、インジウムを含まない酸化亜鉛膜であることを特徴とする。 1. Transparent conductive layer 1-1. First Zinc Oxide Film The first zinc oxide film is a zinc oxide film that does not contain indium.
More specifically, as shown in FIGS. 1A and 1C, the zinc oxide film 16 is formed on at least one surface of the substrate 12 and is a zinc oxide film not containing indium. And

（１）構成
　第１の酸化亜鉛膜を構成する元素としては、酸化亜鉛を主成分として含んでいれば特に制限はなく、導電性を向上させるために、さらにガリウム、アルミニウム、ホウ素、ケイ素、錫、ゲルマニウム、アンチモン、イリジウム、レニウム、セリウム、ジルコニウム、マグネシウム、チタン、バナジウム、マンガン、鉄、コバルト、ニッケル、銅、ニオブ、モリブデン、テクネチウム、ルテニウム、ロジウム、パラジウム、銀、ランタノイド、ハフニウム、タンタル、タングステン、白金、金、ビスマス、アクチノイド、スカンジウム及びイットリウムから選択される少なくとも１種を含んでいることが好ましい。
　特に、電気特性に優れる点から、第１の酸化亜鉛膜が、ガリウムをドープしてなる酸化亜鉛膜（以下ＧＺＯ膜と称する場合がある）であることが好ましい。 (1) Structure The element constituting the first zinc oxide film is not particularly limited as long as it contains zinc oxide as a main component. In order to improve conductivity, gallium, aluminum, boron, silicon, tin , Germanium, antimony, iridium, rhenium, cerium, zirconium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, lanthanoid, hafnium, tantalum, tungsten It is preferable that at least one selected from platinum, gold, bismuth, actinoid, scandium and yttrium is contained.
In particular, from the viewpoint of excellent electrical characteristics, the first zinc oxide film is preferably a zinc oxide film doped with gallium (hereinafter sometimes referred to as a GZO film).

　また、第１の酸化亜鉛膜が、ガリウムをドープしてなる酸化亜鉛膜である場合、含まれる各種添加元素の配合量は、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量の合計量（１００ａｔｏｍ％）に対して、ガリウム量を０．１～１０ａｔｏｍ％の範囲内の値とすることが好ましい。
　この理由は、ガリウム量が、上記範囲外の値となると、電気特性が劣る場合があるためである。
　したがって、第１の酸化亜鉛膜が、ガリウムをドープしてなる酸化亜鉛膜である場合、亜鉛量、ガリウム量、酸素量の合計量（１００ａｔｏｍ％）に対して、ガリウム量を０．５～８ａｔｏｍ％の範囲内の値とすることがより好ましく、１～７ａｔｏｍ％の範囲内の値であることがさらに好ましい。 Further, when the first zinc oxide film is a zinc oxide film doped with gallium, the amount of various additive elements contained is the total amount of zinc, gallium, and oxygen by XPS elemental analysis. The amount of gallium is preferably set to a value in the range of 0.1 to 10 atom% with respect to (100 atom%).
This is because the electrical characteristics may be inferior when the amount of gallium falls outside the above range.
Therefore, when the first zinc oxide film is a zinc oxide film doped with gallium, the amount of gallium is 0.5 to 8 atoms relative to the total amount of zinc, gallium and oxygen (100 atom%). % Is more preferable, and a value within the range of 1 to 7 atom% is more preferable.

　なお、第１の酸化亜鉛膜には、インジウムを含まないことを特徴とする。
　ここで、本願発明において、「インジウムを含まない」とは、具体的には、第１の酸化亜鉛膜に含まれる上述の各種添加元素の配合量において、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を０ａｔｏｍ％、または０を超えて０．０１ａｔｏｍ％未満の範囲内の値であればよい。
　また、ＸＰＳの元素分析測定による各元素量は、透明導電層全体において、深さ方向のＸＰＳ分析によって測定される、各深さにおける元素量の平均値を意味する。 Note that the first zinc oxide film does not contain indium.
Here, in the present invention, “does not contain indium” specifically refers to the amount of zinc by XPS elemental analysis and gallium in the blending amount of the above-mentioned various additive elements contained in the first zinc oxide film. The amount of indium may be 0 atom% or a value in the range of more than 0 and less than 0.01 atom% with respect to the total amount (100 atom%) of the amount, oxygen amount, and indium amount.
Moreover, each element amount by XPS elemental analysis measurement means the average value of the element amount in each depth measured by the XPS analysis of the depth direction in the whole transparent conductive layer.

（２）膜厚
　また、第１の酸化亜鉛膜の膜厚が１０～３００ｎｍの範囲内の値であることが好ましい。
　この理由は、第１の酸化亜鉛膜の膜厚が１０ｎｍ未満の値となると、酸化亜鉛膜の安定的形成が困難となる場合があるためである。
　一方、第１の酸化亜鉛膜の膜厚が３００ｎｍを超えた値になると、酸化亜鉛膜の形成に過度に時間を要し、生産性が低下したり、下地に対する密着性が低下し、膜反りが生じたりする場合があるためである。
　したがって、第１の酸化亜鉛膜の膜厚が２０～２５０ｎｍの範囲内の値であることがより好ましく、３０～２００ｎｍの範囲内の値であることがさらに好ましい。
　なお、第１の酸化亜鉛膜の膜厚（ｄ）は、実施例１において具体的に説明するように、分光エリプソメーターを用いて、測定することができる。 (2) Film thickness The film thickness of the first zinc oxide film is preferably in the range of 10 to 300 nm.
This is because when the thickness of the first zinc oxide film is less than 10 nm, it may be difficult to stably form the zinc oxide film.
On the other hand, when the film thickness of the first zinc oxide film exceeds 300 nm, it takes an excessive amount of time to form the zinc oxide film, resulting in a decrease in productivity and adhesion to the base, resulting in film warpage. This is because there is a case where the problem occurs.
Therefore, the thickness of the first zinc oxide film is more preferably in the range of 20 to 250 nm, and still more preferably in the range of 30 to 200 nm.
The film thickness (d) of the first zinc oxide film can be measured using a spectroscopic ellipsometer, as will be specifically described in Example 1.

（３）比抵抗
　また、第１の酸化亜鉛膜１６の初期の比抵抗（ρ0）を１×１０-4～１×１０-2Ω・ｃｍの範囲内の値とすることが好ましい。
　この理由は、透明導電層の初期の比抵抗が１×１０-4Ω・ｃｍ未満の値になると、成膜条件が複雑になる場合があるためである。
　一方、透明導電層の初期の比抵抗が１×１０-2Ω・ｃｍを超えた値になると、好適な導電性が得られない場合があるためである。
　したがって、透明導電膜層の初期の比抵抗を３×１０-4～８×１０-3Ω・ｃｍの範囲内の値とすることが、より好ましく、５×１０-4～５×１０-3Ω・ｃｍの範囲内の値とすることがさらに好ましい。
　なお、透明導電層の比抵抗（ρ）は、実施例１において具体的に説明するように、透明導電性積層体の膜厚（ｄ）および測定した表面抵抗率（Ｒ）より、算出することができる。 (3) Specific Resistance The initial specific resistance (ρ 0 ) of the first zinc oxide film 16 is preferably set to a value in the range of 1 × 10 −4 to 1 × 10 −2 Ω · cm.
This is because the film forming conditions may be complicated when the initial specific resistance of the transparent conductive layer is less than 1 × 10 −4 Ω · cm.
On the other hand, when the initial specific resistance of the transparent conductive layer exceeds 1 × 10 −2 Ω · cm, suitable conductivity may not be obtained.
Accordingly, the initial specific resistance of the transparent conductive film layer is more preferably set to a value in the range of 3 × 10 −4 to 8 × 10 −3 Ω · cm, and 5 × 10 −4 to 5 × 10 −3. More preferably, the value is within the range of Ω · cm.
The specific resistance (ρ) of the transparent conductive layer should be calculated from the film thickness (d) of the transparent conductive laminate and the measured surface resistivity (R), as specifically described in Example 1. Can do.

１－２．第２の酸化亜鉛膜
　第２の酸化亜鉛膜は、インジウムを含む酸化亜鉛膜であることを特徴とする。
　より具体的には、図１(ａ)、（ｃ）に示すように、第１の酸化亜鉛膜１６上に形成される酸化亜鉛膜１０であって、インジウムを含む酸化亜鉛膜であることを特徴とする。 1-2. Second Zinc Oxide Film The second zinc oxide film is a zinc oxide film containing indium.
More specifically, as shown in FIGS. 1A and 1C, the zinc oxide film 10 formed on the first zinc oxide film 16 is a zinc oxide film containing indium. Features.

（１）構成
　第２の酸化亜鉛膜を構成する元素としては、酸化亜鉛を主成分とし、インジウムを含んでいれば特に制限はないが、導電性を向上させるために、さらにガリウム、アルミニウム、ホウ素、ケイ素、錫、ゲルマニウム、アンチモン、イリジウム、レニウム、セリウム、ジルコニウム、マグネシウム、チタン、バナジウム、マンガン、鉄、コバルト、ニッケル、銅、ニオブ、モリブデン、テクネチウム、ルテニウム、ロジウム、パラジウム、銀、ランタノイド、ハフニウム、タンタル、タングステン、白金、金、ビスマス、アクチノイド、スカンジウム及びイットリウムから選択される少なくとも１種を含んでいることが好ましい。
　特に、電気特性および湿熱特性に優れる点から、第２の酸化亜鉛膜が、酸化亜鉛を含むとともにインジウムおよびガリウムをドープしてなる酸化亜鉛膜（以下Ｉｎ－ＧＺＯ膜と称する場合がある）であることが好ましい。 (1) Structure The element constituting the second zinc oxide film is not particularly limited as long as it contains zinc oxide as a main component and contains indium. However, in order to improve conductivity, further gallium, aluminum, boron , Silicon, tin, germanium, antimony, iridium, rhenium, cerium, zirconium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, lanthanoid, hafnium It is preferable that at least one selected from tantalum, tungsten, platinum, gold, bismuth, actinoid, scandium and yttrium is contained.
In particular, the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with indium and gallium (hereinafter sometimes referred to as an In-GZO film) because of its excellent electrical characteristics and wet heat characteristics. It is preferable.

