WO2015087895A1

WO2015087895A1 - Transparent conductive body

Info

Publication number: WO2015087895A1
Application number: PCT/JP2014/082621
Authority: WO
Inventors: 仁一粕谷; 一成多田; 健一郎平田
Original assignee: コニカミノルタ株式会社
Priority date: 2013-12-11
Filing date: 2014-12-10
Publication date: 2015-06-18
Also published as: JPWO2015087895A1

Abstract

The present invention addresses the problem of providing a transparent conductive body that has outstanding moisture resistance and that allows electricity to be stably removed from the surface of the transparent conductive body. In order to solve the problem, the present invention provides a transparent conductive body comprising, in the stated order, the following: a transparent substrate; a first high-refractive-index layer that contains an oxide semiconductor material or a dielectric material having a refractive index for light with a wavelength of 570 nm that is higher than the transparent-substrate refractive index for light with a wavelength of 570 nm; a transparent metal film; and a second high-refractive-index layer that contains zinc sulfide and a conductive material.

Description

Transparent conductor

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

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

As a material of such a transparent conductor, metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , TiO ₂ , SnO _2. Oxide semiconductors such as ZnO and ITO (indium tin oxide) are known.

Here, in the touch panel type display device, a transparent conductor (wiring) is disposed on the image display element. For this reason, the transparent conductor is required to have light transmittance, and an ITO film is frequently used for the transparent conductor. However, in recent years, a capacitive touch panel display device has been developed, and it is required to further reduce the surface electrical resistance of the transparent conductor. The ITO film has a problem that it is difficult to sufficiently reduce the surface electrical resistance value.

Then, development of Ag thin film with high electroconductivity and high light transmittance is advancing (patent document 1). In order to increase the light transmittance of the transparent conductor, the Ag film is made of a film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium oxide / zinc oxide), ICO (indium cerium oxide), a- It is also considered to sandwich the film between GIO (a film made of gallium, indium, and oxygen) (Patent Documents 2 to 4, Non-Patent Document 1). Furthermore, it has been studied to sandwich an Ag film with a ZnS film, or sandwich a ZnS—SiO ₂ film (Non-patent

Documents

2 and 3, and Patent Document 5).

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-15623 A JP 2008-226581 A Chinese Patent Application No. 1026777012

However, a transparent conductor made of a transparent metal film (Ag film) alone, or a transparent conductor in which a transparent metal film is sandwiched between niobium oxide films, IZO films, etc., has insufficient moisture resistance, and humidity outside the transparent conductor As a result, there is a problem that the transparent metal film is easily corroded. On the other hand, when a transparent metal film is sandwiched between films containing ZnS, moisture resistance is likely to increase, and corrosion of the transparent metal film is suppressed. However, a film containing ZnS has low conductivity. Therefore, the transparent conductor having such a configuration has a problem that it is difficult to take out electricity from the surface of the transparent conductor.

The present invention has been made in view of such a situation. An object of this invention is to provide the transparent conductor which is excellent in moisture resistance and can take out electricity stably from the surface of a transparent conductor.

That is, this invention relates to the following transparent conductors.
[1] A transparent substrate, a first high refractive index layer containing a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate, and a transparent metal film And a second high refractive index layer containing a conductive material in this order, and at least one of the first high refractive index layer or the second high refractive index layer contains ZnS.
[2] The conductive _{_{_{_{material, TiO 2, ITO, In 2}}}} O 3, ZnO, Nb 2 O 5, ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3 , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO, AZO, GZO, ATO, ICO, IGZO, ZTO, Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , a-GIO The transparent conductor according to [1], comprising one or more metals selected from the group consisting of metal oxides selected from the group consisting of Ag, Cu, Al, and Au.
[3] The transparent conductor according to [2], wherein the conductive material is the metal oxide, and the amount of the metal oxide with respect to the mass of the second high refractive index layer is 30% by mass or more.
[4] The transparent conductor according to [2], wherein the conductive material is the metal, and the amount of the metal with respect to the mass of the second high refractive index layer is 5% by mass or less.
[5] The transparent conductor according to any one of [1] to [4], wherein the transparent metal film has a thickness of 20 nm or less.

According to the present invention, a transparent conductor that is excellent in moisture resistance and that can stably take out electricity from the surface can be obtained.

It is a schematic sectional drawing which shows an example of a laminated constitution of the transparent conductor of this invention. It is a schematic sectional drawing which shows the other example of the laminated constitution of the transparent conductor of this invention. It is a schematic diagram which shows an example of the pattern which consists of a conduction area | region and an insulation area | region of the transparent conductor of this invention.

Examples of the layer structure of the transparent conductor of the present invention are shown in FIGS. As shown in FIG. 1 and FIG. 2, the transparent conductor 100 of the present invention has a transparent substrate 1 / first high refractive index layer 2 / transparent metal film 3 / second high refractive index layer 4 laminated in this order. It consists of a laminate. The second high refractive index layer 4 of the transparent conductor 100 contains a conductive material, and one or both of the first high refractive index layer 2 and the second high refractive index layer 4 contain ZnS. It is.

