JP2016108581A - Production method of transparent electric conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a transparent electric conductor for producing a transparent electric conductor having a high production efficiency (vapor deposition velocity) that is excellent in light permeability and humidity resistance in a high temperature and humidity environment.SOLUTION: In a production method of a transparent electric conductor, at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are formed on a transparent substrate in that order. The first high refractive index layer contains a sulfide, while the second high refractive index layer contains a metal oxide. All layers of the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are formed by a vapor deposition method.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a transparent conductor. More specifically, the present invention relates to a method for producing a transparent conductor that produces a transparent conductor having high productivity, high light transmittance, and excellent durability when stored in a high temperature and high humidity environment.

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 (EL) displays, touch panels, solar cells, and the like.

  In a touch panel type display device or the like, wiring including a transparent conductor is disposed on the image display surface of the display element. Therefore, the transparent conductor is required to have high light transmittance. For such various display devices, a transparent conductor using ITO (indium tin oxide) having high light transmittance is often used.

  Under such circumstances, a capacitive touch panel display device has been developed, and it is required to further reduce the surface electrical resistance of the transparent conductor. However, the conventional ITO film has a problem that the surface electric resistance cannot be sufficiently lowered.

  In view of this, studies have been actively conducted on a method in which a silver deposition layer (hereinafter also referred to as an Ag layer) is applied as a transparent metal layer.

For example, Patent Document 1 discloses a method for producing a multilayer conductive thin film produced by laminating a ZnS—SiO ₂ layer, a silver layer, and a ZnS—SiO ₂ layer on a glass substrate or a flexible substrate by sputtering. ing. According to this method, a low sheet resistance value and a high light transmittance can be obtained by annealing at a temperature of 200 ° C. in order to obtain good optical and electrical characteristics. It has been reported that the moisture stability is also good. However, since the ZnS · SiO ₂ layer provided adjacent to the silver layer is an insulating layer, it cannot be applied as a transparent conductor for a touch panel, and ZnS provided adjacent to both sides of the silver layer. The SiO ₂ layer contains sulfur atoms, and the silver layer receives sulfidation due to the sulfur atoms and has a problem that the light transmittance decreases due to yellowing or the like. In addition, the method disclosed in Patent Document 1 is a film forming method in which magnetron sputtering or RF (radio frequency) sputtering is applied to all the constituent layers, and the film forming speed is low and the production efficiency is poor. There is.

In Non-Patent Document 1, in order to increase the light transmittance of the transparent conductor, the silver layer is formed of a film having a high refractive index (for example, Nb ₂ O ₅ (niobium oxide), IZO (indium / zinc oxide), ICO A structure in which the film is sandwiched between (indium / cerium oxide), a-GIO (gallium / indium oxide), or the like has also been proposed. In the transparent conductor having the structure disclosed in Non-Patent Document 2, a good IZO layer can be obtained with respect to light transmittance by forming a silver layer with high output, but it is disclosed in Non-Patent Document 1. The Nb ₂ O ₅ , silver layer, and IZO layer are all formed by sputtering, and there is a problem that the film formation rate is low and the production efficiency is poor.

  In Non-Patent Document 2, it is proposed to sandwich the Ag layer with a layer containing zinc sulfide (hereinafter also referred to as a ZnS-containing layer or a zinc sulfide-containing layer).

  In the method disclosed in Non-Patent Document 2, all the films are formed by vapor deposition, and there is no problem in terms of productivity. However, in the transparent conductor having the above configuration, the transparent substrate and the ZnS-containing layer are formed. Adhesiveness is insufficient, and electrical conductivity is insufficient.

Chinese Patent No. 1026777012

Transparent Conductive Film Nb2O5 / Ag / IZO with an Anti-Reflection Design, Ywh-Tang Leu, et al. , SID 2012 DIGEST p. 352-353 Xuanjie Liu, et al. , 2003, Thin Solid Films 441, 200-206

  The present invention has been made in view of the above-mentioned problems, and its solution is high production efficiency (film formation rate), excellent light transmittance, and transparency that is excellent in moisture resistance under a high temperature and high humidity environment. It is providing the manufacturing method of the transparent conductor which manufactures a conductor.

  As a result of intensive studies in view of the above problems, the present inventor has, as a result, a first high refractive index layer containing at least a sulfide, a transparent metal layer, and a second high refractive index containing a metal oxide on a transparent substrate. In the manufacturing method of forming the layers in this order, at least the first high refractive index layer contains a sulfide, the second high refractive index layer contains a metal oxide, and the first high refractive index layer includes All the layers, the transparent metal layer and the second high-refractive index layer are formed by vapor deposition, so that the transparent conductor has a high production efficiency (film formation rate), light transmittance and It has been found that a transparent conductor excellent in moisture resistance under a high temperature and high humidity environment can be produced, and the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A method for producing a transparent conductor, comprising forming at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on a transparent substrate,
The first high refractive index layer contains sulfide, the second high refractive index layer contains metal oxide,
And all the layers of the said 1st high refractive index layer, a transparent metal layer, and a 2nd high refractive index layer are formed by a vapor deposition method, The manufacturing method of the transparent conductor characterized by the above-mentioned.

  2. 2. The method for producing a transparent conductor according to claim 1, wherein an intermediate layer containing tin oxide is formed by vapor deposition between the transparent metal layer and the second high refractive index layer.

  3. The method for producing a transparent conductor according to item 1 or 2, wherein tin oxide is contained in the second high refractive index layer.

  4). The method for producing a transparent conductor according to any one of Items 1 to 3, wherein zinc sulfide is contained as the sulfide in the first high refractive index layer.

  5. The method for producing a transparent conductor according to any one of Items 1 to 4, wherein an adhesion layer is formed between the transparent substrate and the first high refractive index layer.

  6). 6. The transparent conductor according to any one of items 1 to 5, wherein an indium tin oxide layer (ITO layer) is formed on the second high refractive index layer by a vapor deposition method. Manufacturing method.

  7). The method for producing a transparent conductor according to any one of Items 1 to 6, wherein a silver thin film layer is formed from silver or an alloy containing silver as a main component as the transparent metal layer.

  By the above means of the present invention, there is provided a transparent conductor production method for producing a transparent conductor having high production efficiency (film formation rate), excellent light transmission, and excellent moisture resistance in a high temperature and high humidity environment. can do.

  The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  In order to give good conductivity to ITO, which is a transparent conductive film, it is necessary to closely match the amount of oxygen deficiency in the composition, and good conductive performance could not be obtained except by sputtering. However, the sputtering method has a problem that the target breaks at the time of high power film formation, so that it cannot be produced at a high speed and it is difficult to reduce the production cost. In addition, since the material has a high processing cost for sintering and bonding the material target, and the material cost: processing cost accounts for a ratio of 3: 7, the material cost is high as a result.

  On the other hand, in a transparent conductor using Ag, since the Ag layer ensures conductivity, it is not necessary to adjust the composition as required for ITO. For this reason, a film can be formed even by a vapor deposition method in which composition adjustment is difficult. If the vapor deposition method can be used in the above film formation, the film formation speed is improved as compared with the case of using sputtering, and as a result, the cost is greatly reduced. However, the electrical connection method and the reliability of the Ag layer have been problems. In order to solve this, the first high refractive index layer is made of sulfide to improve reliability, and the second high refractive index layer can be electrically connected, and is made of a metal oxide that improves reliability. It was set as the composition.