　また、第２の酸化亜鉛膜が、酸化亜鉛を含むとともにインジウムおよびガリウムをドープしてなる酸化亜鉛膜である場合、含まれる各種添加元素の配合量は、透明導電層は、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を０．０１～２５ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を０．１～１０ａｔｏｍ％の範囲内の値とすることが好ましい。
　この理由は、透明導電層におけるインジウム量が上記範囲内の値であれば、良好な湿熱特性と電気特性を得ることができるためである。
　また、ガリウム量が、上記範囲外の値となると、電気特性が劣る場合があるためである。
　すなわち、透明導電層におけるインジウム量が０．０１～２５ａｔｏｍ％の範囲内の値であれば、電気特性と湿熱特性の両方のバランスがよく、湿熱特性に優れる透明導電性積層体を得ることができる。 Further, when the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with indium and gallium, the amount of various additive elements contained is determined by the XPS elemental analysis measurement. The zinc content, the gallium content, the oxygen content, and the total content (100 atom%) of the indium content are set to a value in the range of 0.01 to 25 atom%, and the gallium content is 0.1 to 10 atom%. It is preferable to set the value within the range of%.
This is because if the amount of indium in the transparent conductive layer is a value within the above range, good wet heat characteristics and electrical characteristics can be obtained.
Moreover, it is because an electrical property may be inferior when the amount of gallium becomes a value outside the above range.
That is, when the amount of indium in the transparent conductive layer is a value within the range of 0.01 to 25 atom%, it is possible to obtain a transparent conductive laminate having a good balance between electrical characteristics and wet heat characteristics and excellent wet heat characteristics. .

　なお、湿熱特性を良好なものとする点から、透明導電層において、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を０．０２～８ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を０．５～１０ａｔｏｍ％の範囲内の値とすることが好ましく、インジウム量を０．１～７ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を１～１０ａｔｏｍ％の範囲内の値とすることがより好ましく、インジウム量を０．１～６ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を１～７ａｔｏｍ％の範囲内の値とすることが特に好ましい。
　また、湿熱特性および電気特性とのバランスを考慮した場合、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を、８ａｔｏｍ％を超えて２５ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を０．５～１０ａｔｏｍ％の範囲内の値とすることが好ましく、インジウム量を９～２２ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を１～１０ａｔｏｍ％の範囲内の値とすることがより好ましく、インジウム量を１０～２０ａｔｏｍ％の範囲内の値とし、かつ、ガリウム量を１～７ａｔｏｍ％の範囲内の値とすることが特に好ましい。 In order to improve the wet heat characteristics, in the transparent conductive layer, the amount of indium with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement The value is preferably in the range of 0.02 to 8 atom%, the gallium content is preferably in the range of 0.5 to 10 atom%, and the indium content is in the range of 0.1 to 7 atom%. More preferably, the gallium content is in the range of 1 to 10 atom%, the indium content is in the range of 0.1 to 6 atom%, and the gallium content is in the range of 1 to 7 atom%. It is particularly preferable to set the value of.
In consideration of the balance between wet heat characteristics and electrical characteristics, the amount of indium is 8 atom% relative to the total amount (100 atom%) of zinc, gallium, oxygen and indium measured by XPS elemental analysis. And a value in the range of 25 atom%, and preferably the gallium content is in the range of 0.5 to 10 atom%, the indium content is in the range of 9 to 22 atom%, and More preferably, the amount of gallium is set to a value within the range of 1 to 10 atom%, the amount of indium is set to a value within the range of 10 to 20 atom%, and the amount of gallium is set to a value within the range of 1 to 7 atom%. Is particularly preferred.

（２）膜厚
　また、第２の酸化亜鉛膜の膜厚が１０～３００ｎｍの範囲内の値であることが好ましい。
　この理由は、第２の酸化亜鉛膜の膜厚が１０ｎｍ未満の値となると、酸化亜鉛膜の安定的形成が困難となる場合が生じるばかりか、湿熱特性等が、著しく低下する場合があるためである。
　一方、第２の酸化亜鉛膜の膜厚が３００ｎｍを超えた値になると、酸化亜鉛膜の形成に過度に時間を要し、生産性が低下したり、下地に対する密着性が低下して、膜反りが生じたりする場合があるためである。
　したがって、第２の酸化亜鉛膜の膜厚が２０～２５０ｎｍの範囲内の値であることがより好ましく、３０～２００ｎｍの範囲内の値であることがさらに好ましい。
　なお、第２の酸化亜鉛膜の膜厚（ｄ）は、実施例１において具体的に説明するように、分光エリプソメーターを用いて、測定することができる。 (2) Film thickness The film thickness of the second zinc oxide film is preferably a value within the range of 10 to 300 nm.
The reason for this is that when the thickness of the second zinc oxide film is less than 10 nm, stable formation of the zinc oxide film may become difficult, and wet heat characteristics and the like may be significantly reduced. It is.
On the other hand, when the thickness of the second zinc oxide film exceeds 300 nm, it takes an excessive amount of time to form the zinc oxide film, and the productivity decreases or the adhesion to the base decreases. This is because warping may occur.
Therefore, the thickness of the second zinc oxide film is more preferably in the range of 20 to 250 nm, and still more preferably in the range of 30 to 200 nm.
The film thickness (d) of the second zinc oxide film can be measured using a spectroscopic ellipsometer, as will be specifically described in Example 1.

（３）比抵抗
　また、第２の酸化亜鉛膜１０の初期の比抵抗（ρ0）を５×１０-4Ω・ｃｍを超えて、２．１×１０-1Ω・ｃｍ以下の値とすることが好ましい。
　この理由は、第２の酸化亜鉛膜の初期の比抵抗が５×１０-4Ω・ｃｍ以下の値になると、成膜条件が複雑になる場合があるためである。
　一方、第２の酸化亜鉛膜の初期の比抵抗が１×１０-1Ω・ｃｍを超えた値になると、好適な導電性が得られない場合があるためである。
　したがって、第２の酸化亜鉛膜の初期の比抵抗を５．５×１０-4Ω・ｃｍ～１×１０-2Ω・ｃｍの範囲内の値とすることが、より好ましく、６×１０-4Ω・ｃｍ～５×１０-3Ω・ｃｍの範囲内の値とすることがさらに好ましい。
　なお、第２の酸化亜鉛膜の比抵抗（ρ）は、実施例１において具体的に説明するように、透明導電性積層体の膜厚（ｄ）および測定した表面抵抗率（Ｒ）より、算出することができる。 (3) Specific resistance The initial specific resistance (ρ 0 ) of the second zinc oxide film 10 exceeds 5 × 10 −4 Ω · cm and is less than 2.1 × 10 −1 Ω · cm. It is preferable to do.
This is because, when the initial specific resistance of the second zinc oxide film becomes a value of 5 × 10 −4 Ω · cm or less, the film forming conditions may be complicated.
On the other hand, if the initial specific resistance of the second zinc oxide film exceeds 1 × 10 −1 Ω · cm, suitable conductivity may not be obtained.
Therefore, the initial specific resistance of the second zinc oxide film is more preferably set to a value in the range of 5.5 × 10 −4 Ω · cm to 1 × 10 −2 Ω · cm, more preferably 6 × 10 − More preferably, the value is within the range of 4 Ω · cm to 5 × 10 −3 Ω · cm.
The specific resistance (ρ) of the second zinc oxide film is determined from the film thickness (d) of the transparent conductive laminate and the measured surface resistivity (R), as specifically described in Example 1. Can be calculated.

２.基材
（１）種類
　図１に例示する基材１２としては、透明性に優れるものであれば特に限定されず、ガラス、セラミック、樹脂フィルム等が挙げられる。樹脂フィルムの材料としては、ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリオレフィン、ポリエステル、ポリカーボネート、ポリスルフォン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリアリレート、アクリル系樹脂、シクロオレフィン系コポリマ、シクロオレフィン系ポリマ、芳香族系重合体、ポリウレタン系ポリマ等が挙げられる。
　特に、本発明の透明導電性積層体が柔軟性に優れるものとするためには、基材が、樹脂フィルムであることが好ましい。
　また、これら樹脂フィルムの中でも、透明性に優れ、柔軟性および汎用性があることから、ポリエステル、ポリカーボネート、ポリイミド、ポリアミド又はシクロオレフィン系ポリマ、ポリエーテルスルフォンからなる群から選ばれる少なくとも１種であることが好ましく、ポリエステル又はシクロオレフィン系ポリマがより好ましい。
　より具体的には、ポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート等が挙げられる。
　また、ポリアミドとしては、全芳香族ポリアミド、ナイロン６、ナイロン６６、ナイロン共重合体等が挙げられる。
　また、シクロオレフィン系ポリマとしては、ノルボルネン系重合体、単環の環状オレフィン系重合体、環状共役ジエン系重合体、ビニル脂環式炭化水素重合体、及びこれらの水素化物が挙げられる。例えば、アぺル(三井化学社製のエチレン－シクロオレフィン共重合体)、アートン（ＪＳＲ社製のノルボルネン系重合体）、ゼオノア（日本ゼオン社製のノルボルネン系重合体）等が挙げられる。 2. Type of base material (1) The base material 12 illustrated in FIG. 1 is not particularly limited as long as it is excellent in transparency, and examples thereof include glass, ceramics, and resin films. Resin film materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane Examples thereof include olefin copolymers, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like.
In particular, in order for the transparent conductive laminate of the present invention to be excellent in flexibility, the substrate is preferably a resin film.
Among these resin films, since they are excellent in transparency and have flexibility and versatility, they are at least one selected from the group consisting of polyesters, polycarbonates, polyimides, polyamides, cycloolefin polymers, and polyether sulfones. It is preferable that a polyester or a cycloolefin polymer is more preferable.
More specifically, examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Examples thereof include apell (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), arton (a norbornene polymer manufactured by JSR), zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like.

