WO2015111327A1 - Transparent conductor - Google Patents

Abstract

The objective of the present invention is to provide a transparent conductor which has excellent moisture resistance and is capable of suppressing the occurrence of warp. This transparent conductive is provided with a transparent substrate (1) and conductive layers (6) which are provided on both surfaces of the transparent substrate (1). This transparent conductor is characterized in that at least one of the conductive layers (6) is a laminate that comprises a transparent metal layer (3) and a first high-refractive-index layer (2) or a second high-refractive-index layer (4), each of which contains zinc sulfide.

Description

Transparent conductor

The present invention relates to a transparent conductor including a transparent metal layer. In particular, the present invention relates to a transparent conductor that has excellent moisture resistance and can suppress the occurrence of warpage.

In recent years, transparent conductors are used in various devices such as liquid crystal displays, plasma displays, display devices such as inorganic and organic electroluminescence displays, touch panels, solar cells, and the like.

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

As such a transparent conductor, for example, a metal oxide layer and a metal layer are laminated on a transparent polymer film, and a transparent ion that suppresses intrusion of halogen ions or moisture existing in the environment is further formed thereon. There is provided a structure in which resin layers are laminated (see, for example, Patent Document 1).

However, according to the above-described conventional technology, the function of suppressing the intrusion of moisture and the like is not sufficient, and the corrosion of the metal layer or the like occurs, so that the appearance of the transparent conductor is impaired or the light transmittance is reduced. There is a problem that. In addition, when each layer is provided only on one side of the transparent polymer film, there is a problem that stress is generated in the transparent conductor and warpage occurs.

JP 2007-196552 A

The present invention has been made in view of the above problems and situations, and a solution to that problem is to provide a transparent conductor that has excellent moisture resistance and can suppress the occurrence of warpage.

As a result of examining the cause of the above-mentioned problem in order to solve the above-mentioned problem according to the present invention, it comprises a transparent substrate and a conductive layer provided on both surfaces of the transparent substrate, and at least one of the conductive layers is: It has been found that a transparent conductor that has excellent moisture resistance and can suppress the occurrence of warpage is obtained by being a laminate including a transparent metal layer and a zinc sulfide-containing layer.
That is, the subject concerning this invention is solved by the following means.

1. A transparent substrate;
A conductive layer provided on both sides of the transparent substrate,
A transparent conductor, wherein at least one of the conductive layers is a laminate including a transparent metal layer and a zinc sulfide-containing layer.

2. 2. The transparent conductor according to item 1, wherein an anti-sulfurization layer is provided between the transparent metal layer and the zinc sulfide-containing layer.

3. The transparent conductor according to item 1 or 2, wherein the conductive layer or the transparent metal layer is patterned.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in moisture resistance and can provide the transparent conductor which can suppress generation | occurrence | production of curvature.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
Since at least one of the conductive layers provided on both surfaces of the transparent substrate includes a zinc sulfide-containing layer, the zinc sulfide-containing layer suppresses moisture permeation and improves the moisture resistance of the transparent conductor. be able to. Thereby, corrosion of a transparent metal layer can be suppressed and it can suppress that the external appearance of a transparent conductor is impaired, the transmittance | permeability falls, or resistance value rises.
Moreover, since the conductive layer is provided on both surfaces of the transparent substrate, the stress generated on both surfaces of the transparent conductor can be offset, and the occurrence of warpage can be suppressed.

Schematic sectional view showing an example of the layer structure of the transparent conductor of the present invention Schematic sectional view showing another example of the layer structure of the transparent conductor of the present invention The schematic diagram which shows an example of the pattern which consists of a conduction | electrical_connection area | region and an insulation area | region of the transparent conductor of this invention. Graph showing admittance locus of wavelength 570nm of transparent conductor

The transparent conductor of the present invention comprises a transparent substrate and conductive layers provided on both sides of the transparent substrate, and at least one of the conductive layers is a laminate including a transparent metal layer and a zinc sulfide-containing layer. It is characterized by being. This feature is a technical feature common to or corresponding to each of claims 1 to 4.
In the present invention, it is preferable that a sulfidation prevention layer is provided between the transparent metal layer and the zinc sulfide-containing layer. Thereby, it can suppress that a metal sulfide is produced | generated and can improve the light transmittance of a transparent conductor.
In the present invention, the conductive layer or the transparent metal layer is preferably patterned. Thereby, a transparent conductor can be used for various optoelectronic devices.

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

1. Layer configuration of transparent conductor An example of the layer configuration of the transparent conductor of the present invention is shown in FIGS. 1 and 2. As shown in FIGS. 1 and 2, the transparent conductor 100 of the present invention includes a first high refractive index layer 2 / a transparent metal layer 3 / a second high height on both sides of the transparent substrate 1 from the transparent substrate 1 side. A refractive index layer 4 is provided. In the transparent conductor 100 of the present invention, either one or both of the first high refractive index layer 2 and the second high refractive index layer 4 constitute a zinc sulfide-containing layer containing zinc sulfide. . And it is preferable that the sulfide prevention layer 5 (5a and 5b) is provided between the first high refractive index layer 2 or the second high refractive index layer 4 containing zinc sulfide and the transparent metal layer 3. .
In the transparent conductor 100 shown in FIGS. 1 and 2, the first high refractive index layer 2 and the second high refractive index layer 4 both contain zinc sulfide, and the first high refractive index layer 2 and the transparent metal layer 3. In this example, the first sulfidation preventing layer 5 a is provided between the transparent metal layer 3 and the second high refractive index layer 4.
Further, in the transparent conductor 100 shown in FIGS. 1 and 2, the first high refractive index layer 2, the first antisulfurization layer 5a, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. 4 constitutes the conductive layer 6.

When the transparent metal layer and the layer containing zinc sulfide are formed adjacent to each other, a metal sulfide derived from a metal constituting the transparent metal layer is likely to be generated, and the light transmittance of the transparent conductor is likely to be lowered. The metal sulfide is presumed to be produced as follows.