  Further, since the vapor deposition method is not as high-energy film formation as the sputtering method, the vapor deposition method eliminates the need for an anti-sulfurization layer between the Ag layer and the sulfide, and the second high refractive index layer is also used. Since the film can be formed without damaging the Ag layer, the film can be formed at a high speed without reducing the film formation speed of the second high refractive index layer. Thus, the combination of the vapor deposition method and the material has made it possible to produce an Ag-based transparent conductor having good electrical connection and low production cost without impairing reliability.

Schematic sectional view showing an example of the configuration of the transparent conductor according to the present invention Schematic sectional view showing another example of the configuration of the transparent conductor according to the present invention Schematic sectional view showing another example of the configuration of the transparent conductor according to the present invention Schematic configuration diagram showing an example of the configuration of an ion-plating vapor deposition apparatus that is one of vapor deposition methods applicable to the present invention The perspective view which shows an example of a structure of the touchscreen provided with the transparent conductor which has the patterned electrode which concerns on this invention

  The method for producing a transparent conductor of the present invention is a method for producing a transparent conductor in which at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are formed in this order on a transparent substrate, The first high refractive index layer contains a sulfide, the second high refractive index layer contains a metal oxide, and all of the first high refractive index layer, the transparent metal layer, and the second high refractive index layer The layer is formed by a vapor deposition method. This feature is a technical feature common to the inventions according to claims 1 to 7.

  As an embodiment of the present invention, an intermediate layer containing tin oxide is formed by a vapor deposition method between the transparent metal layer and the second high-refractive index layer from the viewpoint of more manifesting the intended effect of the present invention. By doing so, the durability under a high temperature and high humidity environment is further improved, the influence of the second high refractive index layer on the transparent metal layer can be suppressed, plasmon absorption is less likely to occur, and higher light transmittance is obtained. It is preferable in that

  In addition, it is preferable that the second high refractive index layer contains tin oxide from the viewpoint of producing a transparent conductor further improved in durability under a high temperature and high humidity environment.

  In addition, it is preferable that the first high refractive index layer is formed by containing at least zinc sulfide as a sulfide from the viewpoint of forming an excellent high refractive index layer.

  In addition, forming an adhesion layer between the transparent substrate and the first high refractive index layer can prevent the occurrence of film peeling when subjected to stress due to bending, and has excellent film peeling resistance. It is preferable from the viewpoint that a transparent conductor can be manufactured.

  In addition, it is possible to form an indium tin oxide layer (ITO layer) on the second high refractive index layer by a vapor deposition method, for example, to provide moisture resistance when a transparent optical adhesive layer (OCA) is provided as a touch panel. It is preferable from the viewpoint that an excellent transparent conductor can be produced.

  In addition, forming a transparent metal layer from a silver or silver-based alloy as a main component of a silver thin film layer has a low resistance, has a high uniformity, and stably forms a transparent metal layer without improper absorption. It is preferable because it can be used.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

《Basic structure of transparent conductor》
First, the basic configuration of the transparent conductor according to the present invention will be described with reference to the drawings. In addition, the number described in parentheses after each component represents the code of the component described in each figure.

  The transparent conductor according to the present invention includes a first high refractive index layer containing at least a sulfide, a transparent metal layer, and a second high refractive index layer containing a metal oxide in this order on a transparent substrate. And all of the first high refractive index layer, the transparent metal layer and the second high refractive index layer are formed by vapor deposition.

  FIG. 1 is a schematic cross-sectional view showing a configuration of a transparent conductor according to the present invention.

  The transparent conductor (1) shown in FIG. 1 includes a first high refractive index layer (3D) formed by vapor deposition, containing at least sulfide on the transparent substrate (2), and a transparent metal layer formed by vapor deposition. (4D) and a second high-refractive-index layer (5D) formed by a vapor deposition method, containing at least a metal oxide, are stacked in this order.

  FIG. 2 is a schematic cross-sectional view showing another example of a preferred configuration of the transparent conductor according to the present invention.

  The transparent conductor (1) shown in FIG. 2 is further provided between the transparent metal layer (4D) formed by the vapor deposition method and the second high refractive index layer (5D) formed by the vapor deposition method with respect to the configuration shown in FIG. The structure which has the intermediate | middle layer (6D) containing the tin oxide formed by the vapor deposition method is shown.

  FIG. 3 is a schematic cross-sectional view showing another example of a preferred configuration of the transparent conductor according to the present invention.

  The transparent conductor (1) shown in FIG. 3 has an adhesive layer (7) between the transparent substrate (2) and the first high refractive index layer (3D) formed by the vapor deposition method in addition to the configuration shown in FIG. And an ITO layer (8) formed by the vapor deposition method as the outermost layer on the second high refractive index layer (5D) formed by the vapor deposition method.

  In FIG. 3, the adhesion layer (7) may be an adhesion layer (7D) formed by an evaporation method, or may be an adhesion layer (7S) formed by a sputtering method, for example. Similarly, the ITO layer (8) may be an ITO layer (8D) formed by a vapor deposition method or an ITO layer (8S) formed by a sputtering method. In FIG. The adhesion layer (7D) formed by (1) and the ITO layer (8D) formed by vapor deposition are shown.

  The “transparent” as used in the transparent conductor according to the present invention refers to a visible light wavelength region measured by a method according to JIS K 7361-1: 1997 (a test method for the total light transmittance of a plastic-transparent material). It means that the total light transmittance is 70% or more.

<< Each component of transparent conductor >>
Next, details of each component constituting the transparent conductor (1) according to the present invention shown in FIGS. 1 to 3 will be described.

[Transparent substrate]
As the transparent substrate (2) applicable to the transparent conductor (1) according to the present invention, materials applied to the transparent substrates of various display devices can be appropriately used.

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

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

  The term “transparent” as used in the transparent substrate (2) means that the average light transmittance of light having a wavelength of 450 to 800 nm is 70% or more, preferably 80% or more, and more preferably 85% or more. . When the average light transmittance of light of the transparent substrate (2) is 70% or more, the light transmittance of the transparent conductor (1) is likely to increase. Moreover, it is preferable that the average optical absorptance of the light of wavelength 450-800 nm of a transparent substrate (2) is 10% or less, More preferably, it is 5% or less, More preferably, it is 3% or less.

  In the present invention, the average light transmittance is obtained by measuring the refractive index of transmitted light when light is incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate (2).

On the other hand, the average light absorptance is measured by measuring the average reflectance of the transparent substrate (2) by making light incident from the same angle as the average light transmittance.
Average light absorptance (%) = 100− (average light transmittance + average reflectance) (%)
Calculate as The average light transmittance and the average reflectance can be measured using a spectrophotometer (for example, U4100: manufactured by Hitachi High-Technologies Corporation).

  The refractive index of the transparent substrate (2) with respect to light having a wavelength of 570 nm is preferably in the range of 1.40 to 1.95, more preferably in the range of 1.45 to 1.75, and still more preferably. It is in the range of 1.45 to 1.70. The refractive index of the transparent substrate (2) is usually determined by the material of the transparent substrate (2).