（２）膜厚
　また、図１に例示する基材１２の膜厚は、使用目的等に応じて決定すればよいが、柔軟性および取り扱いが容易であるという点から、１～１０００μｍの範囲内の値とすることが好ましく、５～２５０μｍの範囲内の値とすることがより好ましく、１０～２００μｍの範囲内の値とすることがさらに好ましい。 (2) Film thickness The film thickness of the substrate 12 illustrated in FIG. 1 may be determined according to the purpose of use, etc., but is within the range of 1 to 1000 μm from the viewpoint of flexibility and easy handling. The value is preferably in the range of 5 to 250 μm, more preferably in the range of 10 to 200 μm.

（３）添加剤
　また、基材には、上述した樹脂成分の他に、透明性等を損なわない範囲で、酸化防止剤、難燃剤、滑剤等の各種添加剤を含んでも良い。 (3) Additives In addition to the resin component described above, the base material may contain various additives such as an antioxidant, a flame retardant, and a lubricant as long as transparency and the like are not impaired.

３．他層
　さらに、本発明の透明導電性積層体には、必要に応じて、各種他層を設けることができる。
　このような他層としては、例えば、ガスバリア層、プライマー層、平坦化層、ハードコート層、保護層、帯電防止層、防汚層、防眩層、カラーフィルター、接着剤層、装飾層、印刷層等が挙げられる。
　ここで、プライマー層は、基材と透明導電層の密着性を向上させるために設ける層であり、材料としては、例えば、ウレタン系樹脂、アクリル系樹脂、シランカップリング剤、エポキシ系樹脂、ポリエステル系樹脂、紫外線硬化型樹脂等の公知のものを用いることができる。 3. Other layers Furthermore, various other layers can be provided in the transparent conductive laminate of the present invention as necessary.
Examples of such other layers include gas barrier layers, primer layers, planarization layers, hard coat layers, protective layers, antistatic layers, antifouling layers, antiglare layers, color filters, adhesive layers, decorative layers, and printing. Layer and the like.
Here, a primer layer is a layer provided in order to improve the adhesiveness of a base material and a transparent conductive layer, As a material, a urethane type resin, an acrylic resin, a silane coupling agent, an epoxy resin, polyester, for example Known resins such as a resin and an ultraviolet curable resin can be used.

　また、ガスバリア層は、基材と透明導電層の間に設けることが好ましく、ガスバリア層を構成する材料としては、酸素および水蒸気の透過を阻止するものではれば、特に制約はないが、透明性がよく、ガスバリア性が良好なものが好ましい。
　より具体的には、構成材料としては、例えば、アルミニウム、マグネシウム、ジルコニウム、チタン、亜鉛、錫等の金属；酸化ケイ素、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化亜鉛、酸化インジウム、酸化錫、酸化亜鉛錫等の無機酸化物；窒化ケイ素等の無機窒化物；無機酸窒化物；無機炭化物；無機硫化物；無機酸窒化炭化物；高分子化合物およびこれらの複合体から選ばれる少なくとも１種であることが好ましい。
　そして、これらの中でも、ガスバリア層が、酸化ケイ素、窒化ケイ素、酸窒化ケイ素、酸化亜鉛錫（ＺＴＯ）から選ばれる少なくとも１種から構成されることがより好ましい。
　また、かかるガスバリア層は、各種高分子樹脂、硬化剤、老化防止剤、光安定剤、難燃剤等の他の配合成分を含んでいても良い。 Further, the gas barrier layer is preferably provided between the base material and the transparent conductive layer, and the material constituting the gas barrier layer is not particularly limited as long as it prevents the permeation of oxygen and water vapor. It is preferable that the gas barrier property is good.
More specifically, examples of the constituent material include metals such as aluminum, magnesium, zirconium, titanium, zinc, and tin; silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, indium oxide, tin oxide, and oxide. Inorganic oxides such as zinc tin; inorganic nitrides such as silicon nitride; inorganic oxynitrides; inorganic carbides; inorganic sulfides; inorganic oxynitride carbides; at least one selected from polymer compounds and composites thereof Is preferred.
Among these, the gas barrier layer is more preferably composed of at least one selected from silicon oxide, silicon nitride, silicon oxynitride, and zinc tin oxide (ZTO).
The gas barrier layer may contain other compounding components such as various polymer resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.

　また、ガスバリア層を形成する方法としては、特に限定されず、例えば、上述の材料を蒸着法、スパッタリング法、イオンプレーティング法、熱ＣＶＤ法、プラズマＣＶＤ法等により基材上に形成する方法や、上記材料を有機溶剤に溶解または分散した溶液を公知の塗布方法によって基材上に塗布し、得られた塗膜を適度に乾燥して形成する方法、得られた塗膜に対して、大気圧プラズマやイオン注入法、ランプアニール処理等の表面改質を行って形成する方法等が挙げられる。 In addition, the method for forming the gas barrier layer is not particularly limited. For example, a method for forming the above-described material on a substrate by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, or the like. A method in which a solution obtained by dissolving or dispersing the above-described material in an organic solvent is applied onto a substrate by a known application method, and the resulting coating film is appropriately dried to form a coating film. Examples thereof include a method of performing surface modification such as atmospheric pressure plasma, ion implantation, and lamp annealing.

　また、ガスバリア層の厚みは特に制限されるものではなく、通常２０ｎｍ～５０μｍの範囲内の値であることが好ましい。
　この理由は、このような所定膜厚のガスバリア層とすることによって、さらに優れたガスバリア性や密着性が得られるとともに、柔軟性と、被膜強度とを両立させることができるためである。
　したがって、ガスバリア層の膜厚を、３０ｎｍ～１μｍの範囲内の値とすることがより好ましく、４０ｎｍ～５００ｎｍの範囲内の値とすることがさらに好ましい。 Further, the thickness of the gas barrier layer is not particularly limited, and is usually preferably a value within the range of 20 nm to 50 μm.
The reason for this is that by using such a gas barrier layer having a predetermined film thickness, further excellent gas barrier properties and adhesion can be obtained, and at the same time, both flexibility and coating strength can be achieved.
Therefore, the film thickness of the gas barrier layer is more preferably set to a value within the range of 30 nm to 1 μm, and further preferably set to a value within the range of 40 nm to 500 nm.

　また、ガスバリア層の４０℃、相対湿度９０％の雰囲気下で測定される水蒸気透過率を０．１ｇ／ｍ2／ｄａｙ以下の値とすることが好ましく、０．０５ｇ／ｍ2／ｄａｙ以下の値とすることがより好ましく、０．０１ｇ／ｍ2／ｄａｙ以下の値とすることがさらに好ましい。
　この理由は、このような水蒸気透過率の値とすることによって、透明導電層が劣化することを防ぎ、耐湿熱性に優れたガスバリア性が得られるためである。
　なお、ガスバリア層の水蒸気透過率としては、公知方法で測定することができ、例えば、市販の水蒸気透過率測定装置を用いて測定することができる。 Further, 40 ° C. of the gas barrier layer, a water vapor permeability as measured in an atmosphere of 90% RH is preferably not more than the value 0.1g / m 2 / day, 0.05g / m 2 / day or less of More preferably, the value is 0.01 g / m 2 / day or less.
The reason for this is that by setting such a value of water vapor transmission rate, the transparent conductive layer can be prevented from deteriorating and gas barrier properties excellent in moisture and heat resistance can be obtained.
In addition, it can measure by a well-known method as a water vapor transmission rate of a gas barrier layer, For example, it can measure using a commercially available water vapor transmission rate measuring apparatus.