As described above, in a conventional transparent conductor in which a transparent metal film is sandwiched between high refractive index layers made of ZnS or ZnS—SiO ₂ , the insulating properties of the high refractive index layer are increased. Therefore, electricity cannot be taken out from the surface of the transparent conductor, and it is necessary to separately provide wiring for taking out electricity from the transparent metal film. On the other hand, in the present invention, since the second high refractive index layer 4 includes a conductive material, the conductivity of the second high refractive index layer 4 is increased, and the transparent conductor 100 on the second high refractive index layer 4 side is increased. Electricity can be stably extracted from the surface. On the other hand, since either one or both of the first high refractive index layer 2 and the second high refractive index layer 4 contain ZnS, the moisture resistance of the transparent conductor 100 is increased, and the transparent metal film 3 is corroded. Is suppressed.

In the transparent conductor 100 of the present invention, the transparent metal film 3 may be formed on the entire surface of the transparent substrate 1 as shown in FIG. 1, and is patterned into a desired shape as shown in FIG. It may be. In the transparent conductor 100 of the present invention, the region a where the transparent metal film 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, as shown in FIG. 2, the region b not including the transparent metal film 3 is an insulating region.

The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductor 100. For example, when the transparent conductor 100 is applied to an electrostatic touch panel, as shown in FIG. 3, the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. sell.

Further, the transparent conductor 100 (laminated body) of the present invention may include layers other than the transparent substrate 1, the first high refractive index layer 2, the transparent metal film 3, and the second high refractive index layer 4. . For example, between the first high refractive index layer 2 and the transparent metal film 3 or between the transparent metal film 3 and the second high refractive index layer 4, a sulfidation preventing layer (for preventing sulfidation of the transparent metal film 3 ( (Not shown) may be included. However, the layers included in the transparent conductor 100 of the present invention are all layers made of an inorganic material except for the transparent substrate 1. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 4, the laminated body from the transparent substrate 1 to the second high refractive index layer 4 is the transparent conductor 100 of the present invention. .

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

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

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

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

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

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

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

1-2) First High Refractive Index Layer The first high refractive index layer 2 is a layer for suppressing reflection on the surface of the transparent conductor 100. The reflectance of the surface of the transparent conductor 100 greatly depends on the layer configuration of the transparent conductor 100. When the transparent metal film 3 is sandwiched between layers having a relatively high refractive index (the first high refractive index layer 2 and the second high refractive index layer 4), the reflectance of the surface of the transparent conductor 100 is reduced, and the transparent metal film 3 is transparent. The light transmittance of the conductor 100 is increased.

Therefore, the first high refractive index layer 2 is preferably included at least in the conductive region a of the transparent conductor, that is, the region where the transparent metal film 3 is formed, and if necessary, the insulating region of the transparent conductor 100 Also included in b.

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

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 may be an insulating material or a conductive material. The dielectric material or the oxide semiconductor material may be a metal sulfide or metal oxide having the above refractive index. Examples of the metal sulfide or metal oxide having the above refractive index include ZnS, TiO ₂ , ITO (indium tin oxide), ZnO, In ₂ O ₃ , Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O. ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium oxide / zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO) ), ATO (Sb-doped SnO), ICO (indium cerium oxide), IGZO (indium gallium zinc oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , a-GIO (Amorphous oxide composed of gallium, indium, and oxygen) and the like. The first high refractive index layer 2 may contain only one kind of the metal sulfide or metal oxide, or may contain two or more kinds.

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably ZnS. When ZnS is contained in the first high refractive index layer 2, it becomes difficult for moisture to permeate from the transparent substrate 1 side to the transparent metal film 3 side, and corrosion of the transparent metal film 3 is suppressed.

However, ZnS has relatively high crystallinity, and a film made only of ZnS has low flexibility. Therefore, when the transparent conductor 100 is required to have flexibility, a compound for making ZnS amorphous may be included. The compound for making ZnS amorphous is preferably a compound that does not impair the light transmittance of ZnS even when mixed with ZnS, and may be, for example, a metal oxide, a metal fluoride, or a metal nitride. _{_{_{_{Specifically, SiO 2, Na 5 Al 3}}}} F 14, Na 3 AlF 6, AlF 3, MgF 2, CaF 2, BaF 2, Al 2 O 3, YF 3, LaF 3, CeF 3, NdF 3, ZrO ₂ , SiO, MgO, Y ₂ O ₃ , SiN, AlN, and the like. Only one of these may be included in the first high refractive index layer 2, or two or more thereof may be included. These compounds are particularly preferably SiO _2. These compounds are particularly preferably SiO _2.

When ZnS and other compounds are contained in the first high refractive index layer 2, it is preferable that ZnS is contained in an amount of 50% by mass or more and 90% or less with respect to the mass of the first high refractive index layer 2, and more preferably. It is 70 to 90% by mass, and more preferably 80 to 90% by mass. When the first high refractive index layer 2 contains 50 mass% or more of ZnS, the moisture resistance of the first high refractive index layer 2 is likely to increase. A layer containing ZnS is easily formed by sputtering or vapor deposition. If ZnS is contained in an amount of 50% by mass or more, the film formation rate of the first high refractive index layer 2 is likely to increase. On the other hand, when the ZnS is 90% by mass or less, the flexibility of the first high refractive index layer 2 is likely to increase.

The thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm. When the thickness of the first high refractive index layer 2 is 15 nm or more, the first high refractive index layer 2 suppresses surface reflection of the conduction region a of the transparent conductor 100. On the other hand, when the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease. Moreover, if the thickness of the 1st high refractive index layer 2 is 150 nm or less, the flexibility of the 1st high refractive index layer 2 will increase easily, and the flexibility of the transparent conductor 100 will increase easily. The thickness of the first high refractive index layer 2 is measured with an ellipsometer.