When a transparent metal layer is formed on a zinc sulfide-containing layer (first high refractive index layer) by a vapor deposition method such as sputtering or vapor deposition, the unreacted sulfur component in the zinc sulfide-containing layer is a transparent metal. It is sputtered into the film forming atmosphere by the material of the layer (metal material). Then, the ejected sulfur component reacts with the metal, and metal sulfide is deposited on the zinc sulfide-containing layer. Moreover, when forming a zinc sulfide content layer and a transparent metal layer continuously, the sulfur component contained in the film-forming atmosphere of a zinc sulfide content layer remains in a transparent metal layer atmosphere. And this sulfur component and a metal react, and a metal sulfide deposits on a zinc sulfide content layer.

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

On the other hand, in the transparent conductor 100 of the present invention, for example, as shown in FIG. 1, the first antisulfurization layer 5 a is laminated on the first high refractive index layer 2. In this configuration, since the first high refractive index layer 2 is protected by the first antisulfurization layer 5a, the sulfur component in the first high refractive index layer 2 is not easily ejected when the transparent metal layer 3 is formed. Even if the first high-refractive index layer 2 and the transparent metal layer 3 are continuously formed, the sulfur component contained in the film formation atmosphere of the first high-refractive index layer 2 is the configuration of the first antisulfurization layer 5a. It reacts with the component or is adsorbed by the component of the first antisulfurization layer 5a. Therefore, the film forming atmosphere of the transparent metal layer 3 hardly contains sulfur, and the generation of metal sulfide is suppressed.

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

In the transparent conductor of the present invention, the transparent metal layer 3 may be laminated on the entire surface of the transparent substrate 1 as shown in FIG. 1, or the transparent metal layer 3 has a desired shape as shown in FIG. It may be patterned. In the transparent conductor of the present invention, the region a where the transparent metal layer 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 where the transparent metal layer 3 is not included 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. possible.

Further, the transparent conductor 100 of the present invention may be provided with a layer other than the transparent substrate 1, the first high refractive index layer 2, the transparent metal layer 3, the second high refractive index layer 4, and the antisulfurization layer 5. good. For example, an underlayer that can be a growth nucleus when forming the transparent metal layer 3 may be provided adjacent to the transparent metal layer 3 between the transparent metal layer 3 and the first high refractive index layer 2. .

Hereinafter, each layer and its material constituting the transparent conductor 100 of the present invention will be described.

<Transparent substrate>
The transparent substrate 1 may be a transparent substrate and may be the same as the transparent substrate of various conventionally known display devices.
Here, in the present invention, “transparent” means that the average transmittance of light having a wavelength of 550 nm is 50% or more.

As the transparent substrate 1, for example, a glass substrate, a cellulose ester resin (for example, triacetyl cellulose, diacetyl cellulose, acetyl propionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Ltd.)), cyclo Olefin resins (for example, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resins (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex (Sumitomo) Chemical)), polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate), polyether sulfone, ABS / AS resin MBS resins, polystyrene, methacrylic resins, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resins), such as a transparent resin film comprising a styrene block copolymer resins. When the transparent substrate 1 is a transparent resin film, the transparent resin film may contain two or more kinds of resins.

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

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

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

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

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

The thickness of the transparent substrate 1 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the transparent substrate is 1 μm or more, the strength of the transparent substrate 1 is increased, and it is possible to prevent the first high refractive index layer 2 from being cracked or torn. On the other hand, if 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.

<< First high refractive index layer >>
The first high refractive index layer 2 is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor 100, that is, the region where the transparent metal layer 3 is formed. It is formed in the conduction region a. The first high refractive index layer 2 may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of ensuring the visibility of the pattern composed of the conductive region a and the insulating region b, only the conductive region a. It is preferable to be formed.

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

The dielectric material or the oxide semiconductor material included in the first high refractive index layer 2 may be an insulating material or a conductive material. A metal oxide can be used as the dielectric material or the oxide semiconductor material. Examples of metal _oxides, TiO _2, ITO (indium tin _{oxide), ZnO, Nb 2 O 5} , ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3 _{, TiO, SnO 2, La 2} Ti 2 O 7, IZO ( indium zinc oxide), AZO (aluminum oxide zinc), GZO (gallium oxide, zinc), ATO (antimony tin oxide), ICO (indium cerium 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), IGZO (InGaZnO), and the like can be given. The first high refractive index layer 2 may contain only one kind of the metal oxide or two or more kinds.

As described above, zinc sulfide can be used as the dielectric material or the oxide semiconductor material included in the first high refractive index layer 2. When zinc sulfide is contained in the first high refractive index layer 2, moisture permeation to the transparent metal layer 3 can be suppressed and corrosion of the transparent metal layer 3 can be suppressed. The first high refractive index layer 2 may contain only zinc sulfide, or may contain other materials together with zinc sulfide. Material contained together with zinc sulphide, a metal oxide or SiO ₂ or the like which can be used as the dielectric material or an oxide semiconductor material, as will be described later, particularly preferably SiO _2. When SiO ₂ is contained together with zinc sulfide, the first high refractive index layer 2 is likely to be amorphous, and the flexibility of the transparent conductor 100 is likely to be enhanced.

When the first high refractive index layer 2 contains other materials together with zinc sulfide, the content of zinc sulfide is 0. 0 relative to the total number of moles of all materials constituting the first high refractive index layer 2. The content is preferably 1 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass. When the content of zinc sulfide is large, the sputtering rate is increased and the formation rate of the first high refractive index layer 2 is increased. On the other hand, when many components other than zinc sulfide are contained, the amorphous nature of the first high refractive index layer 2 is increased, and cracking of the first high refractive index layer 2 is suppressed.

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

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

Further, when the first high refractive index layer 2 is a layer patterned into 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 placing a mask having a desired pattern on the film formation surface, It may be a layer patterned by an etching method.

(Amorphized metal material)
The first high refractive index layer 2 preferably contains zinc sulfide, but more preferably contains amorphous zinc sulfide. Since the amorphous zinc sulfide is contained in the first high refractive index layer 2, stress generated in the transparent conductor 100 can be reduced, and warpage of the transparent conductor 100 can be suppressed. It is possible to suppress the generation of cracks when the transparent conductor 100 is bent. Furthermore, since the first high refractive index layer 2 contains amorphous zinc sulfide, the light transmittance of the first high refractive index layer 2 can be improved.