４．透明導電性積層体
（１）態様
　図１（ａ）に例示される透明導電性積層体５０は、基材１２上の片面または両面に透明導電層１８を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第１の酸化亜鉛膜１６と、第２の酸化亜鉛膜１０とが順次に形成されており、第１および第２の酸化亜鉛膜が上述の構成を備えることを特徴とする。
　また、図１（ｃ）に示すように、第２の酸化亜鉛膜１０上に、さらに第１の酸化亜鉛膜１６´を積層することも好ましい態様である。
　このように、インジウムを含まない第１およびインジウムを含む第２の酸化亜鉛膜を組み合わせて複層化することにより、透明導電性積層体の湿熱特性を好適かつ緻密に調整することができる。
　なお、本発明において、透明導電層の透明性に関して、所定厚さ、例えば、２０～６００ｎｍのいずれかにおいて、波長５５０ｎｍの光線透過率が７０％以上の値であることが好ましく、８０％以上の値であることがより好ましく、９０％以上の値であることがさらに好ましい。
　また、透明導電性積層体の透明性に関して、所定厚さ、例えば１０μｍ～１ｍｍのいずれかにおいて、波長５５０ｎｍの光線透過率が５０％以上の値であることが好ましく、６０％以上の値であることがより好ましく、７０％以上の値であることがさらに好ましい。 4). Transparent Conductive Laminate (1) Aspect The transparent conductive laminate 50 illustrated in FIG. 1A is a transparent conductive laminate in which a transparent conductive layer 18 is formed on one side or both sides on a substrate 12. In the transparent conductive layer, the first zinc oxide film 16 and the second zinc oxide film 10 are sequentially formed from the base material side along the film thickness direction. A zinc oxide film has the above-described configuration.
In addition, as shown in FIG. 1C, it is also a preferable aspect that a first zinc oxide film 16 ′ is further laminated on the second zinc oxide film 10.
Thus, the wet heat characteristic of a transparent conductive laminated body can be adjusted suitably and precisely by combining the 2nd zinc oxide film | membrane which contains the 1st and indium containing indium which do not contain indium.
In the present invention, regarding the transparency of the transparent conductive layer, the light transmittance at a wavelength of 550 nm is preferably 70% or more at a predetermined thickness, for example, any of 20 to 600 nm, and 80% or more. More preferably, the value is 90% or more.
Further, regarding the transparency of the transparent conductive laminate, the light transmittance at a wavelength of 550 nm is preferably 50% or more at a predetermined thickness, for example, 10 μm to 1 mm, and is a value of 60% or more. More preferably, the value is more preferably 70% or more.

（２）湿熱特性
また、本発明の透明導電性積層体における透明導電層１８における初期の比抵抗をρ0とし、６０℃、相対湿度９５％の条件下で、５００時間、保管した後の比抵抗をρ1としたときに、ρ1/ρ0で表わされる比率を１．３以下の値とすることが好ましい。
　より具体的には、本願発明は、透明導電層が、電気特性に優れるインジウムを含まない第１の酸化亜鉛膜と、湿熱特性に優れるインジウムを含む第２の酸化亜鉛膜とから形成されてなるため、第２の酸化亜鉛膜を湿熱劣化抑制層として用いることで、２層の相乗効果により、透明導電性積層体の初期の比抵抗を増加させることなく、良好な湿熱特性を有する透明導電性積層体を得ることができる。
　なお、透明導電層の比抵抗（ρ0、ρ1）は、実施例１において具体的に説明するように、表面抵抗測定装置を用いて、測定することができる。 (2) Wet heat characteristics The initial resistivity of the transparent conductive layer 18 in the transparent conductive laminate of the present invention is ρ 0, and the ratio after storage for 500 hours at 60 ° C. and 95% relative humidity. When the resistance is ρ 1 , the ratio represented by ρ 1 / ρ 0 is preferably set to a value of 1.3 or less.
More specifically, in the present invention, the transparent conductive layer is formed of a first zinc oxide film not containing indium having excellent electrical characteristics and a second zinc oxide film containing indium having excellent wet heat characteristics. Therefore, by using the second zinc oxide film as a moist heat deterioration suppressing layer, the transparent conductivity having good moist heat characteristics without increasing the initial specific resistance of the transparent conductive laminate by the synergistic effect of the two layers. A laminate can be obtained.
In addition, the specific resistance (ρ 0 , ρ 1 ) of the transparent conductive layer can be measured using a surface resistance measuring device as specifically described in Example 1.

　ここで、図２を参照して、透明導電性積層体における第２の透明導電膜の膜厚と、環境試験前後における比抵抗の変化との関係を説明する。
　すなわち、図２の横軸に、第２の酸化亜鉛膜の膜厚が採って示してあり、縦軸に、６０℃、相対湿度９５％の条件下での保管経過時間が採って示してあり、縦軸に、ρ1/ρ0で表わされる比率が採って示してある。
　かかる特性曲線より、湿熱劣化抑制層として第２の酸化亜鉛膜を第１の酸化亜鉛膜に備えることによって、著しく透明導電性積層体の湿熱特性が向上していることが理解される。
　なお、各試料は、実施例に詳細を記載するが、基材上に、第１の酸化亜鉛膜として、ＺｎＯ：Ｇａ2Ｏ3＝９４．３重量％：５．７重量％の重量比を有する焼結体を用いて厚さ１００ｎｍに成膜し、さらに第２の酸化亜鉛膜として、ＺｎＯ：Ｇａ2Ｏ3：Ｉｎ2Ｏ3＝９３.３重量％：５.７重量％：１．０重量％の重量比を有する焼結体を用いて各膜厚に成膜した透明導電性積層体を用いている。 Here, with reference to FIG. 2, the relationship between the film thickness of the 2nd transparent conductive film in a transparent conductive laminated body, and the change of the specific resistance before and behind an environmental test is demonstrated.
That is, the horizontal axis of FIG. 2 shows the thickness of the second zinc oxide film, and the vertical axis shows the elapsed storage time under conditions of 60 ° C. and relative humidity 95%. On the vertical axis, the ratio represented by ρ 1 / ρ 0 is taken.
From this characteristic curve, it is understood that the wet heat characteristics of the transparent conductive laminate are remarkably improved by providing the first zinc oxide film with the second zinc oxide film as the wet heat deterioration suppressing layer.
Each sample is described in detail in Example, on a substrate, a first zinc oxide film, ZnO: Ga 2 O 3 = 94.3 wt%: 5.7 wt% of the weight ratio The second zinc oxide film is formed as ZnO: Ga 2 O 3 : In 2 O 3 = 93.3% by weight: 5.7% by weight: 1. The transparent conductive laminated body formed into a film in each film thickness using a sintered body having a weight ratio of 0% by weight is used.

（３）表面抵抗率
　また、本発明の透明導電性積層体の表面抵抗率（Ｒ）は、１０００Ω／□以下の値であることが好ましい。
　より具体的には、透明導電性積層体の表面抵抗率が１０００Ω／□を超えた値となると、透明導電性積層体として好適な導電性が得られない場合があるためである。
　したがって、透明導電性積層体の表面抵抗率が、５００Ω／□以下の値であることがより好ましく、２００Ω／□以下の値であることがさらに好ましい。
　なお、表面抵抗率の測定方法については、実施例で具体的に説明するように、表面抵抗測定装置を用いて測定することができる。 (3) Surface resistivity Moreover, it is preferable that the surface resistivity (R) of the transparent conductive laminated body of this invention is a value of 1000 ohms / square or less.
More specifically, when the surface resistivity of the transparent conductive laminate is a value exceeding 1000 Ω / □, conductivity suitable for the transparent conductive laminate may not be obtained.
Therefore, the surface resistivity of the transparent conductive laminate is more preferably a value of 500Ω / □ or less, and further preferably a value of 200Ω / □ or less.
In addition, about the measuring method of surface resistivity, it can measure using a surface resistance measuring apparatus so that it may demonstrate concretely in an Example.

［第２の実施形態］
　第２の実施形態は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体である。
　以下、第２の実施形態の透明導電性積層体につき、適宜図面を参照して具体的に説明する。 [Second Embodiment]
The second embodiment is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of a base material, and the transparent conductive layer is second oxidized along the film thickness direction from the base material side. A zinc film and a first zinc oxide film are sequentially formed, the first zinc oxide film is a zinc oxide film not containing indium, and the second zinc oxide film is zinc oxide containing indium. A transparent conductive laminate characterized by being a film.
Hereinafter, the transparent conductive laminate of the second embodiment will be specifically described with reference to the drawings as appropriate.

　より具体的には、図１（ｂ）に例示される透明導電性積層体５０´は、基材１２上の片面または両面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、基材側から膜厚方向に沿って、第２の酸化亜鉛膜１０と、第１の酸化亜鉛膜１６とが順次に形成されている。
　また、図１（ｄ）に示すように、第１の酸化亜鉛膜１６上に、さらに第２の酸化亜鉛膜１０´を積層することも好ましい態様である。
　このようにインジウムを含まない第１およびインジウムを含む第２の酸化亜鉛膜を、組み合わせて複層化することにより、透明導電性積層体の湿熱特性を好適かつ緻密に調整することができる。
　なお、第１および第２の酸化亜鉛膜は、それぞれ、上述の構成と同じであり、また、透明導電性積層体としての特性も上述と同様であるため、詳細については省略する。 More specifically, the transparent conductive laminate 50 ′ illustrated in FIG. 1B is a transparent conductive laminate in which a transparent conductive layer is formed on one side or both sides of the substrate 12, In the transparent conductive layer, the second zinc oxide film 10 and the first zinc oxide film 16 are sequentially formed along the film thickness direction from the substrate side.
Further, as shown in FIG. 1D, it is also a preferable aspect that a second zinc oxide film 10 ′ is further laminated on the first zinc oxide film 16.
Thus, the wet heat characteristic of a transparent conductive laminated body can be adjusted suitably and precisely by combining the 2nd zinc oxide film | membrane which contains the 1st and indium which do not contain indium in combination.
The first and second zinc oxide films have the same structure as described above, and the characteristics as the transparent conductive laminate are the same as those described above, and thus the details are omitted.