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

Here, when the first high-refractive index layer 2 includes a plurality of compounds, a mixture obtained by previously mixing the compounds at a predetermined ratio may be used as a vapor deposition source or a sputtering target. Alternatively, each compound may be prepared individually and used as a vapor deposition source or a sputtering target.

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

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

The metal contained in the transparent metal film 3 is not particularly limited as long as it is a highly conductive metal, and may be, for example, silver, copper, gold, platinum group, titanium, chromium, or the like. The transparent metal film may contain only one kind of these metals or two or more kinds. From the viewpoint of high conductivity, the transparent metal film 3 is preferably made of silver or an alloy containing 90 at% or more of silver. The metal combined with silver can be germanium, bismuth, platinum group, copper, gold, molybdenum, zinc, gallium, tin, indium, aluminum, manganese, neodymium, and the like. For example, when silver and zinc are combined, the sulfidation resistance of the transparent metal film is enhanced. When silver and gold are combined, salt resistance (NaCl) resistance increases. Furthermore, when silver and copper are combined, the oxidation resistance increases.

The thickness of the transparent metal film 3 is preferably 20 nm or less, more preferably 10 nm or less, further preferably 3 to 9 nm, and particularly preferably 5 to 8 nm. When the transparent metal film 3 has a thickness of 20 nm or less, particularly 10 nm or less, the metal inherent reflection hardly occurs in the transparent metal film 3. Furthermore, when the thickness of the transparent metal film 3 is 10 nm or less, the surface reflection of the conduction region a of the transparent conductor 100 is easily adjusted by the first high refractive index layer 2 and the second high refractive index layer 4. The thickness of the transparent metal film 3 is measured with an ellipsometer.

The transparent metal film 3 can be a film formed by any film forming method, but as described above, in order to make the transparent metal film 3 thin and smooth, it was formed by sputtering. It is preferable that the film is formed after growth nuclei are formed on the film formation surface of the transparent metal film 3.

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

On the other hand, even when growth nuclei are formed on the film formation surface of the transparent metal film 3, it is easy to obtain a dense and smooth transparent metal film 3. If growth nuclei are formed on the first high refractive index layer 2, the film grows with the growth nuclei as a starting point, so that a smooth transparent metal film 3 can be easily obtained even if the thickness is small.

The growth nuclei preferably contain palladium, molybdenum, zinc, germanium, niobium or indium; or alloys of these metals with other metals, oxides or sulfides of these metals (for example, ZnS). The growth nucleus may contain only one kind or two or more kinds. The amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the growth nucleus is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When the growth nucleus contains 20% by mass or more of the metal, the affinity between the growth nucleus and the transparent metal film 3 formed thereon is likely to increase.

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

The thickness of the growth nucleus is 3 nm or less, preferably 0.5 nm or less, and more preferably a monoatomic film. The growth nucleus may also be a film in which metal atoms are attached to the first high refractive index layer 2 so as to be separated from each other. If the growth nucleus adhesion amount is 3 nm or less, the growth nucleus hardly affects the light reflectivity of the transparent conductor 100. The presence or absence of growth nuclei is confirmed by the ICP-MS method. The thickness of the growth nucleus is calculated from the product of the film formation speed and the film formation time.

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

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

When the transparent metal film 3 is formed on the growth nucleus, the film forming method is not particularly limited, and a general gas phase such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It may be a film forming method.

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

1-4) Second High Refractive Index Layer The second high refractive index layer 4 is a layer for suppressing light reflection on the surface of the transparent conductor 100 together with the first high refractive index layer 2 described above. The second high refractive index layer 4 may be formed in the conductive region a of the transparent conductor 100, and the second high refractive index layer 4 may be formed in the insulating region b of the transparent conductor 100.

The second high refractive index layer 4 includes a conductive material. The conductive material here refers to a material having an effect of transmitting the conductivity of the transparent metal film 3 to the surface of the transparent conductor, and it is not essential that the material itself is conductive. The conductive material contained in the second high refractive index layer 4 can be a metal oxide or a metal. TiO _2, ITO (indium tin _{_{_{_{oxide), ZnO, In 2 O 3}}}} , Nb 2 O 5, ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3, TiO, _{_{_{_{SnO 2, La 2 Ti 2 O}}}} 7, IZO ( indium-zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ATO (Sb-doped SnO), ICO (indium cerium oxide), IGZO (indium -Gallium / zinc oxide), ZTO (zinc tin composite oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , a-GIO (non-comprising gallium, indium, and oxygen) A metal oxide selected from the group consisting of (crystalline oxide), particularly preferably ITO, AZO, GZO or IZO. In the second high refractive index layer 4, only one kind of the metal oxide may be contained, or two or more kinds may be contained.

When the conductive material contained in the second high refractive index layer 4 is the metal oxide, the metal oxide is preferably contained in an amount of 30% by mass or more based on the mass of the second high refractive index layer 4. Preferably it is 40 mass% or more, More preferably, it is 60 mass% or more. When the metal oxide is contained in an amount of 30% by mass or more, the conductivity of the second high refractive index layer 4 is likely to be sufficiently increased.

On the other hand, the metal that can be the conductive material is Ag, Cu, Al, or Au, and particularly preferably Cu or Al. The second high refractive index layer 4 may contain only one kind of the metal or two or more kinds.