By making the first high refractive index layer 2 contain an amorphous metal material such as metal oxide, metal nitride or metal fluoride together with zinc sulfide, the zinc sulfide can be made amorphous. As the amorphized metal material, it is possible to achieve amorphization of zinc sulfide by mixing 1 to 50% by mass with respect to zinc sulfide, and it is preferable to mix 5 to 20% by mass. Further, the refractive index of light can be changed by appropriately adjusting the content of the amorphized metal material. Therefore, the light transmittance can be set as desired. Specifically, the first high refractive index layer 2 is not made amorphous by including, for example, TiO ₂ or Nb ₂ O ₅ which is a transparent material having a higher refractive index than zinc sulfide as an amorphized metal material. That is, the reflection band can be expanded as compared with the first high refractive index layer made of crystalline zinc sulfide alone. This facilitates adjustment of the optical characteristics of the transparent conductor 100.

In addition, zinc sulfide that has been amorphized using an amorphized metal material has better durability. Therefore, the transparent metal layer 3 can be protected more reliably. Therefore, for example, by containing Si ₃ N ₄ or Al ₂ O ₃ as an amorphized metal material together with zinc sulfide in the first high refractive index layer 2, it is possible to improve the scratch resistance of the transparent conductor 100. Become.

As the amorphized metal material, for example, a metal oxide, a metal fluoride, a metal nitride, or the like can be used.

Examples of the metal oxide used as the amorphized metal material include TiO ₂ , In ₂ O ₅ , ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , and Ti ₄ O _7. , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , ITO (InSnO), IGZO (InGaZnO), IZO (InZnO), AZO (AlZnO), GZO (GaZnO), ATO (AlSnO), ICO ( InCeO), Bi ₂ O ₃ , a-GIO (GaInO), 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.

Among these, SiO ₂ and TiO ₂ are preferable. When SiO ₂ is used, zinc sulfide can be made amorphous even if its content is small. Therefore, by incorporating the SiO _2, it is possible to after amorphization of zinc sulfide, particularly well exhibited a high adhesion (peeling resistance) and high durability (such as against moisture, etc.). In addition, since TiO ₂ exhibits a particularly high refractive index among transparent materials, by using TiO ₂ , the reflection band can be widened to increase the reflectance, and the reflection characteristics can be improved.

Examples of the metal fluoride used as the amorphized metal material 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.

Furthermore, examples of the metal nitride used as the amorphized metal material include Si ₃ N ₄ and AlN. Among these, Si ₃ N ₄ is preferable. Since Si ₃ N ₄ has high hardness, it is possible to improve the scratch resistance of the first high refractive index layer 2 by using Si ₃ N ₄ .

Note that these amorphized metal materials may be used alone, or two or more of them may be used in any ratio and combination.

In order to obtain the amorphized zinc sulfide, there is no particular limitation on the amount of the amorphized metal material contained with respect to the crystalline zinc sulfide. For example, although it cannot be generally described because it varies depending on the type of amorphized metal material, when SiO ₂ is used as the amorphized metal material, it is usually 1% by mass or more, more preferably 5% by mass with respect to crystalline zinc sulfide. % Or more and usually 99% by mass or less, and more preferably 95% by mass or less of SiO ₂ can be used to make amorphous zinc sulfide.

<First antisulfuration layer>
When the first high refractive index layer 2 contains zinc sulfide, it is preferable that a first sulfidation preventing layer 5a is provided between the first high refractive index layer 2 and the transparent metal layer 3, as shown in FIG. . The first sulfidation preventing layer 5a may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of ensuring the visibility of the pattern made up of the conductive region a and the insulating region b, only the conductive region a is provided. Preferably it is formed.

As the material of the first antisulfurization layer 5a, for example, metal oxide, metal nitride, metal fluoride, or Zn can be used. The first sulfidation preventing layer 5a may contain only one kind or two or more kinds. However, when the first high refractive index layer 2, the first antisulfurization layer 5a, and the transparent metal layer 3 are continuously formed, the first antisulfurization layer is composed of a compound capable of reacting with sulfur, It preferably contains a compound capable of adsorbing sulfur. When the material contained in the first sulfurization prevention layer is a compound that reacts with sulfur, the reaction product with sulfur preferably has a high visible light transmittance.

Examples of the metal oxide include TiO ₂ , ITO, ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO _2. , La ₂ Ti ₂ O ₇ , IZO, AZO, GZO, ATO, ICO, Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , IGZO, M3 (registered trademark, manufactured by Merck Japan, a mixture of aluminum oxide and lanthanum oxide), In ₂ O _{5 and the} like can be mentioned.
Examples of the metal fluoride include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like. Can do.
Examples of the metal nitride include Si ₃ N ₄ and AlN.
Among them, as the material constituting the first anti-sulfuration layer 5a, preferably a metal oxide, in _{particular, ZnO, ITO, IGZO, Ga} 2 O 3, Nb 2 O 5, SnO 2, Y 2 O 3 , and M3 are preferably . Thereby, adhesiveness with the zinc sulfide contained in the 1st high refractive index layer 2 or the 2nd high refractive index layer 4 can be improved, and durability can be improved more.

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

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

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

《Transparent metal layer》
The transparent metal layer 3 is a layer for conducting electricity in the transparent conductor 100. As described above, the transparent metal layer 3 may be formed on the entire surface of the transparent substrate 1 or may be patterned into a desired shape.

The metal contained in the transparent metal layer 3 is not particularly limited as long as it is a highly conductive metal. For example, silver, copper, gold, platinum group, titanium, chromium, palladium, ruthenium, bismuth, tantalum, or the like is used. Can do. The transparent metal layer 3 may contain only one kind of these metals or two or more kinds.