  The refractive index of a transparent substrate (2) can be calculated | required by measuring in 25 degreeC environment using an ellipsometer.

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

  The thickness of the transparent substrate (2) is preferably in the range of 1 μm to 20 mm, more preferably in the range of 10 μm to 2 mm, and still more preferably in the range of 25 to 150 μm. If the thickness of the transparent substrate (2) is 1 μm or more, the strength of the transparent substrate (2) increases, and the first high refractive index layer (3D) is cracked or torn when formed by vapor deposition. Can be prevented. On the other hand, if the thickness of the transparent substrate (2) is 20 mm or less, sufficient flexibility of the transparent conductor (1) can be obtained. Furthermore, the thickness of the touch panel etc. provided with the transparent conductor (1) according to the present invention can be reduced. Moreover, the touch panel using the transparent conductor (1) according to the present invention can be reduced in weight.

  In the present invention, the transparent substrate (2) to be used was previously removed from the moisture contained in the transparent substrate and the remaining solvent by using a cryopump or the like before forming each constituent layer. Thereafter, it is preferably used in the forming step.

  Further, from the viewpoint of obtaining the smoothness of the first high refractive index layer (3D) formed on the transparent substrate (2) applied to the present invention, a clear hard coat layer (abbreviation: CHC layer) having a known configuration. ) May be provided.

[First high refractive index layer]
The first high-refractive index layer (3D) according to the present invention is a layer formed by a vapor deposition method and contains at least a sulfide, and has a refractive index higher than the refractive index of a transparent substrate for light having a wavelength of 570 nm. It is preferable that it is the structure which has a rate, and also it is preferable that it is a layer (ZnS containing layer) which zinc sulfide contains at least as a sulfide.

(Sulfide-containing layer)
The first high refractive index layer (3D) formed by the vapor deposition method according to the present invention is characterized in that it is a layer containing at least a sulfide, and it is a preferred embodiment that the sulfide is zinc sulfide. .

  By containing ZnS in the first high refractive index layer (3D) according to the present invention, the continuous film-forming property when using a metal element that is a constituent material of the transparent metal layer (4D), particularly silver, is improved. Plasmon absorption can be reduced. Moreover, it becomes difficult to permeate | transmit a water | moisture content from the transparent substrate (2) side, and corrosion of a transparent metal layer (4D) can be suppressed.

  Further, the first high refractive index layer (3D) containing ZnS may contain a metal oxide together with zinc sulfide. The metal oxide contained together with zinc sulfide is a dielectric material or an oxide semiconductor material.

  The refractive index with respect to light having a wavelength of 570 nm of ZnS, dielectric material or oxide semiconductor material contained in the first high refractive index layer (3D) is preferably higher than 1.5 and in the range of 1.7 to 2.5. It is more preferable that it is in the range of 1.8 to 2.5. When the refractive index of ZnS, dielectric material or oxide semiconductor material is higher than 1.5, the optical admittance of the transparent conductor (1) is sufficiently adjusted by the first high refractive index layer (3D).

  In addition, the refractive index of a 1st high refractive index layer (3D) can be adjusted with the refractive index of the material to comprise, a film thickness, and the density of the material to comprise.

As a dielectric material or an oxide semiconductor material preferably used for forming the first high refractive index layer (3D) containing ZnS, ZnS · SiO ₂ , ZnS · SnO, ZnS · ZnO · Ga, in addition to ZnS alone. _{2 O 3, ZnS · In 2} O 3 · ZnO · Ga 2 O 3 and the like.

  The dielectric material or the oxide semiconductor material included in the first high refractive index layer (3D) containing ZnS may be an insulating material or a conductive material.

Examples of the dielectric material or the oxide semiconductor material include the following metal oxides (including inorganic oxides), such as 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, ( indium zinc oxide), AZO (aluminum zinc Oxide), GZO (gallium / zinc oxide), ATO (antimony / tin oxide), ICO (indium / cerium oxide), Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , a-GIO (gallium indium oxide) and the like. Among the above metal oxides, silicon dioxide (SiO ₂ ) is particularly preferable.

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

(Formation method of the first high refractive index layer: evaporation method)
Generally, as a thin film formation method by a dry method,
1) Physical vapor deposition (PVD): vacuum deposition, ion plating, sputtering, laser ablation, molecular beam epitaxy, etc.
2) Chemical vapor deposition (CVD): plasma CVD, thermal CVD, metal organic CVD, photo CVD, and the like can be mentioned. In the present invention, among the above film forming methods, vapor deposition is used. One feature is to form one high refractive index layer.

  The vapor deposition method (hereinafter also referred to as a vacuum vapor deposition method) is a film forming material for the first high refractive index layer, such as ZnS, in a vacuum, a resistance heating method, an electron beam method, a high frequency induction method, a laser method, etc. In this method, the first high refractive index layer is formed by heating, evaporating or sublimating, and the generated vapor reaches the resin substrate and deposits. In this vacuum deposition method, the vaporized material component reaches the resin substrate as it is without being electrically applied to the film-forming substance or the resin substrate, so that the damage to the resin substrate is small and the first high purity is high. A refractive index layer can be formed.

  The vapor deposition method has a film formation rate several times faster than the sputtering method (detailed explanation is omitted here), so that the production efficiency is excellent, the structure as the vapor deposition device is simple, and the high vacuum. Among them, there are many advantages such as that a film with high purity can be formed and that there is no damage to a resin substrate or a film already formed by plasma such as sputtering.

  In the present invention, it is preferable to use an ion plating method as the vapor deposition method.

  The ion-plating method has almost the same principle as the above-described vapor deposition method, but a different structure is formed by heating, evaporating or sublimating a film forming material of the first high refractive index layer, for example, ZnS, in a vacuum. After the film material particles are generated, the film material particles are passed through the plasma space, so that a positive charge is applied, and a negative charge is applied to the substrate support that holds the resin substrate on the film formation side. This is a method of forming a first high refractive index layer by applying and attracting film-forming substance particles (+ charges) that have passed through the plasma space and depositing them. A film formed by this ion-plating method can form a denser and higher adhesion film than the vapor deposition method. In addition, it has features such that adhesion can be obtained even at a relatively low temperature, and a variety of film forming conditions can be obtained. In addition, the ion plating effect can realize high-reactive film formation and improve the film quality denseness and smoothness due to the surface diffusion effect.

  In addition, the ion plating method as used in the field of this invention refers to the vapor deposition method in general which has the above plasma assists. The form of plasma assist to be applied is not particularly limited, and examples thereof include a plasma gun system and an RF plasma system.

  Hereinafter, a vapor deposition apparatus applicable by the ion-plating method will be described with reference to the drawings.

  FIG. 4 is a schematic configuration diagram showing an example of a film forming principle by an ion plating method applicable to the present invention.

  In FIG. 4, the ion-plating device (10) is provided with a substrate holder (12) holding a resin substrate (13) in the upper part of the vacuum vessel (11), and an applied power source (19 ), A negative (−) charge is applied to the substrate support base (12).

  On the other hand, in the lower part of the vacuum vessel (11), for example, ZnS is loaded as a film forming substance (15) in a resistance heating type heating boat (14). A plasma forming part (17) to which a high-frequency power source (16) is connected is disposed in an intermediate part in the vacuum vessel (11). By applying a high frequency voltage to the plasma forming part (17), a plasma discharge space (18) is formed around the plasma forming part (17).