When the conductive material contained in the second high refractive index layer 4 is the above metal, the metal is preferably contained in an amount of 5% by mass or less with respect to the mass of the second high refractive index layer 4, and more preferably It is 01 or more and less than 1% by mass, and more preferably 0.01 to 0.05% by mass. When the amount of the metal is 5% by mass or less, even if the transparent conductor 100 is used in a humid heat environment, it is difficult for the second high refractive index layer to have a poor appearance. On the other hand, when the amount of the conductive material contained in the second high refractive index layer 4 is 0.01% by mass or more, the conductivity of the second high refractive index layer 4 is likely to be sufficiently increased.

The second high refractive index layer 4 may contain both the metal oxide and the metal, but preferably contains ZnS together with the metal oxide or metal. The second high refractive index layer 4 preferably contains 0.1 to 80% by mass of ZnS. The amount of ZnS is more preferably 65% by mass or less, and further preferably 35% or less. When ZnS is contained in the second high refractive index layer 4 in an amount of 0.1% by mass or more, moisture hardly penetrates from the second high refractive index layer 4 side to the transparent metal film 3 side.

As described above, ZnS has relatively high crystallinity, and a film containing a large amount of ZnS has low flexibility. Therefore, when the transparent conductor 100 is required to have flexibility, a compound for making ZnS amorphous may be further included. The compound for amorphizing ZnS is preferably a compound that does not impair the light transmittance of ZnS even when mixed with ZnS, and is the same as the compound for amorphizing ZnS of the first high refractive index layer. It can be.

The compound for amorphizing ZnS is preferably contained in an amount of 5 to 40 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of ZnS. When the compound is contained in an amount of 5 parts by mass or more with respect to 100 parts by mass of ZnS, the flexibility of the second high refractive index layer 4 is likely to increase.

The thickness of the second high refractive index layer 4 is preferably 15 nm or more and 150 nm or less. The thickness of the second high refractive index layer 4 is more preferably 15 to 150 nm, still more preferably 20 to 80 nm. When the thickness of the second high refractive index layer 4 is 15 nm or more, the surface reflection of the conduction region a of the transparent conductor 100 is easily suppressed by the second high refractive index layer 4. On the other hand, if the thickness of the second high refractive index layer 4 is 150 nm or less, the light transmittance of the region including the second high refractive index layer 4 is unlikely to decrease. Furthermore, the flexibility of the second high refractive index layer 4 is likely to increase. The thickness of the second high refractive index layer 4 is measured with an ellipsometer.

The film formation method of the second high refractive index layer 4 is not particularly limited, and is formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. Layer. From the viewpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a film formed by sputtering.

Here, at the time of forming the second high refractive index layer 4, a mixture in which ZnS, SiO ₂ , a conductive material, and the like are mixed in advance at a desired ratio may be used as an evaporation source or a sputtering target. Alternatively, ZnS, SiO ₂ , and a conductive material may be separately prepared, and these may be used as an evaporation source and a sputtering target, respectively.

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

1-5) Sulfidation-preventing layer As described above, the transparent conductor of the present invention includes the transparent metal film 3 and the second high refractive index layer 4 between the first high refractive index layer 2 and the transparent metal film 3. In between, a sulfidation preventing layer for preventing sulfidation of the transparent metal film 3 may be included. The sulfidation prevention layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b.

When the transparent metal film 3 and the layer containing ZnS (the first high-refractive index layer 2 or the second high-refractive index layer 4) are formed adjacent to each other, When the refractive index layer 4 is formed, the metal in the transparent metal film 3 is sulfided to produce a metal sulfide, and the light transmittance of the transparent conductor 100 may be lowered. On the other hand, when an antisulfurization layer is included between the first high refractive index layer 2 and the transparent metal film 3 or between the transparent metal film 3 and the second high refractive index layer 4, the metal sulfide Generation is suppressed.

The sulfidation prevention layer may be a layer containing metal oxide, metal nitride, metal fluoride, or Zn. Only one of these may be contained in the antisulfurization layer, or two or more of them may be contained.

Examples of metal _{_{_{_{oxides, TiO 2, ITO, ZnO,}}}} In 2 O 3, Nb 2 O 5, ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3 , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO, AZO, GZO, ATO, ICO, Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , and the like.

Examples of metal fluorides include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like. .
Examples of the metal nitride include Si ₃ N ₄ , AlN, and the like.

The thickness of the sulfidation preventing layer is not particularly limited as long as the formation of the metal sulfide can be suppressed when the transparent metal film 3 is formed or when the second high refractive index layer 4 is formed. However, ZnS contained in the first high refractive index layer 2 and the second high refractive index 4 has high affinity with the metal contained in the transparent metal film 3. Therefore, when the thickness of the antisulfurization layer is very thin and a part of the transparent metal film 3 is slightly exposed, the adhesion between the layers tends to increase. That is, the antisulfurization layer is preferably relatively thin, preferably 0.1 nm to 10 nm, more preferably 0.5 nm to 5 nm, and even more preferably 1 nm to 3 nm. The thickness of the antisulfurization layer is measured with an ellipsometer.

The anti-sulfurization layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method or the like.

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

2. Regarding the physical properties of the transparent conductor In the transparent conductor of the present invention, the surface electrical resistance of the conduction region a measured by bringing a resistivity meter into contact with the surface of the second high refractive index layer 4 is preferably 50 Ω / □ or less. More preferably, it is 20 Ω / □ or less. A transparent conductor having a surface electric resistance value of 50 Ω / □ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value is a value measured at 24 ° C. and 30% Rh, and is a value measured within 5 seconds from the start of measurement. The surface electrical resistance value of the conduction region a is measured according to, for example, JIS K7194, ASTM D257, and the like. It is also measured by a commercially available surface electrical resistivity meter.