From the viewpoint of obtaining high conductivity, the transparent metal layer is preferably made of silver or an alloy containing 90 at% or more of silver.
As a metal combined with silver, for example, zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, nickel, iron, cobalt, tungsten, tantalum, chromium, indium, titanium, or the like can be used. Among these, bismuth, palladium or copper is preferable. The transparent metal layer 3 may contain a simple substance or compound of silver and a simple substance or compound of bismuth, palladium, or copper, or is included in the form of an alloy of silver and at least one of these metals. However, it is preferably included in the form of an alloy. Moreover, it is preferable that all of the materials constituting the transparent metal layer 3 are an alloy of silver and at least one of these metals. By including at least one of these metals in the transparent metal layer 3, the durability, peel resistance, etc. of the transparent conductor 100 can be further improved.
For example, when the transparent metal layer 3 contains an alloy of silver and zinc, the sulfidation resistance of the transparent metal layer 3 can be improved. For example, when the transparent metal layer 3 contains an alloy of silver and gold, the salt resistance (NaCl) resistance of the transparent metal layer 3 can be improved. Furthermore, for example, when the transparent metal layer 3 contains an alloy of silver and copper, the oxidation resistance of the transparent metal layer 3 can be improved.

The plasmon absorptivity of the transparent metal layer 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region a of the transparent conductor 100 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 3 is measured by the following procedure.
(I) Platinum palladium is formed to 0.1 nm on a glass substrate by a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the sputtering apparatus. After that, a 20 nm thick metal film is formed by sputtering on the substrate to which platinum palladium is attached.
(Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal line of the surface of the obtained metal film, and the transmittance and reflectance of the metal film are measured. Then, absorption rate = 100− (transmittance + reflectance) is calculated from the transmittance and reflectance at each wavelength, and this is used as reference data. The transmittance and reflectance are measured with a spectrophotometer.
(Iii) Subsequently, a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, the transmittance | permeability and a reflectance are measured similarly. The reference data is subtracted from the obtained absorption rate, and the calculated value is defined as the plasmon absorption rate.

The layer thickness of the transparent metal layer 3 is 10 nm or less, preferably 3 to 9 nm, and more preferably 5 to 8 nm. When the thickness of the transparent metal layer 3 is 10 nm or less, the optical admittance of the transparent conductor 100 can be easily adjusted by the first high refractive index layer 2 and the second high refractive index layer 4, and light on the surface of the conduction region a can be adjusted. The reflection of is easy to be suppressed. The layer thickness of the transparent metal layer 3 is measured with an ellipsometer.

The transparent metal layer 3 may be formed by any method, but is preferably a layer formed by a sputtering method from the viewpoint of increasing the average transmittance of the transparent metal layer. Preferably, the layer is formed on the underlying layer.

In the sputtering method, since the material collides with the deposition target at high speed during formation, a dense and smooth film can be easily obtained, and the light transmittance of the transparent metal layer 3 can be improved. Further, when the transparent metal layer 3 is a layer formed by sputtering, the transparent metal layer 3 is hardly corroded even in a high temperature and low humidity environment. The type of the sputtering method is not particularly limited, and 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 can be used. The transparent metal layer 3 is particularly preferably a layer formed by a counter sputtering method. When the transparent metal layer 3 is a layer formed by a counter sputtering method, the transparent metal layer 3 becomes dense and the surface smoothness is likely to be increased. As a result, the surface electrical resistance of the transparent metal layer 3 can be further reduced, and the light transmittance can be improved.

On the other hand, when the transparent metal layer 3 is a layer formed on an underlayer to be described later, the underlayer becomes a growth nucleus when the transparent metal layer 3 is formed, or wettability with respect to the transparent metal is increased. The transparent metal layer 3 tends to be a smooth layer. As a result, even if the transparent metal layer 3 is thin, plasmon absorption is less likely to occur. In this case, the method for forming the transparent metal layer 3 is not particularly limited. For example, a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method is used. Can do.

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

<Second anti-sulfur layer>
When the second high refractive index layer 4 contains zinc sulfide, it is preferable to provide a second antisulfurization layer 5b between the transparent metal layer 3 and the second high refractive index layer 4 as shown in FIG. .
Since the second sulfidation preventing layer 5b is configured in the same manner as the first sulfidation preventing layer 5a, the description of common points will be omitted, and only the points different from the first sulfidation preventing layer 5a will be described below. .

The layer thickness of the second antisulfurization layer 5b is preferably a layer thickness that can protect the surface of the transparent metal layer 3 from an impact when the second high refractive index layer 4 is formed. The metal contained in the transparent metal layer 3 and the zinc sulfide that can be contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfurization layer 5b is very thin and a part of the transparent metal layer 3 is slightly exposed, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. Adhesion with 4 tends to increase. Therefore, the specific layer thickness of the second sulfidation preventing layer 5b is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and still more preferably 1 to 3 nm. The layer thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.

<< Second high refractive index layer >>
The second high refractive index layer 4 is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor 100, that is, the region where the transparent metal layer 3 is formed, and at least the transparent conductor 100 conductive regions a are formed.
Since the second high-refractive index layer 4 is configured in the same manner as the first high-refractive index layer 2, description of common points is omitted, and only differences from the first high-refractive index layer 2 are described below. Explained.

As described above, the second high-refractive index layer 4 may contain zinc sulfide. If the second high-refractive index layer 4 contains zinc sulfide, moisture permeation into the transparent metal layer 3 is prevented. It is possible to suppress the corrosion of the transparent metal layer 3.

The second high refractive index layer 4 can be formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, etc. From the viewpoint of reducing the moisture permeability of the high refractive index layer 4, the second high refractive index layer 4 is particularly preferably formed by a sputtering method.

《Stress adjustment layer》
The transparent conductor 100 is provided on at least one surface of both surfaces of the transparent conductor 100, thereby adjusting the stress on the surface and reducing the stress difference between both surfaces of the transparent conductor 100 (not shown). ) May be further provided. The stress adjustment layer is preferably configured such that the difference in refractive index between adjacent layers is low. For example, the difference in refractive index between the stress adjustment layer and adjacent layers is within 20%. It is preferable that

The stress adjustment layer may be any material as long as the stress of the transparent conductor 100 can be adjusted. For example, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer High polymer, polystyrene, polyimide, polyamide, polybutylene terephthalate, polyethylene naphthalate, polysulfone, polyethersulfone, polyetheretherketone, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, cycloolefin polymer, etc. Molecular materials can be used. Among these, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, and the like are preferable from the viewpoints of transparency, durability, workability, and the like. Only one of these may be included in the stress adjusting layer, or two or more thereof may be included.