After reducing the pressure in the vacuum vessel (11) to about 1 × 10 ⁻⁴ Pa, for example, the heating boat (14) is energized to evaporate the film-forming substance (15) and scatter the film-forming substance particles. Then, the film-forming substance particles (20) are charged positively (+) by passing through the plasma discharge space (18). The positively (+) charged film-forming substance particles (20) are deposited on the resin substrate (13) held on the negatively (−) charged substrate support (12) and have high adhesion. 1 A high refractive index layer (21) is formed.

  As a vapor deposition apparatus applicable to the present invention, for example, a BMC-800T vapor deposition machine manufactured by Shincron, a vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd., and a pulse laser vapor deposition apparatus are sold by Matsubo. Examples of Coldab (registered trademark) manufactured by Picodeon (Finland) and ion plating apparatus include roll-to-roll plasma assist vapor deposition apparatus manufactured by Tsukishima Kikai Co., Ltd., SUPLaDUO (registered trademark) manufactured by Chugai Furnace Co., Ltd. Can do.

(Transparent metal layer)
The transparent metal layer (4D) according to the present invention is a layer composed of a metal element. In the present invention, the transparent metal layer (4D) is formed of silver or an alloy containing silver as a main component. It is preferable that it is a silver thin film layer. The transparent metal layer (4D) is a layer for conducting electricity in the transparent conductor (1). The transparent metal layer (4D) may be formed on the entire surface of the transparent substrate (2) as shown in FIGS. 1 to 3, but is preferably configured to be patterned into a predetermined shape.

  In the present invention, the silver-based alloy means that the silver content is 60 at% (atomic%) or more. The silver content is preferably 90 at% or more, more preferably 95 at% or more from the viewpoint of conductivity, and the transparent metal layer (4D) is preferably composed of silver alone.

  Examples of the metal that forms an alloy in combination with silver include zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, platinum, titanium, and chromium. For example, when silver and zinc are combined, the sulfide resistance of the transparent metal layer (4D) is increased. When silver and gold are combined, the salt resistance (NaCl) is increased, and when silver and copper are combined, Increases oxidation resistance.

  The plasmon absorption rate of the transparent metal layer (4D) 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 transparent conductor (1) is easily colored.

  The layer thickness of the transparent metal layer (4D) is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm. In the transparent conductor (1), when the thickness of the transparent metal layer (4D) is 10 nm or less, the original reflection of the metal hardly occurs in the transparent metal layer (4D). Moreover, the optical admittance of the transparent conductor (1) is easily adjusted by the first high refractive index layer (3D), for example, the ZnS-containing layer and the second high refractive index layer (5D) described later, and the surface of the conductive region a is adjusted. The reflection of light is easy to be suppressed.

  The layer thickness of the transparent metal layer (4D) can be determined by measurement using an ellipsometer.

  One of the features of the transparent metal layer (4D) is that the transparent metal layer (4D) is formed by vapor deposition in the same manner as the first high refractive index layer (3D) described above. The vapor deposition method applicable to the transparent metal layer (4D) can include the same method as the vapor deposition method used for forming the first high refractive index layer (3D).

By applying the vapor deposition method to the formation of the transparent metal layer (4D) according to the present invention, the transparent metal layer (4D) having high planarity can be formed at an extremely high formation rate. Further, when the transparent metal layer (4D) is formed on the first high refractive index layer (3D), for example, the ZnS-containing layer, if the layer formation speed is high, a metal, for example, a silver sulfide is not easily generated. Therefore, the formation rate of the transparent metal layer (4D) containing silver as a main component is preferably 0.3 nm / second or more. The formation rate of the transparent metal layer (4D) is more preferably in the range of 0.5 to 30 nm / second, and particularly preferably in the range of 1.0 to 15 nm / second. The temperature during film formation is preferably in the range of −25 to 25 ° C. The ultimate vacuum before the start of film formation is preferably 3 × 10 ⁻³ Pa or less, and more preferably 7 × 10 ⁻⁴ Pa or less.

  The transparent metal layer (4D) can be a film patterned into a desired shape when applied to an electronic device or the like, and the patterning method is not particularly limited. The transparent metal layer (4D) may be, for example, a layer formed by arranging a mask having a desired pattern, or may be a film patterned by a known etching method.

<< Second high refractive index layer >>
The second high-refractive index layer (5D) according to the present invention contains at least a metal oxide and is formed by a vapor deposition method in the same manner as the first high-refractive index layer (3D) and the transparent metal layer (4D) described above. It is characterized by forming. Furthermore, it is a preferable aspect to contain a tin oxide.

  The second high refractive index layer (5D) preferably has a refractive index higher than the refractive index of the transparent substrate (2) for light having a wavelength of 570 nm, and the refractive index of the second high refractive index layer (5D) is: It is preferably higher in the range of 0.1 to 1.1 than the refractive index of the transparent substrate (2), and more preferably in the range of 0.4 to 1.0.

  When the transparent conductor (1) has such a refractive index relationship, reflection by a metal contained in the transparent metal layer (4D), for example, silver can be offset.

  Specifically, the higher the refractive index of the second high refractive index layer (5D), the higher the reflection generated on the surface of the second high refractive index layer (5D), and the more the silver reflected light in the transparent metal layer (4D) is reflected. It becomes possible to cancel. Therefore, the second high refractive index layer (5D) is required to have a refractive index higher than that of the transparent substrate (2).

  The layer thickness of the second high refractive index layer (5D) is preferably in the range of 1 to 150 nm, more preferably in the range of 10 to 100 nm, and still more preferably in the range of 10 to 50 nm. When the layer thickness of the second high refractive index layer (5D) is 1 nm or more, the moisture resistance is improved. On the other hand, when the layer thickness of the second high refractive index layer (5D) is 150 nm or less, the light transmittance is hardly lowered.

[Metal oxide]
Examples of metal oxides include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti _2. O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), ATO (antimony tin oxide) , ICO (Indium / Cerium Oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , In ₂ O ₃ , GIO (Gallium Indium Oxide), etc. Among the metal oxides, it is preferable to contain a metal compound having an atomic number of 40 or less, and it is particularly preferable to contain a zinc component. The zinc component preferably contains zinc oxide (ZnO) as a main component. Among the metal oxides exemplified above, IZO (indium / zinc oxide), AZO (aluminum / zinc oxide), GZO ( Gallium / zinc oxide) is more preferable. _{Further, ZnO · In 2 O 3 ·} Ga 2 O 3 · GeO 2 ( e.g., O: Zn: In: Ga : Ge = 48: 34: 3: 12: 3 ( atomic ratio)) metal compound composed of Groups can also be used.

[Amorphous metal oxide]
For the second high refractive index layer (5D) according to the present invention, a conductive amorphous metal oxide can be used as an example of the metal oxide. The conductivity referred to in the present invention means a specific resistance of less than 1000 Ω · cm, preferably less than 1 Ω · cm, and more preferably less than 0.1 Ω · cm.