The average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor of the present invention is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more. In addition, when the transparent metal film 3 is patterned and the transparent conductor 100 includes the conductive region a and the insulating region b, the average transmittance is preferably 80% or more in any region. When the average transmittance of light having a wavelength of 400 to 1000 nm is 80% or more, the transparent conductor is also applied to applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. can do.

In particular, the average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductor is preferably 83% or more, more preferably 85% or more, and even more preferably in both the conduction region a and the insulation region b. Is 88% or more. When the average transmittance in the above wavelength range is 85% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

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

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

In addition, when the conductive region a and the insulating region b are included in the transparent conductor 100, it is preferable that the reflectance of the conductive region a and the reflectance of the insulating region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conductive region a and the luminous reflectance of the insulating region b is preferably 3% or less, more preferably 1% or less, and even more preferably 0. .3% or less. On the other hand, the luminous reflectances of the conductive region a and the insulating region b are each preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation).

In addition, when the transparent conductor 100 includes the conduction region a and the insulation region b, the a * value and the b * value in the L * a * b * color system are preferably within ± 30 in any region. More preferably, it is within ± 5, more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a * value and the b * value in the L * a * b * color system are within ± 30, both the conduction region a and the insulation region b are observed as colorless and transparent. The a * value and b * value in the L * a * b * color system are measured with a spectrophotometer.

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

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

[Example 1]
A first high refractive index layer, a transparent metal film, and a second high refractive index layer are formed on a transparent substrate made of Kimoto's HCPET film model number 125G1SBF (refractive index of light having a wavelength of 570 nm: 1.68) by the following method. Was deposited.

(First high refractive index layer)
Using a magnetron sputtering apparatus of Osaka Vacuum Co., on the transparent substrate, ZnS is RF sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.8 ３ / s. did. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of ZnS was 2.37, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.37.

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

(Second high refractive index layer)
On the transparent metal film, using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS-ITO at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.0 Å / s. Was RF sputtered. The target-substrate distance was 90 mm. The ratio (mass ratio) of ZnS and ITO was 20:80, and the refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.11.

[Example 2]
A transparent conductor was produced in the same manner as in Example 1 except that the ratio (mass ratio) of ZnS and ITO of the second high refractive index layer was 10:90. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.08.

[Example 3]
The transparent substrate was changed to PET (Cosmo Shine A4300 thickness 50 μm, light refractive index of wavelength 570 nm: 1.58) manufactured by Toyobo Co., Ltd., and the ratio (mass ratio) of ZnS and ITO of the second high refractive index layer was 35: A transparent conductor was produced in the same manner as in Example 1 except that 65. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.15.

[Example 4]
The transparent substrate was changed to PET made by Toyobo Co., Ltd. (Cosmo Shine A4300 thickness 50 μm, light refractive index of wavelength 570 nm: 1.58), and the ratio (mass ratio) of ZnS and ITO of the second high refractive index layer was 55: A transparent conductor was produced in the same manner as in Example 1 except that it was 45. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.215.

[Example 5]
The transparent substrate was changed to PET made by Toyobo Co., Ltd. (Cosmo Shine A4300 thickness 50 μm, light refractive index of wavelength 570 nm: 1.58), and the ratio (mass ratio) of ZnS and ITO of the second high refractive index layer was 65: A transparent conductor was produced in the same manner as in Example 1 except that 35 was used. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.225.

[Example 6]
The transparent substrate was changed to PET (Cosmo Shine A4300 thickness 50 μm, light refractive index of wavelength 570 nm: 1.58) manufactured by Toyobo Co., Ltd., and the ratio (mass ratio) of ZnS and ITO of the second high refractive index layer was 35: A transparent conductor was produced in the same manner as in Example 1 except that 65. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.155.

[Example 7]
The transparent substrate was changed to a PC film manufactured by Asahi Glass Co., Ltd. (refractive index of light with a wavelength of 570 nm: 1.59), and the second high refractive index layer was transparent in the same manner as in Example 1 except that it was formed by the following method. A conductor was produced.

(Second high refractive index layer)
On the transparent metal film, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS—ZnO at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.0 Å / s. Was RF sputtered. The target-substrate distance was 90 mm. The ratio (mass ratio) of ZnS and ZnO was 10:90, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was 2.08.

[Example 8]
A transparent conductor was produced in the same manner as in Example 7 except that the ratio (mass ratio) of ZnS and ZnO in the second high refractive index layer was 55:45. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.215.

[Example 9]
A transparent conductor was produced in the same manner as in Example 7, except that the ratio (mass ratio) of ZnS and ZnO in the second high refractive index layer was 65:35. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.245.

[Example 10]
The transparent substrate was changed to a Konica Minolta TAC film (refractive index of light having a wavelength of 570 nm: 1.48), and a first high refractive index layer and a second high refractive index layer were formed by the following methods, respectively. A transparent conductor was produced in the same manner as in Example 1 except for the above.

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

(Second high refractive index layer)
On the transparent metal film, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS-SiO _{2 with} Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.0 Å / s. -RF sputtered ITO. The target-substrate distance was 90 mm.
The ratio (mass ratio) between ZnS and SiO ₂ was 80:20, and the ratio (mass ratio) between ZnS—SiO ₂ and ITO was 20:80. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.066.