Further, the stress adjusting layer may be a deposited film or a sputtered film such as SiO ₂ , ITO, IGZO, ZnO or ZnS, or may be a hard coat layer or a layer coated with a polymer. In particular, from the viewpoint of optical adjustment, the stress adjustment layer is preferably a deposited film or a sputtered film.

The layer thickness of the stress adjusting layer may be set as long as the stress of the transparent conductor 100 can be adjusted, and is appropriately set according to the material and the forming method.
In addition, the stress adjustment layer may be provided on the outermost surface of the transparent conductor 100, or may be provided between any layers of each layer within a range not impairing the function of each layer constituting the transparent conductor 100. good. Moreover, the stress adjustment layer may be provided on both surfaces of the transparent substrate, and in that case, the layer thickness and the material may be different from each other.

<Underlayer>
As described above, the transparent conductor 100 may further include an underlayer (not shown) that becomes a growth nucleus when the transparent metal layer 3 is formed. The underlayer is provided adjacent to the transparent metal layer 3 on the transparent substrate 1 side, specifically, between the first high refractive index layer 2 and the transparent metal layer 3 or the first antisulfurization layer 5a. It is provided between the transparent metal layer 3. The underlayer is preferably formed at least in the conductive region a of the transparent conductor 100, but may be formed in the insulating region b of the transparent conductor 100.

If the transparent conductor 100 is provided with a base layer, the smoothness of the surface of the transparent metal layer 3 can be enhanced even if the thickness of the transparent metal layer 3 is thin.

Here, the underlayer includes palladium, molybdenum, zinc, germanium, niobium, indium, alloys of these metals with other metals, oxides or sulfides of these metals (for example, zinc sulfide). It is preferable that Among these, it is particularly preferable that palladium or molybdenum is contained. Further, the underlayer may contain a nitrogen-containing organic compound or the like. The underlayer may contain only one kind or two or more kinds.

When the base layer contains an alloy of palladium, molybdenum, zinc, germanium, niobium, or indium and another metal, the other metal is not particularly limited. For example, a platinum group other than palladium, gold Cobalt, nickel, titanium, aluminum, chromium, etc. can be used.

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

<Low refractive index layer>
The transparent conductor 100 may further include a low refractive index layer (not shown) that adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor on the second high refractive index layer 4. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

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

The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is preferably less than 1.8, more preferably 1.30 to 1.6, Particularly preferred is 1.35 to 1.5. The refractive index of the low refractive index layer is mainly adjusted by the refractive index of the material included in the low refractive index layer and the density of the material included in the low refractive index layer.

Examples of the dielectric material or oxide semiconductor material included in the low refractive index layer include MgF ₂ , SiO ₂ , AlF ₃ , CaF ₂ , CeF ₃ , CdF ₃ , LaF ₃ , LiF, NaF, NdF ₃ , and YF _3. , YbF ₃ , Ga ₂ O ₃ , LaAlO ₃ , Na ₃ AlF ₆ , Al ₂ O ₃ , MgO, or ThO ₂ . Among them, MgF ₂ , SiO ₂ , CaF ₂ , CeF ₃ , LaF ₃ , LiF, NaF, NdF ₃ , Na ₃ AlF ₆ , Al ₂ O ₃ , MgO or ThO ₂ are preferable, and a viewpoint that the refractive index is low. To MgF ₂ or SiO ₂ is particularly preferred. Only one of these materials may be included in the low refractive index layer, or two or more of these materials may be included.

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

The low refractive index layer can be formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method. From the viewpoint of easiness of layer formation, etc., the low refractive index layer is preferably formed by electron beam evaporation or sputtering.

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

<< 3rd high refractive index layer >>
The transparent conductor 100 may further include a third high-refractive index layer (not shown) that adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor 100 on the low refractive index layer. . The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

The third high refractive index layer preferably includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 and the refractive index of the low refractive index layer.
The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the third high refractive index layer is preferably greater than 1.5, more preferably 1.7 to 2.5, It is preferably 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the third high refractive index layer. The refractive index of the third high refractive index layer is adjusted by the refractive index of the material included in the third high refractive index layer and the density of the material included in the third high refractive index layer.

The dielectric material or oxide semiconductor material contained in the third high refractive index layer may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material contained in the third high refractive index layer is preferably a metal oxide or ZnS. As a metal oxide, the metal oxide contained in the above-mentioned 1st high refractive index layer 2 or the 2nd high refractive index layer 4 is mentioned, for example. The third high refractive index layer may contain only one kind of the metal oxide or ZnS, or may contain two or more kinds. Further, a dielectric material such as SiO ₂ may be contained together with the metal oxide or ZnS.

The layer thickness of the third high refractive index layer is not particularly limited, and is preferably 1 to 40 nm, and more preferably 5 to 20 nm. When the layer thickness of the third high refractive index layer is within the above range, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted. The layer thickness of the third high refractive index layer is measured with an ellipsometer.

The method for forming the third high refractive index layer is not particularly limited, and the third high refractive index layer can be formed by the same method as that for the first high refractive index layer 2 and the second high refractive index layer 4.

As described above, the transparent conductor 100 may include a low refractive index layer and a third high refractive index layer, but an optical adjustment layer in which a plurality of high refractive index layers and low refractive index layers are stacked. It is good also as what is equipped with.

2. About the optical admittance of the transparent conductor The reflectance R of the surface of the conductive region a of the transparent conductor (the surface opposite to the transparent substrate 1 in the transparent conductor 100) is the optical admittance Y _{env of the} medium on which light is incident, determined from the equivalent admittance Y _E of the surface of the conductive region a transparent conductor. Here, the medium on which light is incident refers to a member or environment through which light incident on the transparent conductor passes immediately before the incident, and is a member or environment made of an organic resin. The relationship between the optical admittance Y _{env of the} medium on which light is incident and the equivalent admittance Y _E of the surface of the transparent conductor is expressed by the following equation.