  The term “amorphous” as used in the present invention refers to measured X-ray diffraction with little three-dimensional regularity as atoms or molecules constituting a solid when XRD analysis (X-ray diffraction method) of the formed thin film is performed. In the spectrum, only a halo pattern is observed, and it is defined as a substance that does not show a specific diffraction line peak indicating crystallinity.

  The amorphous material applicable to the second high-refractive index layer (5D) is preferably an amorphous dielectric material or an oxide semiconductor material, and with respect to light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material. The refractive index is preferably higher than 1.5, more preferably 1.7 to 2.5, and still more preferably 1.8 to 2.5.

Examples of amorphous metal oxides that can be suitably used for the second high refractive index layer (5D) include IGZO (amorphous-indium-gallium-zinc oxide) and IZO (amorphous-indium-zinc oxide). And the like. ZSnO (amorphous-zinc / tin oxide) can also be used. In addition, amorphous ZnO.In ₂ O ₃ .SnO ₂ (for example, O: Zn: In: Sn = 48: 32: 16: 4 (atomic ratio)), ZnO.In ₂ O ₃ SnO ₂ .TiO ₂ (for example, O: Ti: Zn: In: Sn = 57: 2: 8: 23: 10 (atomic ratio)), ZnO.In ₂ O ₃ .Ga ₂ O ₃ .GeO ₂ ( For example, O: Zn: In: Ga: Ge = 48: 34: 3: 12: 3 (atomic ratio)), ZnO.In ₂ O ₃ (for example, O: Zn: In = 54: 29: 17 (atom) Number ratio)) and the like.

(Formation method)
One feature of the second high refractive index layer (5D) according to the present invention is that the second high refractive index layer (5D) is formed by a vapor deposition method in the same manner as the first high refractive index layer (3D) and the transparent metal layer (4D) described above. As the vapor deposition method applicable to the second high refractive index layer (5D), the vapor deposition method described in the formation of the first high refractive index layer (3D) can be similarly applied.

《Other constituent layers》
[Middle layer]
In the transparent conductor according to the present invention, an intermediate layer (6D) containing tin oxide between the transparent metal layer (4D) and the second high refractive index layer (5D) as shown in FIG. 2 or FIG. It is a preferable aspect to form by vapor deposition.

  In the present invention, the intermediate layer (6D) preferably has a layer thickness in the range of 0.1 to 10 nm. When the thickness is 0.1 nm or more, the transparent metal layer (4D) can be protected from bombardment during the high power film formation of the second high refractive index layer (5D) to be laminated next. Moreover, if the layer thickness of the intermediate layer is 10 nm or less, it is preferable because high productivity is not hindered.

  In the present invention, the intermediate layer (6D) is also preferably formed by vapor deposition. As a vapor deposition method applicable to the present invention, the vapor deposition method described in the above-mentioned formation of each constituent layer can be applied.

  The intermediate layer (6D) is a layer formed directly on the transparent metal layer (4D), particularly the silver layer. When a layer is formed on the silver layer, an attack to the silver layer by the plasma generated at that time, a bombardment (attack) of the film forming material itself to silver, and a bombardment to Ag by oxygen atoms occur, It will roughen the surface of the silver layer. As a result, plasmon absorption occurred on the surface of the roughened silver layer, and the transmittance was reduced. However, the above effect can be suppressed by providing an intermediate layer.

[ITO layer]
On the second high refractive index layer (5D) according to the present invention, as shown in FIG. 3, for the purpose of further improving mechanical and chemical durability, indium tin oxide is used as the third high refractive index layer. It is a preferable aspect that a physical layer (ITO layer, 8D) is provided. This ITO layer (8D) can prevent erosion of the transparent metal layer, particularly the silver layer and the second high refractive index layer, due to the components in the transparent optical adhesive layer (OCA) when the touch panel is produced.

  The ITO layer (8D) is an oxide film that is easier to increase the conductivity than the second high refractive index layer (5D) and has excellent chemical properties. By laminating such an ITO layer (8D), the conductivity of the entire second high refractive index layer (5D) can be further increased.

  The refractive index of the ITO layer varies depending on its composition, and is approximately in the range of 1.7 to 2.3.

  The thickness of the ITO layer (8D) is preferably in the range of 10 to 70 nm, more preferably in the range of 10 to 50 nm, from the viewpoint of optical properties, giving the ITO layer a function as a protective layer. Particularly preferably, it is in the range of 15 to 30 nm.

  The ITO layer (8D) according to the present invention is preferably formed by an evaporation method or a sputtering method using an ITO sintered body. In particular, the evaporation method described in the formation of each constituent layer described above, for example, an ion It is preferable to apply a plating method or the like.

[Adhesion layer]
As shown in FIG. 3, the transparent conductor (1) according to the present invention is improved in adhesion improvement between the transparent substrate (2) and the ZnS-containing layer constituting the first high refractive index layer (3D). The adhesion layer (7) can be formed on the transparent substrate (2). The adhesion layer (7) may be any layer as long as the first high-refractive index layer (3D), which is a ZnS-containing layer, has a property of firmly adhering to the transparent substrate (2).

  The adhesion layer (6) contains the dielectric material, oxide semiconductor material, insulating or conductive material exemplified in the first high refractive index layer (3D) and the second high refractive index layer (5D). May be. The dielectric material or oxide semiconductor material is preferably a metal oxide, metal sulfide, or metal nitride. Among these, it is more preferable that a zinc compound is contained.

  When the first high refractive index layer (3D) containing ZnS is formed by vapor deposition, it is particularly preferable to provide the adhesion layer (7). Although the clear mechanism of action has not been clarified, the energy required for film formation is smaller when the film is formed by the vapor deposition method than when the film is formed by the sputtering method. ) And the first high refractive index layer (3D).

Specific examples of the adhesion layer (7) include a SiO ₂ film, a ZnO film, a ZnS—SiO ₂ film, and a GZO film.

  The layer thickness of the adhesion layer (7) is not particularly limited, and is preferably in the range of 0.01 to 15 nm, more preferably in the range of 0.1 to 3 nm.

  The method for forming the adhesion layer is not particularly limited and may be a vapor deposition method or a sputtering method, but is preferably a vapor deposition method.

《Field of application of transparent conductors》
The transparent conductor (1) according to the present invention having the above-described configuration includes various displays such as a liquid crystal system, a plasma system, an organic electroluminescence system, a field emission system, a touch panel, a mobile phone, electronic paper, various solar cells, and various electro It can be preferably used for substrates of various optoelectronic devices such as luminescence light control elements.

  In the configuration of a touch panel or the like, the surface of the transparent conductor (1) (for example, the surface opposite to the transparent substrate (2)) is connected to other members via an OCA sheet having a transparent optical adhesive layer (OCA). It may be pasted. In this case, it is preferable that the equivalent admittance coordinates of the surface of the transparent conductor (1) and the admittance coordinates of the OCA sheet are approximated respectively. Thereby, reflection at the interface between the transparent conductor and the OCA sheet is suppressed. Specifically, the admittance coordinates on the surface of the transparent conductor (1) are preferably adjusted so that the reflectance at a wavelength of 550 nm is 1% or less. This is because the refractive index of the OCA sheet is generally difficult to adjust largely.