[Example 11]
A transparent conductor was produced in the same manner as in Example 10 except that the transparent substrate was changed to Kimoto HCPET film model 125G1SBF (refractive index of light having a wavelength of 570 nm: 1.68).

[Example 12]
A transparent conductor was produced in the same manner as in Example 10, except that the transparent substrate was changed to a film made of cycloolefin polymer (refractive index of light having a wavelength of 570 nm: 1.50).

[Example 13]
The transparent substrate was changed to a non-alkali glass substrate (EAGLE XG, wavelength 570 nm light refractive index: 1.52) manufactured by Corning, and the ratio (mass ratio) of ZnS-SiO ₂ and ITO of the second high refractive index layer A transparent conductor was prepared in the same manner as in Example 10 except that the ratio was 35:65. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.078.

[Example 14]
The transparent substrate was changed to a non-alkali glass substrate (EAGLE XG, wavelength 570 nm light refractive index: 1.52) manufactured by Corning, and the second high refractive index layer was a film (mass ratio) made of ZnS—SiO ₂ and IZO. 20:80) A transparent conductor was produced in the same manner as in Example 10 except that it was changed to 20:80). The method for forming the second high refractive index layer was the same as the method for forming the second high refractive index layer in Example 10. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.11.

[Example 15]
The transparent substrate was changed to a non-alkali glass substrate (EAGLE XG, wavelength 570 nm light refractive index: 1.52) manufactured by Corning, and the second high refractive index layer was a film (mass ratio) made of ZnS—SiO ₂ and IGZO. 20:80) A transparent conductor was produced in the same manner as in Example 10 except that it was changed to 20:80). The method for forming the second high refractive index layer was the same as the method for forming the second high refractive index layer in Example 10. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.11.

[Example 16]
The transparent substrate was changed to a Konica Minolta TAC film (refractive index of light having a wavelength of 570 nm: 1.48), and the ratio (mass ratio) of ZnS—SiO ₂ and ITO of the second high refractive index layer was changed to 55:45. A transparent conductor was produced in the same manner as in Example 10 except that. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.094.

[Example 17]
The transparent substrate was changed to a Konica Minolta TAC film (refractive index of light having a wavelength of 570 nm: 1.48), and the ratio (mass ratio) of ZnS—SiO ₂ and ITO of the second high refractive index layer was changed to 65:35. A transparent conductor was produced in the same manner as in Example 10 except that. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.102.

[Example 18]
The transparent substrate was changed to PET made by Toyobo Co. (Cosmo Shine A4300 thickness 50 μm, wavelength 570 nm light refractive index: 1.58), and the target material at the time of forming the transparent metal film was an Ag—Bi alloy (amount of Bi: 1 at%), and a transparent conductor was produced in the same manner as in Example 10 except that the film was formed by the following method.

(Transparent metal film)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., an Ag—Bi alloy was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / s. The target-substrate distance was 90 mm.

[Example 19]
The transparent substrate was changed to PET made by Toyobo (Cosmo Shine A4300, thickness 50 μm, light refractive index of wavelength 570 nm: 1.58), and the target material at the time of forming the transparent metal film was Ag-Pd alloy (Fluya alloy AP And a transparent conductor was prepared in the same manner as in Example 10 except that the film was formed in the same manner as the transparent metal film in Example 18.

[Example 20]
The transparent substrate was changed to PET (Cosmo Shine A4300 thickness 50 μm, wavelength 570 nm light refractive index: 1.58) manufactured by Toyobo Co., Ltd., and the target material at the time of forming the transparent metal film was Ag—Pd—Cu alloy (Fluya Metal) APC was manufactured in the same manner as in Example 10 except that the film was formed in the same manner as the transparent metal film in Example 18.

[Example 21]
The transparent substrate was changed to PET (Cosmo Shine A4300 thickness 50 μm, light refractive index of wavelength 570 nm: 1.58) manufactured by Toyobo Co., Ltd., and the target material at the time of forming the transparent metal film was an Ag—Bi—Ge—Au alloy ( Made by Kobelco Research Institute: Ag (98.35 at%) / Bi (0.35 at%) / Ge (0.3%) / Au (1.0 at%)), the same as the transparent metal film of Example 18. A transparent conductor was produced in the same manner as in Example 10 except that the film was formed.

[Example 22]
The transparent substrate is changed to a PC film manufactured by Asahi Glass Co., Ltd. (refractive index of light having a wavelength of 570 nm: 1.59), the target material at the time of forming the transparent metal film is Ag, and the second high refractive index layer is formed by the following method. A transparent conductor was produced in the same manner as in Example 18 except that the film was formed in the same manner as Example 18.

(Second high refractive index layer)
On the transparent metal film, using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS-SiO at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.0 Å / s. _2- Cu was RF sputtered. The target-substrate distance was 90 mm.
The ratio (mass ratio) between ZnS and SiO ₂ was 80:20, and the ratio (mass ratio) between ZnS—SiO ₂ and Cu was 99.97: 0.03. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.13.

[Example 23]
A transparent conductor was produced in the same manner as in Example 22 except that the ratio (mass ratio) of ZnS—SiO ₂ and Cu in the second high refractive index layer was 99: 1. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.13.

[Example 24]
The transparent substrate was changed to a PC film manufactured by Asahi Glass Co., Ltd. (refractive index of light having a wavelength of 570 nm: 1.59), the target material at the time of forming the transparent metal film was Ag, and the second high refractive index layer was ZnS-SiO _2. A transparent conductor was prepared in the same manner as in Example 18 except that the film was made of Al and Al (mass ratio 99.97: 0.03). The method for forming the second high refractive index layer was the same as the method for forming the second high refractive index layer in Example 18. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.13.