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

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

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

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

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

・ When the xth layer is an ideal metal layer

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

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

FIG. 4 includes a transparent substrate / first high refractive index layer (ZnS—SiO ₂ ) / first antisulfurization layer (ITO) / transparent metal layer (Ag) / second high refractive index layer (ZnS—SiO ₂ ). The admittance locus | trajectory of wavelength 570nm of the conduction area | region a of a transparent conductor is shown. The horizontal axis of the graph is the real part when the optical admittance Y of the region is expressed by x + iy, that is, x in the equation, and the vertical axis is the imaginary part of the optical admittance, that is, y in the equation. The first anti-sulfurization layer (ITO) has a sufficiently thin layer thickness, and its optical admittance is ignored.

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

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

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

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

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

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

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

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

Further, when the transparent metal layer 3 is patterned, an equivalent admittance coordinate (x _E , y _E ) of light having a wavelength of 570 nm in the conduction region a and an equivalent admittance coordinate of light having a wavelength of 570 nm in the insulation region b ( And ((x _E −x _b ) ² + (y _E −y _b ) ² ) ^0.5 ) are preferably less than 0.5, more preferably (expressed by (x _b , y _b )) Is 0.3 or less. The coordinates of the equivalent admittance Y _E conductive region a, the coordinate of the equivalent admittance Y _b of the insulating region b is sufficiently close, so these patterns less visible. Furthermore, it is preferable that | (x _env −x _b ) ² + (y _env −y _b ) ² − (x _env −x _E ) ² + (y _env −y _E ) ² | . If the said value is satisfy | filled, both the conduction | electrical_connection area | region a and the insulation area | region b will become difficult to visually recognize.

3. Regarding the physical properties of the transparent conductor The average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductor of the present invention is preferably 75% or more, more preferably 80% in both the conduction region a and the insulation region b. More preferably, it is 85% or more. When the average transmittance in the above wavelength range is 75% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor is preferably 70% or more in both the conduction region a and the insulation region b, more preferably 75% or more, and still more preferably 80%. That's it. When the average transmittance of light having a wavelength of 400 to 1000 nm is 70% or more, the transparent conductor is also used in applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. Can be applied.

On the other hand, the average absorptance of light having a wavelength of 400 to 800 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and still more preferably 10% in both the conduction region a and the insulation region b. It is as follows. In addition, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 to 800 nm is preferably 25% or less, more preferably 20% or less, and still more preferably in both the conduction region a and the insulation region b. 15% or less. On the other hand, the average reflectance of light having a wavelength of 500 to 700 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and still more preferably 5 in both the conduction region a and the insulation region b. % Or less. The lower the average absorptance and average reflectance of the transparent conductor, the higher the aforementioned average transmittance.

The average transmittance and the average reflectance are preferably the average transmittance and the 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. Further, in order to measure the substantial transmittance of the transparent conductor, a correction for removing the reflection on the outermost surface by calculation may be performed. If necessary, the transmittance and the reflectance can be measured with a spectrophotometer by allowing measurement light to enter from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductor. The absorptance is calculated from a calculation formula of 100− (transmittance + reflectance).

In addition, when the conductive region a and the insulating region b are included in the transparent conductor 100, it is preferable that the reflectance of the conductive region a and the reflectance of the insulating region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conduction region a and the luminous reflectance of the insulating region b is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. Especially preferably, it is 0.3% or less. On the other hand, the luminous reflectance of the conduction region a and the insulation region b is preferably 5% or less, more preferably 3% or less, and still more 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 may be within ± 30 in any region. Preferably, it is within ± 5, more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are within ± 30, both the conduction region a and the insulation region b are observed as colorless and transparent. The a ^* value and b ^* value in the L ^* a ^* b ^* color system are measured with a spectrophotometer.

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

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

At this time, the surface of the transparent conductor may be bonded to another member via an adhesive layer or the like. In this case, as described above, it is preferable that the equivalent admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the adhesive layer approximate each other. Thereby, reflection at the interface between the transparent conductor and the adhesive layer is suppressed.

On the other hand, when used in a configuration in which the surface of the transparent conductor is in contact with air, it is preferable that the admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the air approximate each other. Thereby, reflection of light at the interface between the transparent conductor and air is suppressed.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

<< Preparation of transparent conductor 1 >>
A first high refractive index layer (ZnS) / transparent metal layer (Ag) / second high refractive index layer (ZnS) is formed on the front side and back side of a film made of cycloolefin polymer as a transparent substrate by the following method. The layers were laminated in the following order. Thereafter, the laminate was patterned by the following method. The layer thickness of each layer is J.I. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of first high refractive index layer (ZnS))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS was RF sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of ZnS was 2.37, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.37. The thickness of the formed first high refractive index layer was 40 nm.

(Formation of transparent metal layer (Ag))
Using a counter sputtering machine manufactured by FTS Corporation, Ag was counter sputtered at an Ar of 20 sccm, a sputtering pressure of 0.5 Pa, a room temperature, a target power of 150 W, and a film formation rate of 14 K / s. The target-substrate distance was 90 mm. The thickness of the formed transparent metal layer was 7 nm.

(Formation of Second High Refractive Index Layer (ZnS))
The second high refractive index layer was formed by the same method as the first high refractive index layer.

(Laminate patterning)
A resist layer is formed in a pattern on the obtained laminate, and each layer other than the transparent substrate is patterned as shown in FIG. 3 (a pattern including a plurality of conductive regions a and line-shaped insulating regions b separating the conductive regions a). Patterned with an ITO etching solution (manufactured by Hayashi Junyaku). Only the transparent substrate was included in the insulating region. The width of the line-shaped insulating region b was 16 μm. Such patterning was performed on both surfaces of the transparent substrate.

<< Preparation of transparent conductor 2 >>
A transparent conductor 2 was prepared in the same manner as in the production of the transparent conductor 1, except that the thickness of the transparent metal layer was changed as shown in Table 1.