［第３の実施形態］
　第３の実施形態は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、透明導電層が、基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、下記工程（１）～（３）を含むことを特徴とする透明導電性積層体の製造方法である。
（１）基材と、第１の酸化亜鉛膜用の焼結体と、第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２）基材上に、スパッタリング法または蒸着法を用いて、第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、第１の酸化亜鉛膜を形成する工程
（３）第１の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、第２の酸化亜鉛膜用の焼結体から、インジウムを含む、第２の酸化亜鉛膜を形成する工程
　以下、第３の実施形態の透明導電性積層体の製造方法について、具体的に説明する。 [Third Embodiment]
3rd Embodiment is a manufacturing method of the transparent conductive laminated body formed by forming a transparent conductive layer in the at least single side | surface of a base material, Comprising: A transparent conductive layer is a 1st along a film thickness direction from a base material side, A method for producing a transparent conductive laminate, comprising the steps of (1) to (3) described below, wherein a zinc oxide film of 1 and a second zinc oxide film are sequentially formed.
(1) Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2) Sputtering method or vapor deposition method on the substrate (1) A step of forming a first zinc oxide film that does not contain indium from the sintered body for the first zinc oxide film (3) Sputtering or vapor deposition is performed on the first zinc oxide film. Step of forming a second zinc oxide film containing indium from a sintered body for the second zinc oxide film Hereinafter, the manufacturing method of the transparent conductive laminate of the third embodiment will be described in detail. Explained.

１．工程（１）：基材および焼結体を準備する工程
　工程（１）は、基材および焼結体を準備する工程である。
　すなわち、図１(ａ)、（ｃ）に例示される第１の酸化亜鉛膜１６は、酸化亜鉛を主成分とするとともに酸化インジウムを含まない焼結体から成膜することを特徴とする。
　また、第２の酸化亜鉛膜１０は、酸化亜鉛を主成分とするとともに、少なくとも酸化インジウムを含む焼結体から成膜することを特徴とする。
　なお、基材の詳細については、既に記載した通りであるため、省略する。 1. Step (1): Step of Preparing Base Material and Sintered Body Step (1) is a step of preparing the base material and the sintered body.
That is, the first zinc oxide film 16 illustrated in FIGS. 1A and 1C is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide.
The second zinc oxide film 10 is formed from a sintered body containing zinc oxide as a main component and at least indium oxide.
The details of the base material are the same as described above, and will be omitted.

（１）第１の酸化亜鉛膜焼結体
　また、第１の酸化亜鉛膜が、酸化亜鉛を主成分とするとともに、酸化インジウムを含まず、酸化ガリウムを含む焼結体から成膜する場合について、説明する。
　すなわち、第１の酸化亜鉛膜を形成する焼結体において、当該焼結体の全体量に対して、酸化亜鉛の配合量を９０～９９．９重量％の範囲内の値とし、酸化ガリウムの配合量を０．１～１０重量％の範囲内の値とすることが好ましい。
　この理由は、焼結体の全体量に対して、酸化ガリウムの配合量が０．１重量％未満の場合は、成膜後の第１の酸化亜鉛膜に含まれるガリウムの量が著しく少なくなり、十分な電気特性が得られない場合があるためである。
　一方、酸化ガリウムの量が１０重量％を超える場合は、成膜後の第１の酸化亜鉛膜に含まれるガリウムの量が増加するため、比抵抗が大きな値となり、電気特性が低下する場合があるためである。
　したがって、焼結体の全体量に対して、酸化亜鉛の配合量を９２～９９重量％の範囲内の値とし、酸化ガリウムの配合量を１～８重量％の範囲内の値とすることがより好ましい。
　また、焼結体の全体量に対して、酸化亜鉛の配合量を９３～９９重量％の範囲内の値とし、酸化ガリウムの配合量を１～７重量％の範囲内の値とすることがさらに好ましい。 (1) First Zinc Oxide Film Sintered Body Further, the first zinc oxide film is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide but containing gallium oxide. ,explain.
That is, in the sintered body forming the first zinc oxide film, the blending amount of zinc oxide is set to a value within the range of 90 to 99.9% by weight with respect to the total amount of the sintered body, and gallium oxide The blending amount is preferably set to a value within the range of 0.1 to 10% by weight.
The reason for this is that when the amount of gallium oxide is less than 0.1% by weight relative to the total amount of the sintered body, the amount of gallium contained in the first zinc oxide film after film formation is significantly reduced. This is because sufficient electrical characteristics may not be obtained.
On the other hand, when the amount of gallium oxide exceeds 10% by weight, the amount of gallium contained in the first zinc oxide film after film formation increases, so that the specific resistance becomes a large value and the electrical characteristics may be deteriorated. Because there is.
Therefore, the blending amount of zinc oxide is set to a value in the range of 92 to 99% by weight and the blending amount of gallium oxide is set to a value in the range of 1 to 8% by weight with respect to the total amount of the sintered body. More preferred.
Further, with respect to the total amount of the sintered body, the blending amount of zinc oxide is set to a value within the range of 93 to 99% by weight, and the blending amount of gallium oxide is set to a value within the range of 1 to 7% by weight. Further preferred.

（２）第２の酸化亜鉛膜焼結体
　また、第２の酸化亜鉛膜が、酸化亜鉛を主成分とするとともに、酸化インジウムおよび酸化ガリウムをさらに含む焼結体から成膜する場合について、説明する。
　すなわち、第２の酸化亜鉛膜を形成する焼結体において、当該焼結体の全体量に対して、酸化亜鉛の配合量を１５～９９．９８重量％の範囲内の値とし、酸化ガリウムの配合量を０．０１～１５重量％の範囲内の値とし、かつ、酸化インジウムの配合量を０．０１～７０重量の範囲内の値とすることが好ましい。
　この理由は、配合量が制御された酸化亜鉛－酸化ガリウム－酸化インジウムの三元系焼結体を用いることにより、湿熱特性に優れた第２の酸化亜鉛膜を効率的に成膜することができ、ひいては、生産効率を向上させることができるためである。
　より具体的には、焼結体の全体量に対して、酸化インジウムの配合量が０．０１重量％未満の場合は、成膜後の第２の酸化亜鉛膜に含まれるインジウムの量が著しく少なくなり、十分な湿熱特性が得られない場合があるためである。
　一方、酸化インジウムの量が７０重量％を超える場合は、成膜後の第２の酸化亜鉛膜に含まれるインジウムの量が著しく増加してしまう場合があるためである。
　したがって、焼結体の全体量に対して、酸化亜鉛の配合量を２７～９９．４重量％の範囲内の値とし、酸化ガリウムの配合量を０．５～８重量％の範囲内の値とし、かつ、酸化インジウムの配合量を０．１～６５重量の範囲内の値とすることがより好ましい。
　また、焼結体の全体量に対して、酸化亜鉛の配合量を３３～９８.７重量％の範囲内の値とし、酸化ガリウムの配合量を１～７重量％の範囲内の値とし、かつ、酸化インジウムの配合量を０．３～６０重量％の範囲内の値とすることがさらに好ましい。 (2) Second Zinc Oxide Film Sintered Body Also, the case where the second zinc oxide film is formed from a sintered body containing zinc oxide as a main component and further containing indium oxide and gallium oxide will be described. To do.
That is, in the sintered body forming the second zinc oxide film, the blending amount of zinc oxide is set to a value within the range of 15 to 99.98% by weight with respect to the total amount of the sintered body, The blending amount is preferably set to a value within the range of 0.01 to 15% by weight, and the indium oxide content is preferably set to a value within the range of 0.01 to 70% by weight.
The reason for this is that by using a ternary sintered body of zinc oxide-gallium oxide-indium oxide whose amount is controlled, a second zinc oxide film having excellent wet heat characteristics can be efficiently formed. This is because production efficiency can be improved.
More specifically, when the blending amount of indium oxide is less than 0.01% by weight with respect to the total amount of the sintered body, the amount of indium contained in the second zinc oxide film after film formation is remarkably large. This is because there may be a case where sufficient wet heat characteristics are not obtained.
On the other hand, when the amount of indium oxide exceeds 70% by weight, the amount of indium contained in the second zinc oxide film after film formation may increase remarkably.
Accordingly, the zinc oxide content is within the range of 27 to 99.4% by weight and the gallium oxide content is within the range of 0.5 to 8% by weight relative to the total amount of the sintered body. More preferably, the blending amount of indium oxide is set to a value within the range of 0.1 to 65 weight.
The blending amount of zinc oxide is set to a value within the range of 33 to 98.7% by weight, and the blending amount of gallium oxide is set to a value within the range of 1 to 7% by weight with respect to the total amount of the sintered body. Further, it is more preferable that the blending amount of indium oxide is a value within the range of 0.3 to 60% by weight.

２．工程（２）：第１の酸化亜鉛膜の形成工程
　工程（２）は、図１(ａ)に示すように、基材１２の少なくとも片面に第１の酸化亜鉛膜１６を形成する方法である。
　第１の酸化亜鉛膜を形成する方法として、例えば、スパッタリング法や蒸着法に代表される物理的作製法と、化学気相成長法に代表される化学的作製法が挙げられる。
　これらの中でも、簡便に酸化亜鉛膜が形成できることから、スパッタリング法または蒸着法が好ましい。すなわち、スパッタリング法または蒸着法により形成することにより、形成される第１の酸化亜鉛膜の組成を容易に制御することができるため、効率よく第１の酸化亜鉛膜を形成することができる。 2. Step (2): Step of Forming First Zinc Oxide Film Step (2) is a method of forming the first zinc oxide film 16 on at least one surface of the substrate 12 as shown in FIG. .
As a method for forming the first zinc oxide film, for example, a physical manufacturing method typified by a sputtering method or a vapor deposition method and a chemical manufacturing method typified by a chemical vapor deposition method can be given.
Among these, a sputtering method or a vapor deposition method is preferable because a zinc oxide film can be easily formed. That is, since the composition of the first zinc oxide film to be formed can be easily controlled by forming by sputtering or vapor deposition, the first zinc oxide film can be formed efficiently.