[Example 25]
A transparent conductor was produced in the same manner as in Example 24 except that the ratio (mass ratio) of ZnS—SiO ₂ and Al in the second high refractive index layer was 99: 1. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.13.

[Example 26]
On a white substrate of Yamanaka Semiconductor (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), on the same substrate as in Example 1, first high refractive index layer / first antisulfide layer / transparent A metal film / second antisulfuration layer / second high refractive index layer was formed in this order.
The transparent metal film was formed by the same method as in Example 18 except that the target material at the time of film formation was Ag.
The first high refractive index layer was formed in the same manner as in Example 18.
The first sulfurization prevention layer, the second sulfurization prevention layer, and the second high refractive index layer were formed by the following method.

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

(Second high refractive index layer)
On the second sulfidation prevention layer, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.8 Å / s. —SiO ₂ —ZnO was RF sputtered. The target-substrate distance was 90 mm. The ratio (mass ratio) between ZnS—SiO ₂ and ZnO was 55:45, and the refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.215.

[Example 27]
The transparent substrate was changed to a white substrate of Yamanaka Semiconductor (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), the target material at the time of forming the transparent metal film was set to Ag, and the first high refractive index layer And the transparent conductor was produced similarly to Example 18 except having formed into a film with the following method the 2nd high refractive index layer.

(First high refractive index layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., IZO was sputtered with a DC pulse at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 50 W, and deposition rate 0.25 Å / s. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the first high refractive index layer was 2.05.

(Second high refractive index layer)
On the transparent metal film, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS-IZO at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 3.0 Å / s. Was RF sputtered. The target-substrate distance was 90 mm. The ratio (mass ratio) between ZnS and IZO was 20:80, and the refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.11.

[Example 28]
The transparent substrate was changed to a Yamanaka Semiconductor white plate substrate (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), and the first high refractive index layer was formed in the same manner as the second high refractive index of Example 27. A transparent conductor was prepared in the same manner as in Example 27 except that the film was formed and the second high refractive index layer was formed in the same manner as the first high refractive index layer in Example 27.

[Example 29]
Example 22 except that the transparent substrate was changed to a Yamanaka Semiconductor white plate substrate (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), and the second high refractive index layer was formed by the following method. A transparent conductor was prepared in the same manner as described above.

(Second high refractive index layer)
On the second sulfidation prevention layer, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.8 Å / s. —SiO ₂ —Ga ₂ O ₃ was RF sputtered. The target-substrate distance was 90 mm. The ratio (mass ratio) between ZnS—SiO ₂ and Ga ₂ O ₃ was 80:20, and the refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.11.

[Example 30]
A transparent conductor was produced in the same manner as in Example 29 except that the material of the second high refractive index layer was ZnS—SiO ₂ —TiO ₂ . The ratio (mass ratio) between ZnS—SiO ₂ and TiO ₂ was 80:20, and the refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.164.

[Example 31]
The target material at the time of forming the transparent metal film is Ag, the first high refractive index layer is formed by the same method as in Example 1, and the second high refractive index layer is formed by the following method. A transparent conductor was produced in the same manner as in Example 18.

(Second high refractive index layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ITO was sputtered with DC pulses at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 50 W, and deposition rate 0.25 Å / s. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.12.

[Example 32]
A transparent conductor was prepared in the same manner as in Example 18 except that the target material at the time of forming the transparent metal film was Ag and the second high refractive index layer was the same as the second high refractive index layer of Example 28. .

[Example 33]
A transparent conductor as in Example 32 except that the target material at the time of forming the transparent metal film is Ag and the ratio (mass ratio) of ZnS and SiO _{2 of} the first high refractive index layer is 70:30. Was made. The refractive index of light having a wavelength of 570 nm of the first high refractive index layer was 2.083.

[Example 34]
A transparent conductor was produced in the same manner as in Example 32 except that the ratio (mass ratio) of ZnS and SiO _{2 in} the first high refractive index layer was 95: 5. The refractive index of light having a wavelength of 570 nm of the first high refractive index layer was 2.305.

[Example 35]
The transparent substrate was changed to a white substrate of Yamanaka Semiconductor (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), the target material at the time of forming the transparent metal film was set to Ag, and the second high refractive index layer A transparent conductor was produced in the same manner as in Example 18 except that the film was formed by the following method.

(Second high refractive index layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., GZO was sputtered with a DC pulse at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 50 W, and deposition rate 0.25 Å / s. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.04.

[Example 36]
Example 18 except that the transparent substrate was changed to a Yamanaka Semiconductor white plate substrate (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), and the second high refractive index layer was formed by the following method. A transparent conductor was prepared in the same manner as described above.

(Second high refractive index layer)
AZO was sputtered with DC pulses at 20 sccm Ar, 0 sccm O ₂ , sputtering pressure 0.1 Pa, room temperature, target side power 50 W, and deposition rate 0.25 Å / s using an Osaka Vacuum Company magnetron sputtering apparatus. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.05.

[Example 37]
Example 18 except that the transparent substrate was changed to a Yamanaka Semiconductor white plate substrate (φ30 mm, thickness 2 mm, wavelength 570 nm light refractive index: 1.52), and the second high refractive index layer was formed by the following method. A transparent conductor was prepared in the same manner as described above.