  In the present invention, the OCA sheet applicable to the touch panel provided with the transparent conductor according to the present invention is not particularly limited. For example, the pressure-sensitive adhesive may be an acrylic copolymer, an epoxy resin, polyurethane, or silicone. Examples thereof include adhesives or pressure-sensitive adhesives such as polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers. Moreover, a commercial item can also be used, for example, it is acrylic acid-free, and is an OCA film NNZ-50 made by Gunze having suitability for bonding of an ITO electrode film NNZ-50, a highly transparent OCA tape made by 3M, ITO Examples include countermeasure grades 8146-1 to 4, OCR1202, OCR1204 (no substrate, refractive index: 1.48), LUCIACS (registered trademark) CR9707 (polyether adhesive) manufactured by Nitto Denko Corporation.

  Hereinafter, an example in which the transparent conductor (1) according to the present invention is applied to a touch panel will be described.

  The touch panel (22) shown in FIG. 5 is a projected capacitive touch panel. This touch panel (22) is configured to include two transparent electrode units, and the first transparent conductor (1A) forms a specific electrode pattern on one main surface of the transparent substrate (2-1). The first transparent electrode unit (EU-1) is included. Similarly, the second transparent conductor (1B) has a second transparent electrode unit (EU-2) forming a specific electrode pattern on one main surface of the transparent substrate (2-2). ing.

  The touch panel (22) of the present invention has a first OCA sheet (OCA1) between the first transparent conductor (1A) of the present invention and the second transparent conductor (1B) of the present invention from below. Similarly, the second OCA sheet (OCA2) is disposed between the second transparent conductor (1B) and the front plate (23) of the present invention. Even in such a configuration, the transparent conductors (1A and 1B) according to the present invention exhibit excellent durability, and in particular, a touch panel excellent in moisture resistance when stored for a long time in a high temperature and high humidity environment. Can be obtained.

  The transparent conductor (1) according to the present invention can be applied to various types of touch panel touch sensors (also referred to as touch sensor electrode portions) in addition to the projected capacitive touch panel as described above. it can. For example, the present invention can be applied to a surface capacitive touch panel, a resistive touch panel, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

  The layer thickness of each layer was adjusted by adjusting the deposition time when using the evaporation method, and was adjusted by adjusting the sputtering time when using the sputtering method. The layer thickness of each layer is J.I. A. Woollam Co. Inc. It measured with the VB-250 type | mold VASE ellipsometer made from.

  In the production of the transparent conductor described below, the details of the constituent materials and film formation methods described in abbreviations in Tables 1 and 2 are as follows.

(Transparent substrate)
PET / CHC: Polyethylene terephthalate film with clear hard coat manufactured by Kimoto Co., Ltd. (referred to as G1SBF “PET / CHC”. Thickness: 125 μm, refractive index: 1.59)
(Each refractive index layer constituent material)
ZnSnO; ZnO.SnO ₂ (Zn: Sn: O = 28: 15: 57 (at%))
GZO: ZnO mixed with 5.7% by mass of Ga ₂ O ₃ IGZO; In ₂ O ₃ .Ga ₂ O ₃ .ZnO (In: Ga: Zn: O = 1: 1: 1: 4 (at% ratio) ))
ITO; In ₂ O ₃ : SnO ₂ = 90: 10 (mass% ratio)
IZO; In ₂ O ₃ : ZnO = 90: 10 (mass% ratio)
Metal oxide 1; ZnO.In ₂ O ₃ .SnO ₂ (O = 48, Zn = 32, In = 16, Sn = 4 (at%))
Metal oxide 2; ZnO.In ₂ O ₃ .Ga ₂ O ₃ .GeO ₂ (O = 48, Zn = 34, In = 3, Ga = 12, Ge = 3 (at%))
(Film formation method)
<Vapor deposition method>
Vapor Deposition Method (1): Vacuum Deposition Method Vacuum Deposition Device = BMC-800T Vapor Deposition Device manufactured by Syncron Co., Ltd. Vapor Deposition Method (2): Ion Plating Method BMC-800T Vapor Deposition Device, manufactured by Syncron Corp.
Vapor deposition method (3): Pulse laser vapor deposition apparatus Sold by Matsubo, Coldab (registered trademark) manufactured by Picodeon (Finland)
Vapor deposition method (4): Ion-plating method Roll-to-roll plasma-assisted vapor deposition apparatus manufactured by Tsukishima Kikai Co., Ltd. Vapor deposition method (5); Ion-plating method SUPLaDUO (registered trademark) manufactured by Chugai Kogyo Kogyo Co., Ltd.
<< Production of transparent conductor >>
[Preparation of transparent conductor 101]
As a transparent substrate, a polyethylene terephthalate film (G1SBF “PET / CHC” with a clear hard coat manufactured by Kimoto Co., Ltd., thickness: 125 μm, refractive index: 1.59) is used, and the following method is used on the PET / CHC film. Thus, the adhesion layer (ZnO) / first high-refractive index layer (ZnS-containing layer) / transparent metal layer (Ag) / second high-refractive index layer (GZO) were laminated in this order to produce the transparent conductor 101. . All layers of the adhesion layer, the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are formed by the vapor deposition method (1) (vacuum vapor deposition method, BMC-800T vapor deposition device manufactured by Shincron). did.

(Formation of adhesion layer (ZnO))
Using a BMC-800T vapor deposition device manufactured by SYNCHRON as a vacuum vapor deposition device, ZnO was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The electrical heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation rate of 0.1 nm / second to form an adhesion layer (ZnO) having a layer thickness of 1.0 nm.

(Formation of first high refractive index layer (ZnS))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as a vacuum vapor deposition device. A molybdenum resistance heating boat was charged with ZnS as a sulfide, and the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa. Electric current heating was performed, the current heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation speed of 2.0 nm / second to form a first high refractive index layer (ZnS) having a layer thickness of 36 nm.

(Formation of transparent metal layer (Ag))
Using a BMC-800T vapor deposition device manufactured by SYNCHRON as a vacuum vapor deposition device, Ag was loaded into a resistance heating boat made of molybdenum, the vacuum tank was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The electric current heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation rate of 1.0 nm / sec to form a transparent metal layer having a layer thickness of 7.0 nm.

(Formation of second high refractive index layer (GZO))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as a vacuum vapor deposition device. A resistance heating boat made of molybdenum was charged with GZO as a metal oxide, and the vacuum tank was depressurized to 1 × 10 ⁻⁴ Pa. Then, the current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed at a forming speed of 2.0 nm / second to form a second high refractive index layer (GZO) having a layer thickness of 43 nm.

[Production of Transparent Conductor 102]
In the production of the transparent conductor 101, the transparent conductor 102 was produced in the same manner except that the metal oxide used for forming the second high refractive index layer was changed from GZO to IGZO which is an amorphous metal oxide. .

[Preparation of transparent conductor 103]
In the production of the transparent conductor 101, the transparent conductor was formed in the same manner except that the formation material of the adhesion layer was changed from ZnO to SiO ₂ and the formation material of the second high refractive index layer was changed from GZO to ITO. 103 was produced.

[Preparation of transparent conductor 104]
In the preparation of the transparent conductor 103, the material for forming the first high refractive index layer was changed from ZnS in ZnSSiO _2, and the formation material of the second high refractive index layer, is in the same manner except for changing from ITO into SnO ₂ Thus, a transparent conductor 104 was produced.