<< Preparation of transparent conductor 3 >>
In the production of the transparent conductor 1, the transparent conductor 1 was transparent except that the thicknesses of the first high refractive index layer and the second high refractive index layer laminated on the back side of the transparent substrate were changed as shown in Table 1. The conductor 3 was produced.

<< Preparation of transparent conductor 4 >>
In the production of the transparent conductor 1, the transparent conductor 4 was produced in the same manner except that the formation method of the second high refractive index layer was changed to the following formation method.

(Formation of second high refractive index layer (IGZO))
Using Anelva L-430S-FHS, IGZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm.

<< Preparation of transparent conductor 5 >>
In the production of the transparent conductor 1, a transparent conductor 5 was produced in the same manner except that the formation method of the first high refractive index layer and the second high refractive index layer was changed to the following formation method.

(Formation of first high refractive index layer (ZnS + SiO ₂ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS—SiO ₂ 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 3.0 Å / s. The target-substrate distance was 90 mm.
The ratio (molar ratio) between ZnS and SiO ₂ was 80:20, and the refractive index of the first high refractive index layer was 2.14.

(Formation of second high refractive index layer (ZnS + SiO ₂ ))
The second high refractive index layer was formed by the same method as the first high refractive index layer.

<< Preparation of transparent conductor 6 >>
In the production of the transparent conductor 5, a first sulfidation prevention layer is provided between the first high refractive index layer and the transparent metal layer, and a second sulfidation prevention layer is provided between the transparent metal layer and the second high refractive index layer. A transparent conductor 6 was produced in the same manner except that. The first sulfidation prevention layer and the second sulfidation prevention layer were formed as follows.

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

(Formation of second anti-sulfurization layer (ZnO))
The second sulfidation preventing layer was formed in the same manner as the first sulfidation preventing layer.

<< Preparation of transparent conductor 7 >>
In the production of the transparent conductor 6, a transparent conductor 7 was produced in the same manner except that a stress adjusting layer was further provided on the second high refractive index layer laminated on the surface side of the transparent substrate. The stress adjustment layer was formed as follows.

(Formation of stress adjustment layer)
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., SiO ₂ was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 300 W, and deposition rate 3.1 L / s. The target-substrate distance was 90 mm.

<< Preparation of transparent conductor 8 >>
In the production of the transparent conductor 1, a method for forming the first high refractive index layer and the second high refractive index layer laminated on the back side of the transparent substrate, a method for forming the second high refractive index layer of the transparent conductor 4, and A transparent conductor 8 was produced in the same manner except that the method was changed to the same method.

<< Preparation of transparent conductor 9 >>
In the production of the transparent conductor 1, the transparent conductor 9 was produced in the same manner except that the material of the transparent metal layer was changed to APC (an alloy obtained by adding Pd and Cu to Ag).

<< Preparation of Transparent Conductor 10 >>
In the production of the transparent conductor 6, the transparent conductor 10 was produced in the same manner except that the material of the transparent metal layer was changed to APC.

<< Preparation of Transparent Conductor 11 >>
A transparent metal layer (ITO) / stress adjusting layer (SiO ₂ ) was sequentially laminated by the following method on the front side and the back side of the film made of cycloolefin polymer as the transparent substrate. Thereafter, the laminate was patterned in the same manner as the transparent conductor 1. The layer thickness of each layer is J.I. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of transparent metal layer (ITO))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ITO was subjected to DC pulse sputtering at 350 KHz with Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 50 W, and deposition rate 2.5 Å / s. The target-substrate distance was 90 mm.

(Formation of stress adjustment layer (SiO ₂ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., SiO ₂ was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 300 W, and deposition rate 3.1 L / s. The target-substrate distance was 90 mm.

<< Preparation of transparent conductor 12 >>
In the production of the transparent conductor 1, the first high refractive index layer (ZnS) / transparent metal layer (Ag) / second high refractive index layer (ZnS) were formed in the same manner except that they were laminated only on the surface side of the transparent substrate. A transparent conductor 12 was produced.

<< Preparation of transparent conductor 13 >>
TiO ₂ layer / Ag layer / TiO ₂ + PA layer / TiO ₂ layer / Ag layer / TiO ₂ + PA layer / TiO ₂ layer on the front side and back side of the film made of cycloolefin polymer as a transparent substrate by the following method / Ag layer / TiO ₂ + PA layer was sequentially laminated by the following method. Thereafter, the laminate was patterned in the same manner as the transparent conductor 1. The layer thickness of each layer is J.I. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.
Here, the “TiO ₂ layer” in the transparent conductor 13 represents that the layer mainly contains titanium oxide (TiO ₂ ) and does not contain alcohol-soluble polyamide. “TiO ₂ + PA layer” indicates that the layer mainly contains titanium oxide (TiO ₂ ) and contains alcohol-soluble polyamide. Further, “Ag layer” indicates that the layer mainly contains silver.

(Formation of TiO ₂ layer or TiO ₂ + PA layer)
Using a direct gravure coater, the raw material of each layer was applied onto a transparent substrate at a film formation rate of 3 m / min, and then this coated film was dried at 100 ° C. for 80 seconds to form a precursor layer. In the state heated to ° C., a UV lamp [high pressure mercury lamp (240 W / cm), output 100%] was used to irradiate the precursor layer with ultraviolet rays once to form a titanium oxide layer.
At this time, the ultraviolet irradiation rate of the TiO ₂ layer was 3 m / min, and the ultraviolet irradiation rate of the TiO ₂ + PA layer was 2 m / min.

(Formation of Ag layer)
An Ag layer was formed using direct current sputtering. The sputtering conditions were an input power of 1.7 W / cm ² , a vacuum ultimate pressure of 5 × 10 ⁻⁶ torr, and a gas pressure of 2.5 × 10 ⁻³ torr.

In the column of the transparent conductor 13 in Table 1, the material of each layer provided on both sides of the transparent substrate is indicated by “/”, and “/” indicates the boundary between the layers, The numerical value indicates the layer thickness (nm) of each layer.

<< Evaluation of Transparent Conductors 1-13 >>
The transparent conductors 1 to 13 produced as described above were evaluated as follows. The evaluation results are shown in Table 2.