　より具体的なスパッタリング法として、ＤＣスパッタリング法、ＤＣマグネトロンスパッタリング法、ＲＦスパッタリング法、ＲＦマグネトロンスパッタリング法、ＤＣ＋ＲＦ重畳スパッタリング法、ＤＣ＋ＲＦ重畳マグネトロンスパッタリング法、対向ターゲットスパッタリング法、ＥＣＲスパッタリング法、デュアルマグネトロンスパッタリング法等が挙げられる。
　また、より具体的な蒸着法として、抵抗加熱法、電子線加熱法、レーザー加熱法、アーク蒸着法、および誘導加熱法等が挙げられる。 More specific sputtering methods include DC sputtering method, DC magnetron sputtering method, RF sputtering method, RF magnetron sputtering method, DC + RF superposition sputtering method, DC + RF superposition magnetron sputtering method, counter target sputtering method, ECR sputtering method, dual magnetron sputtering method. Etc.
More specific vapor deposition methods include a resistance heating method, an electron beam heating method, a laser heating method, an arc vapor deposition method, and an induction heating method.

　また、スパッタリングまたは蒸着の条件としては、特に限定されないが、背圧としては、１×１０-2Ｐａ以下の値が好ましく、１×１０-3Ｐａ以下の値がより好ましい。
　また、アルゴンガスを系内に導入する形成方法を選択した場合、系内圧力を０．１～５Ｐａ、より好ましくは０．２～１Ｐａの範囲内の値とすることが好ましい。
　さらに、スパッタリング法または蒸着法で、系内に導入するガス種は、アルゴン（Ａｒ）もしくはアルゴン（Ａｒ）と酸素（Ｏ2）の混合ガスを用いることが生産コスト上好ましいが、Ａｒ以外の希ガス、窒素（Ｎ2）等を用いても良い。混合ガスを用いる場合、かかる混合比（Ｏ2／（Ａｒ＋Ｏ2））を０．０１～２０の範囲内の値とすることが好ましく、０．１～１０の範囲内の値とすることがさらに好ましい。
　この理由は、アルゴンと酸素の混合比が上記範囲であれば、比抵抗が低く、反射率が低い導電層を成膜することができるためである。 The conditions for sputtering or vapor deposition are not particularly limited, but the back pressure is preferably 1 × 10 −2 Pa or less, and more preferably 1 × 10 −3 Pa or less.
In addition, when a formation method in which argon gas is introduced into the system is selected, the internal pressure is preferably set to a value in the range of 0.1 to 5 Pa, more preferably 0.2 to 1 Pa.
Furthermore, it is preferable in terms of production cost that argon (Ar) or a mixed gas of argon (Ar) and oxygen (O 2 ) is used as a gas species to be introduced into the system by sputtering or vapor deposition, but rare gases other than Ar are used. Gas, nitrogen (N 2 ), or the like may be used. When a mixed gas is used, the mixing ratio (O 2 / (Ar + O 2 )) is preferably set to a value within the range of 0.01 to 20, and more preferably set to a value within the range of 0.1 to 10. preferable.
This is because when the mixing ratio of argon and oxygen is in the above range, a conductive layer having a low specific resistance and a low reflectance can be formed.

　また、基材上に透明導電層を形成する際の基材の温度を１０～１５０℃の範囲内の値とすることが好ましい。
　この理由は、基材の温度が１０～１５０℃の範囲内の値であれば、軟化点が比較的低い基材であっても、好適に透明導電層を形成することができるためである。 In addition, the temperature of the substrate when forming the transparent conductive layer on the substrate is preferably set to a value within the range of 10 to 150 ° C.
This is because, if the temperature of the substrate is a value within the range of 10 to 150 ° C., the transparent conductive layer can be suitably formed even with a substrate having a relatively low softening point.

３．工程（３）：第２の酸化亜鉛膜の形成工程
　工程（３）は、図１（ａ）に示すように、第１の酸化亜鉛膜１６上に第２の酸化亜鉛膜１０を形成する工程である。
　なお、第２の酸化亜鉛膜の形成方法については、第１の酸化亜鉛膜の形成方法と同様であるため、詳細を省略する。 3. Step (3): Step of Forming Second Zinc Oxide Film Step (3) is a step of forming second zinc oxide film 10 on first zinc oxide film 16 as shown in FIG. It is.
Note that the method for forming the second zinc oxide film is the same as the method for forming the first zinc oxide film, and thus the details thereof are omitted.

４．工程（４）：第１の酸化亜鉛膜の形成工程
　工程（４）は、図１（ｃ）に示すように、第２の酸化亜鉛膜１０上に、上述の第１の酸化亜鉛膜と同一の組成の別の第１の酸化亜鉛膜１６´を形成する工程である。かかる工程は、上述と同様であるため、詳細を省略する。 4). Step (4): Step of Forming First Zinc Oxide Film Step (4) is the same as the first zinc oxide film described above on the second zinc oxide film 10 as shown in FIG. This is a step of forming another first zinc oxide film 16 'having the above composition. Since this process is the same as described above, the details are omitted.

［第４の実施形態］
　第４の実施形態は、基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、透明導電層が、基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、下記工程（１´）～（３´）を含むことを特徴とする透明導電性積層体の製造方法である。
（１´）基材と、第１の酸化亜鉛膜用の焼結体と、第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２´）基材上に、スパッタリング法または蒸着法を用いて、第２の酸化亜鉛膜用の焼結体から、インジウムを含む、第２の酸化亜鉛膜を形成する工程
（３´）第２の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、第１の酸化亜鉛膜を形成する工程 [Fourth Embodiment]
4th Embodiment is a manufacturing method of the transparent conductive laminated body formed by forming a transparent conductive layer in the at least single side | surface of a base material, Comprising: A transparent conductive layer is a film thickness direction from a base material side. A method for producing a transparent conductive laminate, comprising the steps of (1 ′) to (3 ′) below, wherein a zinc oxide film of 2 and a first zinc oxide film are sequentially formed. .
(1 ′) Step of preparing a substrate, a sintered body for the first zinc oxide film, and a sintered body for the second zinc oxide film (2 ′) On the substrate, a sputtering method or Step of forming a second zinc oxide film containing indium from the sintered body for the second zinc oxide film by using a vapor deposition method (3 ′) Sputtering or vapor deposition on the second zinc oxide film Forming a first zinc oxide film not containing indium from the sintered body for the first zinc oxide film using the method

　すなわち、第４の実施形態は、第２の実施形態に記載した、図１（ｂ）、（ｄ）に例示する透明導電性積層体の製造方法であって、基材１２上に、第２の酸化亜鉛膜１０を形成し、次いで第１の酸化亜鉛膜１６を形成する工程を含む透明導電性積層体５０´、５０´´´の製造方法である。 That is, the fourth embodiment is a method for manufacturing the transparent conductive laminate illustrated in FIGS. 1B and 1D described in the second embodiment. The transparent conductive laminates 50 ′ and 50 ″ ″ include the steps of forming the zinc oxide film 10 and then forming the first zinc oxide film 16.

　また、工程（４´）として、図１（ｄ）に示すように、第１の酸化亜鉛膜１６上に、上述の第２の酸化亜鉛膜と同一の組成の別の第２の酸化亜鉛膜１０´を形成する工程を含んでもよい。
　なお、各工程についての詳細は、上述の第１～第３の実施形態の記載と同様であるため、省略する。 Further, as step (4 ′), as shown in FIG. 1D, another second zinc oxide film having the same composition as that of the second zinc oxide film is formed on the first zinc oxide film 16. A step of forming 10 'may be included.
Note that the details of each step are the same as those described in the first to third embodiments, and will be omitted.

［第５の実施形態］
　第５の実施形態は、上述したいずれかの透明導電性積層体を透明電極に用いてなることを特徴とする電子デバイスである。
　より具体的には、所定の透明導電性積層体を備えた透明電極を搭載してなる液晶ディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、電子ペーパー、太陽電池、有機トランジスタ、有機ＥＬ照明、無機ＥＬ照明、熱電変換デバイス、ガスセンサー等が挙げられる。 [Fifth Embodiment]
5th Embodiment is an electronic device characterized by using any one of the transparent conductive laminated bodies mentioned above for a transparent electrode.
More specifically, a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, an organic transistor, an organic EL illumination, and an inorganic EL illumination each having a transparent electrode provided with a predetermined transparent conductive laminate. , Thermoelectric conversion devices, gas sensors and the like.

　すなわち、本発明の電子デバイスは、第１の実施形態に記載の透明導電性積層体を備えているので、湿熱特性や透明性に優れ、かつ、良好な電気特性を発揮することができる。 That is, since the electronic device of the present invention includes the transparent conductive laminate described in the first embodiment, it is excellent in wet heat characteristics and transparency, and can exhibit good electrical characteristics.

　以下、本発明を実施例によってさらに詳細に説明する。但し、以下の説明は、本発明を例示的に示すものであり、本発明はこれらの記載に制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[実施例１]
１．透明導電性積層体の製造
（１）工程（１´）：基材および焼結体を準備する工程
　基材として、無アルカリガラス（コーニング社製、イーグルＸＧ、厚み：７００μｍ）を準備した。
　また、第１の酸化亜鉛膜用焼結体として、酸化亜鉛－酸化ガリウムの二元系焼結体（ＺｎＯ：Ｇａ2Ｏ3＝９４．３重量％：５．７重量％）を準備した。
　また、第２の酸化亜鉛膜用焼結体として、酸化亜鉛－酸化ガリウム－酸化インジウムの三元系焼結体（ＺｎＯ：Ｇａ2Ｏ3：Ｉｎ2Ｏ3＝９３.３重量％：５.７重量％：１．０重量％）を準備した。 [Example 1]
1. Production of Transparent Conductive Laminate (1) Step (1 ′): Step of Preparing Substrate and Sintered Body As the substrate, alkali-free glass (manufactured by Corning, Eagle XG, thickness: 700 μm) was prepared.
In addition, a zinc oxide-gallium oxide binary sintered body (ZnO: Ga 2 O 3 = 94.3% by weight: 5.7% by weight) was prepared as a first sintered body for a zinc oxide film.
Further, as the second sintered body for zinc oxide film, a zinc oxide-gallium oxide-indium oxide ternary sintered body (ZnO: Ga 2 O 3 : In 2 O 3 = 93.3 wt%: 5. 7 wt%: 1.0 wt%) was prepared.