[Preparation of transparent conductor 105]
As a transparent substrate, a polyethylene terephthalate film with a clear hard coat (PET / CHC, supra) manufactured by Kimoto Co., Ltd. is used, and the first high refractive index layer (ZnS-containing layer) / A transparent metal layer (Ag) / intermediate layer (SnO ₂ ) / second high refractive index layer (GZO) was laminated in this order to produce a transparent conductor 105. All layers of the adhesion layer, the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are formed by the vapor deposition method (1) (vacuum vapor deposition method, BMC-800T vapor deposition device manufactured by Shincron). did.

(Formation of first high refractive index layer (ZnS))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as a vacuum vapor deposition device. A molybdenum resistance heating boat was charged with ZnS as a sulfide, and the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa. Electric current heating was performed, the current heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation speed of 2.0 nm / second to form a first high refractive index layer (ZnS) having a layer thickness of 36 nm.

(Formation of transparent metal layer (Ag))
Using a BMC-800T vapor deposition device manufactured by SYNCHRON as a vacuum vapor deposition device, Ag was loaded into a resistance heating boat made of molybdenum, the vacuum tank was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The electric current heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation rate of 1.0 nm / sec to form a transparent metal layer having a layer thickness of 7.0 nm.

(Formation of intermediate layer (SnO ₂ ))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as a vacuum vapor deposition device, SnO ₂ was loaded into a molybdenum resistance heating boat, the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa, and then the resistance heating boat was energized and heated. The electric current heating conditions of the resistance heating boat were adjusted, and vapor deposition was performed at a formation rate of 0.1 nm / second to form an intermediate layer (SnO ₂ ) having a layer thickness of 1.0 nm.

(Formation of second high refractive index layer (GZO))
A BMC-800T vapor deposition device manufactured by SYNCHRON Co., Ltd. was used as a vacuum vapor deposition device. A resistance heating boat made of molybdenum was charged with GZO as a metal oxide, and the vacuum tank was depressurized to 1 × 10 ⁻⁴ Pa. Then, the current heating condition of the resistance heating boat was adjusted, and vapor deposition was performed at a forming speed of 2.0 nm / second to form a second high refractive index layer (GZO) having a layer thickness of 43 nm.

[Preparation of transparent conductor 106]
In the production of the transparent conductor 105, a transparent conductor 106 was produced in the same manner except that the metal oxide used for forming the second high refractive index layer was changed from GZO to IGZO which is an amorphous metal oxide. .

[Preparation of transparent conductor 107]
In the production of the transparent conductor 105, a transparent conductor 107 was produced in the same manner except that the metal oxide used for forming the second high refractive index layer was changed from GZO to ITO.

[Preparation of transparent conductor 108]
As a transparent substrate, a polyethylene terephthalate film with a clear hard coat (PET / CHC, supra) manufactured by Kimoto Co., Ltd. is used, and the first high refractive index layer (ZnS-containing layer) / A transparent metal layer (Ag) / second high refractive index layer (SnO ₂ ) was laminated in this order to produce a transparent conductor 108. In addition, all the layers of the first high refractive index layer, the transparent metal layer, and the second high refractive index layer were formed by a vapor deposition method (2) (ion plating method, BMC-800T vapor deposition apparatus manufactured by SYNCHRON Co., Ltd.).

(Formation of first high refractive index layer (ZnS-containing layer))
A first high refractive index layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus. ZnS was loaded into a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, Ar gas was introduced, and the vacuum chamber was set to 2 × 10 ⁻³ Pa. Next, while heating RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 2.0 nm / sec. A layer (first high refractive index layer) was formed.

(Formation of transparent metal layer (Ag))
A transparent metal layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON Co., Ltd. as a vacuum vapor deposition apparatus. Ag was loaded into a resistance heating boat made of molybdenum, and the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating the RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 1.0 nm / second, and the layer thickness is 7.0 nm. A transparent metal layer was formed.

(Formation of second high refractive index layer (SnO ₂ containing layer))
A first high refractive index layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus. SnO ₂ was loaded into a molybdenum resistance heating boat and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating the RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 2.0 nm / sec, and SnO ₂ with a layer thickness of 43 nm is deposited. The containing layer (second high refractive index layer) was formed.

[Preparation of transparent conductor 109]
In the production of the transparent conductor 108, a transparent conductor 109 was produced in the same manner except that the metal oxide used for forming the second high refractive index layer was changed from SnO ₂ to ITO.

[Preparation of transparent conductor 110]
As the transparent substrate, a polyethylene terephthalate film with clear hard coat (PET / CHC, supra) manufactured by Kimoto Co., Ltd. is used, and the first high refractive index layer (ZnSSiO ₂ containing layer) is formed on the PET / CHC film according to the following method. / Transparent metal layer (Ag) / intermediate layer (SnO ₂ ) / second high refractive index layer (IGZO) were laminated in this order to produce a transparent conductor 110. In addition, all the layers of the first high refractive index layer, the transparent metal layer, and the second high refractive index layer were formed by a vapor deposition method (2) (ion plating method, BMC-800T vapor deposition apparatus manufactured by SYNCHRON Co., Ltd.).

(Formation of first high refractive index layer (ZnS-containing layer))
A first high refractive index layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus. ZnSSiO ₂ was loaded on a resistance heating boat made of molybdenum, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, Ar gas was introduced, and the vacuum chamber was set to 2 × 10 ⁻³ Pa. Then, while burning the RF plasma at 300 W, resistance heating and electrical heating to the boat, by adjusting the energization heating conditions of the resistance heating boat, and deposited in the conditions of forming speed 2.0 nm / sec, the thickness 36 nm ZnSSiO ₂ The containing layer (first high refractive index layer) was formed.

(Formation of transparent metal layer (Ag))
A transparent metal layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON Co., Ltd. as a vacuum vapor deposition apparatus. Ag was loaded into a resistance heating boat made of molybdenum, and the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating the RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 1.0 nm / second, and the layer thickness is 7.0 nm. A transparent metal layer was formed.

(Formation of intermediate layer (SnO ₂ ))
A transparent metal layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON Co., Ltd. as a vacuum vapor deposition apparatus. Ag was loaded into a resistance heating boat made of molybdenum, and the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating the RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 0.1 nm / sec. An intermediate layer (SnO ₂ ) was formed.

(Formation of second high refractive index layer (SnO ₂ containing layer))
A first high refractive index layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus. The molybdenum resistance heating boat was loaded with IGZO and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating conditions of the resistance heating boat are adjusted, and vapor deposition is performed at a formation rate of 2.0 nm / sec. A layer (second high refractive index layer) was formed.

[Preparation of transparent conductor 111]
In the production of the transparent conductor 110, the metal oxide used for forming the second high refractive index layer was changed from IGZO to metal oxide 1 (ZnO.In ₂ O ₃ .SnO ₂ (O = 48, Zn = 32, The transparent conductor 111 was produced in the same manner except that the thickness was changed to In = 16, Sn = 4 (at%)) and the layer thickness was changed to 40 nm.