(Second high refractive index layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., IGZO was sputtered with DC pulses at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 50 W, and deposition rate 0.25 Å / s. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.09.

[Comparative Example 1]
A first high refractive index layer (ITO) / transparent metal film (Ag) / second high refractive index layer (ITO) was laminated in this order on a transparent substrate made of quartz.
The transparent metal film was formed by the same method as in Example 18 using Ag as the target material when forming the transparent metal film.
The first high refractive index layer and the second high refractive index layer were formed by the following methods, respectively.

(First high refractive index layer and second high refractive index layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ITO was sputtered with DC at 20 sccm Ar, ₂ sccm O ₂ , sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 0.5 Å / s. The target-substrate distance was 90 mm. The refractive index of light having a wavelength of 570 nm of the second high refractive index layer was 2.09.

[Comparative Example 2]
On the K9 glass substrate, a first high refractive index layer (ZnS) / transparent metal film (Ag) / second high refractive index layer (ZnS) were laminated in this order.
The transparent metal film was formed by the same method as in Example 18 using Ag as the target material when forming the transparent metal film.
The first high refractive index layer and the second high refractive index layer were both formed in the same manner as the first high refractive index layer of Example 1.

[Evaluation]
About the transparent conductor obtained by each Example and the comparative example, average transmittance | permeability, resistance value stability, and wet heat tolerance were evaluated with the following method. The results are shown in Tables 1 to 3.

(Average transmittance)
The transmittance of the transparent conductor obtained in each example and comparative example was calculated as follows. About the obtained transparent conductor, measurement light was incident from a position inclined by 5 ° with respect to the normal of the surface of the transparent metal film (the surface of the second high refractive index layer). And the transmittance | permeability of the transparent conductor was measured with the spectrophotometer (H4100 by Hitachi High-Tech).

(Resistance value stability)
Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Analytech was brought into contact with the surface (two points) of the second high refractive index layer of each transparent conductor to confirm the stability of the resistance value. The temperature of the measurement environment was 24 ° C., and the humidity was 30% Rh. The stability of the resistance value was evaluated according to the following criteria.
○: The resistance value is stable after 5 seconds from the start of measurement and the resistance value is 20Ω / □ or less. Δ: The resistance value is not stable after 5 seconds from the start of measurement, but the resistance value is within 50Ω / □. The resistance value is not stable after 5 seconds from the start of measurement, and the measured value exceeds 50Ω / □.

(Heat heat resistance)
Each transparent conductor was placed in a moist heat environment of 65 ° C. and 95% Rh for 100 hours. Thereafter, the appearance of the transparent conductor was visually observed and evaluated according to the following criteria.
○: No abnormality in appearance Δ: 1 to 5 spots are observed ×: 6 or more spots are observed

As shown in Table 3, in Comparative Example 1 in which ZnS was not contained in the first high refractive index layer or the second high refractive index layer, the wet heat resistance was low, and appearance defects were caused by humidity and heat. In Comparative Example 2 in which ZnS was contained in the first high refractive index layer and the second high refractive index layer, although resistance to wet heat was high, resistance value stability was low.
On the other hand, as shown in Tables 1 to 3, in Examples 1 to 37 in which the second high refractive index layer contains a conductive material, the surface electrical resistance value was stabilized. Furthermore, since ZnS is contained in either the first high refractive index layer or the second high refractive index layer, poor appearance hardly occurs even in a humid heat environment.

Here, when the conductive material contained in the second high refractive index layer is a metal oxide, the resistance value is stable when the amount of the metal oxide is 40% by mass or more with respect to the total mass of the second high refractive index layer. The properties were particularly likely to increase (Examples 1 to 4, 6 to 8, 10 to 16, 18 to 21, 26 to 28, and 31 to 37). On the other hand, when the conductive material contained in the second high refractive index layer is a metal, if the amount of metal relative to the total mass of the second high refractive index layer is less than 1% by mass, the transparent conductor can be removed even in a humid heat environment. The appearance defect of the transparent conductor was not particularly likely to occur (Examples 22 and 24).

This application claims priority based on Japanese Patent Application No. 2013-256128 filed on Dec. 11, 2013. The contents described in the application specification and the drawings are all incorporated herein.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer 3 Transparent metal film 4 2nd high refractive index layer 100 Transparent conductor

Claims

A transparent substrate;
A first high refractive index layer including a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate;
A transparent metal film,
A second high refractive index layer containing a conductive material, and in this order,
A transparent conductor containing ZnS in at least one of the first high refractive index layer or the second high refractive index layer.
The conductive material is TiO 2 , ITO, In 2 O 3 , ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7 , Ti 2 O 3 , TiO, From the group consisting of SnO 2 , La 2 Ti 2 O 7 , IZO, AZO, GZO, ATO, ICO, IGZO, ZTO, Bi 2 O 3 , Ga 2 O 3 , GeO 2 , WO 3 , HfO 2 , a-GIO The transparent conductor according to claim 1, comprising at least one metal selected from the group consisting of metal oxides selected from the group consisting of Ag, Cu, Al, and Au.
The transparent conductor according to claim 2, wherein the conductive material is the metal oxide, and the amount of the metal oxide with respect to the mass of the second high refractive index layer is 30% by mass or more.
The transparent conductor according to claim 2, wherein the conductive material is the metal, and the amount of the metal with respect to the mass of the second high refractive index layer is 5% by mass or less.
The transparent conductor according to claim 1, wherein the thickness of the transparent metal film is 20 nm or less.