（２）工程（２´）：第２の酸化亜鉛膜の形成工程
　次いで、基材である無アルカリガラスに対し、ＤＣマグネトロンスパッタリング法により、上述の三元系焼結体を用いて、下記スパッタリング条件にて、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜、膜厚：１００ｎｍ）を形成した。
　基材温度：２０℃
　ＤＣ出力：５００Ｗ
　キャリアガス：アルゴン（Ａｒ）
　成膜圧力：０．６Ｐａ
　成膜時間：３５ｓｅｃ． (2) Step (2 ′): Step of forming second zinc oxide film Next, the following sputtering is performed on the alkali-free glass as a base material by the DC magnetron sputtering method using the above-described ternary sintered body. Under the conditions, a second zinc oxide film (In-GZO film, film thickness: 100 nm) was formed.
Substrate temperature: 20 ° C
DC output: 500W
Carrier gas: Argon (Ar)
Deposition pressure: 0.6Pa
Deposition time: 35 sec.

（３）工程（３´）：第１の酸化亜鉛膜の形成工程
　次いで、得られた第２の酸化亜鉛膜に対し、ＤＣマグネトロンスパッタリング法により、上述の二元系焼結体を用いて、上述と同様のスパッタリング条件にて、第１の酸化亜鉛膜（ＧＺＯ膜、膜厚：１００ｎｍ）を形成した。 (3) Step (3 ′): Step of forming first zinc oxide film Next, the obtained second zinc oxide film is subjected to DC magnetron sputtering, using the above-described binary sintered body, A first zinc oxide film (GZO film, film thickness: 100 nm) was formed under the same sputtering conditions as described above.

２．透明導電性積層体の評価
　得られた透明導電性積層体につき、以下の測定を行い、評価した。 2. Evaluation of transparent conductive laminate The obtained transparent conductive laminate was measured and evaluated as follows.

（１）ＸＰＳ分析における元素分析測定
　ＸＰＳ測定分析装置（アルバックファイ社製、Ｑｕａｎｔｕｍ２０００）を用いて、得られた透明導電性積層体における透明導電層の亜鉛、ガリウム、インジウムおよび酸素の元素分析を行った。
　得られた第１の酸化亜鉛膜（ＧＺＯ膜）のＸＰＳ測定による各元素量は、ガリウム量４.４７ａｔｏｍ％であり、亜鉛量５２.１ａｔｏｍ％であった。
　また、得られた第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜）のＸＰＳ測定による各元素量は、インジウム量０．３ａｔｏｍ％であり、ガリウム量４．２７ａｔｏｍ％であり、亜鉛量５１．４ａｔｏｍ％であった。 (1) Elemental analysis measurement in XPS analysis Elemental analysis of zinc, gallium, indium and oxygen in the transparent conductive layer in the transparent conductive laminate obtained using an XPS measurement analyzer (manufactured by ULVAC-PHI, Quantum 2000) It was.
The amount of each element by XPS measurement of the obtained first zinc oxide film (GZO film) was 4.47 atom% of gallium and 52.1 atom% of zinc.
Further, the amount of each element obtained by XPS measurement of the obtained second zinc oxide film (In-GZO film) is an indium amount of 0.3 atom%, a gallium amount of 4.27 atom%, and a zinc amount of 51.4 atom%. Met.

（２）透明導電層の膜厚（ｄ）
　得られた透明導電性積層体の透明導電層における各層の膜厚（ｄ）を、分光エリプソメーターＭ－２０００Ｕ（Ｊ．Ａ．ウーラム・ジャパン社製）を用いて測定した。 (2) Film thickness of transparent conductive layer (d)
The film thickness (d) of each layer in the transparent conductive layer of the obtained transparent conductive laminate was measured using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Japan).

（３）比抵抗およびρ1／ρ0の算出
　得られた透明導電性積層体の透明導電層における初期の表面抵抗率（Ｒ0）を、表面抵抗測定装置として、ＬＯＲＥＳＴＡ－ＧＰ　ＭＣＰ－Ｔ６００（三菱化学（株）製）およびプローブとして、ＰＲＯＢＥ　ＴＹＰＥ　ＡＳＰ（三菱化学アナリテック（株）製）を用いて、温度２３℃、５０％ＲＨの環境条件下、測定した。
　次いで、得られた透明導電性フィルムを、６０℃、９５％ＲＨ環境下に、５００時間置き、取り出し後、２３℃５０％ＲＨ環境下で１日調温・調湿を行い、湿熱試験後の表面抵抗率（Ｒ1）を測定した。
　すなわち、透明導電層における初期表面抵抗率（Ｒ0）および湿熱試験後の表面抵抗率（Ｒ１）、さらには、透明導電性積層体の膜厚（ｄ）を測定し、それらから下式（１）および（２）より、比抵抗（ρ0）および湿熱試験後の比抵抗（ρ1）を算出して、ρ1／ρ0の比率を得た。得られた結果を表１に示す。
Ｒ0＝ρ0／ｄ　　（１）
Ｒ1＝ρ1／ｄ　　（２） (3) Calculation of specific resistance and ρ 1 / ρ 0 The initial surface resistivity (R 0 ) in the transparent conductive layer of the obtained transparent conductive laminate was used as a surface resistance measuring device as a LOCESTA-GP MCP-T600 ( Using PROBE TYPE ASP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) as a probe and a probe (Mitsubishi Chemical Co., Ltd.), the measurement was performed under environmental conditions of a temperature of 23 ° C. and 50% RH.
Next, the obtained transparent conductive film was placed in an environment of 60 ° C. and 95% RH for 500 hours, taken out, then subjected to temperature control and humidity control in a 23 ° C. and 50% RH environment for 1 day. The surface resistivity (R 1 ) was measured.
That is, the initial surface resistivity (R 0 ) and the surface resistivity (R 1 ) after the wet heat test in the transparent conductive layer, and the film thickness (d) of the transparent conductive laminate were measured. From 1) and (2), the specific resistance (ρ 0 ) and the specific resistance after the wet heat test (ρ 1 ) were calculated to obtain a ratio of ρ 1 / ρ 0 . The obtained results are shown in Table 1.
R 0 = ρ 0 / d (1)
R 1 = ρ 1 / d (2)

[実施例２]
　実施例２においては、基材上に第１の酸化亜鉛膜（ＧＺＯ膜、膜厚：１００ｎｍ）を形成し、次いで、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜、膜厚：１００ｎｍ）を形成したこと以外は、実施例１と同様に透明導電フィル
ムを製造し、評価した。得られた結果を表１に示す。 [Example 2]
In Example 2, a first zinc oxide film (GZO film, film thickness: 100 nm) is formed on a substrate, and then a second zinc oxide film (In-GZO film, film thickness: 100 nm) is formed. A transparent conductive film was produced and evaluated in the same manner as in Example 1 except that. The obtained results are shown in Table 1.

[実施例３]
　実施例３においては、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜）の膜厚を２０ｎｍとしたこと以外は、実施例２と同様に、透明導電性積層体を製造し、評価した。得られた結果を表１に示す。 [Example 3]
In Example 3, a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 20 nm. The obtained results are shown in Table 1.

[実施例４]
　実施例４においては、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜）の膜厚を２００ｎｍとしたこと以外は、実施例２と同様に、透明導電性積層体を製造し、評価した。得られた結果を表１に示す。 [Example 4]
In Example 4, a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 200 nm. The obtained results are shown in Table 1.

[比較例１]
　比較例１においては、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜）を形成せず、第１の酸化亜鉛膜（ＧＺＯ膜、膜厚２００ｎｍ）のみ形成した他は、実施例１と同様に透明導電性積層体を製造し、評価した。得られた結果を表１に示す。 [Comparative Example 1]
In Comparative Example 1, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 200 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.

[比較例２]
　比較例２においては、第２の酸化亜鉛膜（Ｉｎ－ＧＺＯ膜）を形成せず、第１の酸化亜鉛膜（ＧＺＯ膜、膜厚１００ｎｍ）のみ形成した他は、実施例１と同様に透明導電性積層体を製造し、評価した。得られた結果を表１に示す。 [Comparative Example 2]
In Comparative Example 2, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 100 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

　実施例１～４においては、第１の酸化亜鉛膜および第２の酸化亜鉛膜の形成順序によらず、いずれも湿熱特性に優れた透明導電性積層体が得られた。
　一方、Ｉｎ－ＧＺＯ膜を有さない比較例１～２は、環境試験後の比抵抗が著しく大きくなった。 In Examples 1 to 4, a transparent conductive laminate excellent in wet heat characteristics was obtained regardless of the order of formation of the first zinc oxide film and the second zinc oxide film.
On the other hand, in Comparative Examples 1 and 2 having no In-GZO film, the specific resistance after the environmental test was remarkably increased.