(1) Evaluation of moisture resistance In order to evaluate the durability of the transparent conductors 1 to 13, the humidity resistance (how much humidity the transparent conductor can withstand), which is a kind of durability, was evaluated. Evaluation of moisture resistance was performed as follows. That is, the produced transparent conductor was allowed to stand in an environment of 65 ° C. and 95% (relative humidity) for 100 hours, and then the transparent conductor was visually observed and evaluated according to the following criteria.
A: No crack or discoloration is observed. ○: Almost no crack or discoloration is observed. Δ: A little crack or discoloration is observed.

(2) Evaluation of transmittance The light was incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent conductors 1 to 13, and the average transmittance was measured. The average transmittance was measured by the VW method using a spectrophotometer U4100 (manufactured by Hitachi High-Technologies Corporation). The average transmittance of 450-800 nm was evaluated according to the following criteria.
◎: 85% or more ○: 80% or more and less than 85% △: 75% or more and less than 80% ×: 75% or less

(3) Evaluation of conductivity The conductive region a of the transparent conductors 1 to 13 was brought into contact with Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Analytech, and the surface electrical resistance of the conductive region a was measured. The measurement results were evaluated according to the following criteria.
◎: Less than 10Ω / □ ○: 10Ω / □ or more and less than 20Ω / □ △: 20Ω / □ or more and less than 30Ω / □ ×: 30Ω / □ or more

(4) Evaluation of warpage suppression The above transparent conductors 1 to 13 were produced using a Matsunami glass sheet glass (50 mm × 10 mm × thickness 0.1 mm) as a transparent base material, and warpage was performed using a laser displacement meter LA2010 manufactured by KEYENCE. The amount was measured. The warp angles at two points 5 cm apart were evaluated according to the following criteria.
◎: Less than 1 mrad ◎: 1 mrad or more and less than 5 mrad ○: 5 mrad or more and less than 10 mrad Δ: 10 mrad or more and less than 20 mrad ×: 20 mrad or more

(5) Evaluation of crack suppression during bending Transparent conductors 1 to 13 were placed on a flat support member, and one end was fixed. Next, the transparent conductors 1 to 13 were bent in a U shape in the forward direction and the reverse direction with respect to the warp. The curvature radius of the bent portion was 5 mm. Then, the other ends of the transparent conductors 1 to 13 were fixed to a sliding plate arranged in parallel with the support member. The sliding plate was reciprocated 1000 times in the length direction of the transparent conductors 1 to 13 while keeping the sliding plate and the support member in parallel. Thereafter, whether or not cracks or the like occurred in each layer of the transparent conductors 1 to 13 was visually confirmed. The confirmation result was evaluated according to the following criteria.
A: No crack was generated in the 30 mm × 30 mm region including the bent portion. ○: One or more cracks were generated in the 30 mm × 30 mm region including the bent portion. Δ: The bent portion was included. 10 or more and less than 50 cracks occurred in an area of 30 mm × 30 mm ×: 50 or more cracks occurred in an area of 30 mm × 30 mm including the bent portion

(6) Summary As shown in Table 1 and Table 2, the transparent layer of the present invention is a laminate in which conductive layers are provided on both surfaces of a transparent substrate, and at least one of the conductive layers includes a transparent metal layer and a zinc sulfide-containing layer. It can be seen that the conductors 1 to 10 are excellent in moisture resistance and the effect of suppressing the occurrence of warping as compared with the transparent conductors 11 to 13 of the comparative example. In other functions as well, it can be seen that the transparent conductors 1 to 10 of the present invention are superior to the transparent conductors 11 to 13 of the comparative example.
Among them, the transparent conductors 6, 7, and 10 of the present invention in which the first sulfidation prevention layer and the second sulfidation prevention layer are provided are more transparent than the transparent conductors 1 to 5, 8, and 9 of the present invention. It turns out that it is excellent. It is considered that the formation of metal sulfide was suppressed by providing the first antisulfurization layer and the second antisulfurization layer.

The transparent conductor 11 of the comparative example has a large thickness and a low transmittance. In the transparent conductor 11 of the comparative example, it is considered that the transmittance can be improved if the thickness of the transparent metal layer is reduced. However, it is predicted that the conductivity is deteriorated when the thickness of the transparent metal layer is reduced. The In addition, the transparent conductor 11 of the comparative example has low crack resistance at the time of bending, which is considered because the layer thickness of the transparent metal layer is large and has crystallinity.
Further, the transparent conductor 12 of the comparative example has a low warpage suppressing effect. This is presumably because the conductive layer is formed only on one surface of the transparent substrate, so that stress is generated in the transparent conductor and warpage occurs. In addition, since the transparent conductor 12 is greatly warped, it is considered that a large stress is applied when the transparent conductor 12 is bent in a direction opposite to the warp, so that cracks are likely to be generated. It is thought that.
Since the transparent conductor 13 of the comparative example has a large thickness, the transmittance is low. Moreover, since the transparent conductor 13 does not include the zinc sulfide-containing layer, the moisture resistance is low. In addition, TiO ₂ has a higher hardness than ZnS and easily generates cracks, and is a film material having a large stress. Therefore, when used as a material for a transparent conductor, cracks and warpage are likely to occur. For this reason, the transparent conductor 13 is greatly warped and has low crack resistance during bending.

As described above, the present invention is suitable for providing a transparent conductor excellent in moisture resistance and capable of suppressing the occurrence of warpage.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer (zinc sulfide content layer)
3 Transparent metal layer 4 Second high refractive index layer (zinc sulfide-containing layer)
5a First sulfidation prevention layer 5b Second sulfidation prevention layer 6 Conductive layer 100 Transparent conductor a Conduction region b Insulation region

Claims (3)

1. A transparent substrate;
   A conductive layer provided on both sides of the transparent substrate,
   A transparent conductor, wherein at least one of the conductive layers is a laminate including a transparent metal layer and a zinc sulfide-containing layer.
2. 2. The transparent conductor according to claim 1, wherein an anti-sulfurization layer is provided between the transparent metal layer and the zinc sulfide-containing layer.
3. The transparent conductor according to claim 1 or 2, wherein the conductive layer or the transparent metal layer is patterned.

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