　以上、詳述したように、本発明の透明導電性積層体によれば、基材上の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、透明導電層が、所定の構成を有する第１の酸化亜鉛膜と第２の酸化亜鉛膜とを有することによって、電気特性が良好で、湿熱特性が優れた透明導電性積層体が効率的に得られるようになった。
　よって、本発明の透明導電性積層体は、所定の湿熱特性が所望される電気製品、電子部品、画像表示装置（有機エレクトロルミネッセンス素子、無機エレクトロルミネッセンス素子、液晶表示装置、電子ペーパー等）、熱電変換デバイス、太陽電池等の各種用途において、透明電極等として、有効に使用されることが期待される。 As described above in detail, according to the transparent conductive laminate of the present invention, it is a transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate, and the transparent conductive layer is a predetermined layer. By having the first zinc oxide film and the second zinc oxide film having the above structure, a transparent conductive laminate having good electrical characteristics and excellent wet heat characteristics can be obtained efficiently.
Therefore, the transparent conductive laminate of the present invention can be used in electrical products, electronic components, image display devices (organic electroluminescent elements, inorganic electroluminescent elements, liquid crystal display devices, electronic paper, etc.), thermoelectrics that require predetermined wet heat characteristics. It is expected to be used effectively as a transparent electrode in various applications such as conversion devices and solar cells.

１０、１０´：第２の酸化亜鉛膜
１６、１６´：第１の酸化亜鉛膜
１２：基材
１８、１８´、１８´´、１８´´´：透明導電層
５０、５０´、５０´´、５０´´´：透明導電性積層体 10, 10 ': second zinc oxide film 16, 16': first zinc oxide film 12: base materials 18, 18 ', 18 ", 18"": transparent conductive layers 50, 50', 50 '', 50 "': Transparent conductive laminate

Claims (13)

　基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、
　前記透明導電層が、前記基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、
　前記第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、
　前記第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体。 A transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate,
The transparent conductive layer is formed by sequentially forming a first zinc oxide film and a second zinc oxide film along the film thickness direction from the substrate side,
The first zinc oxide film is a zinc oxide film not containing indium;
The transparent conductive laminate, wherein the second zinc oxide film is a zinc oxide film containing indium. 　基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体であって、
　前記透明導電層が、前記基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、
　前記第１の酸化亜鉛膜が、インジウムを含まない酸化亜鉛膜であり、
　前記第２の酸化亜鉛膜が、インジウムを含む酸化亜鉛膜であることを特徴とする透明導電性積層体。 A transparent conductive laminate formed by forming a transparent conductive layer on at least one side of a substrate,
The transparent conductive layer is formed by sequentially forming a second zinc oxide film and a first zinc oxide film along the film thickness direction from the substrate side,
The first zinc oxide film is a zinc oxide film not containing indium;
The transparent conductive laminate, wherein the second zinc oxide film is a zinc oxide film containing indium. 　前記第１の酸化亜鉛膜が、ガリウムをドープしてなる酸化亜鉛膜であることを特徴とする請求項１または２に記載の透明導電性積層体。 The transparent conductive laminate according to claim 1 or 2, wherein the first zinc oxide film is a zinc oxide film doped with gallium. 　前記第２の酸化亜鉛膜が、インジウムおよびガリウムをドープしてなる酸化亜鉛膜であることを特徴とする請求項１または２に記載の透明導電性積層体。 3. The transparent conductive laminate according to claim 1, wherein the second zinc oxide film is a zinc oxide film doped with indium and gallium. 　前記第２の酸化亜鉛膜は、ＸＰＳの元素分析測定による亜鉛量、ガリウム量、酸素量、およびインジウム量の合計量（１００ａｔｏｍ％）に対して、インジウム量を０．０１～２５ａｔｏｍ％の範囲内の値とすることを特徴とする請求項１～４のいずれか一項に記載の透明導電性積層体。 The second zinc oxide film has an indium content within a range of 0.01 to 25 atom% with respect to a total amount (100 atom%) of zinc content, gallium content, oxygen content and indium content measured by XPS elemental analysis. The transparent conductive laminate according to any one of claims 1 to 4, wherein the transparent conductive laminate has the following value. 　前記透明導電層における初期の比抵抗をρ0とし、６０℃、相対湿度９５％の条件下で、５００時間、保管した後の比抵抗をρ1としたとき、ρ1/ρ0で表わされる比率を１．３以下の値とすることを特徴とする請求項１～５のいずれか一項に記載の透明導電性積層体。 Wherein the initial resistivity [rho 0 in the transparent electroconductive layer, 60 ° C., under a relative humidity of 95% for 500 hours, when the specific resistance after storage was [rho 1, represented by ρ 1 / ρ 0 6. The transparent conductive laminate according to claim 1, wherein the ratio is a value of 1.3 or less. 　前記第１の酸化亜鉛膜および第２の酸化亜鉛膜の膜厚を、それぞれ１０～３００ｎｍの範囲内の値とすることを特徴とする請求項１～６のいずれか一項に記載の透明導電性積層体。 The transparent conductive film according to any one of claims 1 to 6, wherein the thicknesses of the first zinc oxide film and the second zinc oxide film are set to values in the range of 10 to 300 nm, respectively. Laminate. 　前記基材が、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、シクロオレフィン系コポリマ、シクロオレフィン系ポリマ、ポリエーテルスルフォン、ポリイミドからなる群から選ばれる少なくとも１種であることを特徴とする請求項１～７のいずれか一項に記載の透明導電性積層体。 The base material is at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, cycloolefin polymer, polyether sulfone, and polyimide. The transparent conductive laminate according to any one of the above. 　請求項１～８のいずれか一項に記載の透明導電性積層体を透明電極に用いてなることを特徴とする電子デバイス。 An electronic device comprising the transparent conductive laminate according to any one of claims 1 to 8 as a transparent electrode. 　基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、
　前記透明導電層が、前記基材側から膜厚方向に沿って、第１の酸化亜鉛膜と、第２の酸化亜鉛膜とが順次に形成されてなり、
　下記工程（１）～（３）を含むことを特徴とする透明導電性積層体の製造方法。
（１）前記基材と、前記第１の酸化亜鉛膜用の焼結体と、前記第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２）前記基材上に、スパッタリング法または蒸着法を用いて、前記第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、前記第１の酸化亜鉛膜を形成する工程
（３）前記第１の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、前記第２の酸化亜鉛膜用の焼結体から、インジウムを含む、前記第２の酸化亜鉛膜を形成する工程 A method for producing a transparent conductive laminate comprising a transparent conductive layer formed on at least one side of a substrate,
The transparent conductive layer is formed by sequentially forming a first zinc oxide film and a second zinc oxide film along the film thickness direction from the substrate side,
A method for producing a transparent conductive laminate, comprising the following steps (1) to (3):
(1) Step of preparing the base material, the sintered body for the first zinc oxide film, and the sintered body for the second zinc oxide film (2) Sputtering on the base material Step (3) of forming the first zinc oxide film not containing indium from the sintered body for the first zinc oxide film by using a method or a vapor deposition method (3) on the first zinc oxide film The step of forming the second zinc oxide film containing indium from the sintered body for the second zinc oxide film using a sputtering method or a vapor deposition method 　前記工程（３）の後に、工程（４）として、前記第２の酸化亜鉛膜の表面に、前記第１の酸化亜鉛膜と同一の組成の別の第１の酸化亜鉛膜を、さらに積層する工程を含むことを特徴とする請求項１０に記載の透明導電性積層体の製造方法。 After the step (3), as a step (4), another first zinc oxide film having the same composition as the first zinc oxide film is further laminated on the surface of the second zinc oxide film. The manufacturing method of the transparent conductive laminated body of Claim 10 including a process. 　基材の少なくとも片面に透明導電層を形成してなる透明導電性積層体の製造方法であって、
　前記透明導電層が、前記基材側から膜厚方向に沿って、第２の酸化亜鉛膜と、第１の酸化亜鉛膜とが順次に形成されてなり、
　下記工程（１´）～（３´）を含むことを特徴とする透明導電性積層体の製造方法。
（１´）前記基材と、前記第１の酸化亜鉛膜用の焼結体と、前記第２の酸化亜鉛膜用の焼結体と、を準備する工程
（２´）前記基材上に、スパッタリング法または蒸着法を用いて、前記第２の酸化亜鉛膜用の焼結体から、インジウムを含む、前記第２の酸化亜鉛膜を形成する工程
（３´）前記第２の酸化亜鉛膜上に、スパッタリング法または蒸着法を用いて、前記第１の酸化亜鉛膜用の焼結体から、インジウムを含まない、前記第１の酸化亜鉛膜を形成する工程 A method for producing a transparent conductive laminate comprising a transparent conductive layer formed on at least one side of a substrate,
The transparent conductive layer is formed by sequentially forming a second zinc oxide film and a first zinc oxide film along the film thickness direction from the substrate side,
A method for producing a transparent conductive laminate comprising the following steps (1 ′) to (3 ′):
(1 ′) Step of preparing the base material, the sintered body for the first zinc oxide film, and the sintered body for the second zinc oxide film (2 ′) on the base material Step (3 ′) of forming the second zinc oxide film containing indium from the sintered body for the second zinc oxide film by using a sputtering method or a vapor deposition method (2 ′) A step of forming the first zinc oxide film not containing indium from the sintered body for the first zinc oxide film using a sputtering method or a vapor deposition method; 　前記工程（３´）の後に、工程（４´）として、前記第１の酸化亜鉛膜の表面に、前記第２の酸化亜鉛膜と同一の組成の別の第２の酸化亜鉛膜を、さらに積層する工程を含むことを特徴とする請求項１２に記載の透明導電性積層体の製造方法。 After the step (3 ′), as a step (4 ′), another second zinc oxide film having the same composition as the second zinc oxide film is further formed on the surface of the first zinc oxide film. The manufacturing method of the transparent conductive laminated body of Claim 12 including the process to laminate | stack.
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