[Preparation of transparent conductor 112]
In the production of the transparent conductor 110, the metal oxide used for forming the second high refractive index layer is changed from IGZO to metal oxide 2 (ZnO.In ₂ O ₃ .Ga ₂ O ₃ .GeO ₂ (O = 48 , Zn = 34, In = 3, Ga = 12, Ge = 3 (at%))), the layer thickness is 10 nm, and the third high refractive index layer is formed on the second high refractive index layer according to the following method. A transparent conductor 112 was produced in the same manner except that the refractive index layer (ITO-containing layer) was formed.

(Formation of third high refractive index layer (ITO-containing layer))
A first high refractive index layer was formed by an ion plating method using a BMC-800T vapor deposition apparatus manufactured by SYNCHRON as a vacuum vapor deposition apparatus. ITO was loaded into a resistance heating boat made of molybdenum and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then Ar gas was introduced to set the vacuum chamber to 2 × 10 ⁻³ Pa. Next, while heating the RF plasma at 300 W, the resistance heating boat is energized and heated, the current heating condition of the resistance heating boat is adjusted, and vapor deposition is performed at a formation rate of 2.0 nm / sec. A layer (third high refractive index layer) was formed.

[Preparation of transparent conductor 113]
As a transparent substrate, a polyethylene terephthalate film with a clear hard coat (PET / CHC, supra) manufactured by Kimoto Co., Ltd. is used, and the first high refractive index layer (ZnS-containing layer) / Transparent metal layer (Ag) / intermediate layer (SnO ₂ ) / second high refractive index layer (IGZO) were laminated in this order to produce transparent conductor 113. All layers of the first high refractive index layer, the transparent metal layer and the second high refractive index layer are sold by Matsubo, which is a pulse laser type vapor deposition device, as a vapor deposition method (3), manufactured by Picodeon (Finland). Of Coldab®.

(Formation of first high refractive index layer (ZnS-containing layer))
As a vacuum deposition apparatus, Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type deposition apparatus, is used for deposition at a formation rate of 2.0 nm / second, and a ZnS-containing layer having a layer thickness of 36 nm ( First high refractive index layer) was formed.

(Formation of transparent metal layer (Ag layer))
As a vacuum deposition apparatus, Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type deposition apparatus, is used for deposition at a forming speed of 1.0 nm / second, and a transparent metal having a layer thickness of 7.0 nm. A layer (Ag layer) was formed.

(Formation of intermediate layer (SnO ₂ ))
As a vacuum deposition apparatus, Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type deposition apparatus, is used for deposition at a formation rate of 0.1 nm / second, and an intermediate layer having a layer thickness of 1.0 nm. (SnO ₂ ) was formed.

(Formation of second high refractive index layer (IGZO-containing layer))
As a vacuum vapor deposition apparatus, Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type vapor deposition apparatus, is used for vapor deposition under a condition of a forming speed of 2.0 nm / second, and an IGZO-containing layer having a layer thickness of 43 nm ( The second high refractive index layer) was formed.

[Preparation of transparent conductor 114]
In the production of the transparent conductor 113, instead of Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type vapor deposition method of the vapor deposition method (3), an ion-plating type Tsukishima machine is used. A transparent conductor 114 was produced in the same manner except that a roll-to-roll type plasma-assisted vapor deposition apparatus (referred to as a vapor deposition method (4)) was used.

[Production of transparent conductor 115]
In the production of the transparent conductor 113, instead of Coldab (registered trademark) manufactured by Picodeon (Finland), which is a pulse laser type vapor deposition apparatus of vapor deposition method (3), an ion-plating type central and outer furnace is used. The same applies except that SUPLaDUO (registered trademark) (referred to as vapor deposition method (5)) manufactured by Kogyo Co., Ltd. is used and the metal oxide used for forming the second high refractive index layer is replaced with ITO instead of IGZO. A transparent conductor 115 was produced.

[Production of transparent conductors 116 to 118]
In the production of the transparent conductors 113 to 115, transparent conductors 116 to 118 were produced in the same manner except that the intermediate layer (SnO ₂ ) was removed.

[Preparation of transparent conductor 119]
According to the following method on the transparent substrate PET / CHC film (supra), the first high refractive index layer (ZnS · SiO ₂ , RF sputtering) / transparent metal layer (Ag, 12 nm, DC sputtering) / second A high refractive index layer (ZnS · SiO ₂ , RF sputtering) was laminated in this order to produce a transparent conductor 119.

(Formation of first high refractive index layer (ZnSSiO ₂ ))
Using an Anelva L-430S-FHS sputtering system, ZnSSiO ₂ so that the layer thickness is 40 nm at a formation rate of 0.15 nm / s under Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.). Was sputtered with RF (alternating current, frequency: 13.56 MHz) to form a first high refractive index layer. The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Using an Anelva L-430S-FHS sputtering system, Ar is 20 sccm, sputtering pressure is 0.25 Pa, back pressure is 5 × 10 ⁻⁴ Pa, room temperature (25 ° C.), and the layer thickness of Ag is 0.7 nm / s. DC sputtering was performed to obtain a thickness of 12 nm to form a transparent metal layer. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZnSSiO ₂ ))
Using an Anelva L-430S-FHS sputtering system, ZnSSiO ₂ so that the layer thickness is 40 nm at a formation rate of 0.15 nm / s under Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.). Was sputtered with RF (alternating current, frequency: 13.56 MHz) to form a second high refractive index layer. The target-substrate distance was 86 mm.

  A transparent conductor 119 was produced as described above.

[Preparation of transparent conductor 120]
On the transparent substrate PET / CHC film (supra), according to the following method, the first high refractive index layer (Nb ₂ O ₅ , DC sputtering) / transparent metal layer (Ag, 7.7 nm, DC sputtering) / The second refractive index layer (IZO, DC sputtering) was laminated in this order to produce the transparent conductor 120.

(Formation of the first high refractive index layer (Nb ₂ O ₅ ))
Using an Anelva L-430S-FHS sputtering apparatus, Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.), formation rate 0.15 nm / s, and layer thickness 27.7 nm. Nb ₂ O ₅ (Toshima Seisakusho Co., Ltd.) was DC pulse sputtered. The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Using an Anelva L-430S-FHS sputtering system, Ar is 20 sccm, sputtering pressure is 0.25 Pa, back pressure is 5 × 10 ⁻⁴ Pa, room temperature (25 ° C.), and the layer thickness of Ag is 0.7 nm / s. A transparent metal layer was formed by DC sputtering to a thickness of 7.7 nm. The target-substrate distance was 86 mm.

(Formation of second high refractive index layer (IZO))
Using an L-430S-FHS sputtering apparatus manufactured by Anerva Co., IZO at 20 nm Ar, ₂ sccm O ₂ , sputtering pressure 0.25 Pa, room temperature (25 ° C.), forming rate 1.0 nm / sec, and layer thickness 36 nm. (Pulsed by Toshima Seisakusho Co., Ltd.) was DC pulse sputtered. The deposited film had a target-substrate distance of 86 mm.

  The transparent conductor 120 was produced as described above.

[Preparation of transparent conductor 121]
According to the following method on the transparent substrate PET / CHC film (supra), the first high refractive index layer (ZnSnO, DC sputtering) / transparent metal layer (Ag, 10.0 nm, DC sputtering) / second refraction. Rate layers (ZnSnO, DC sputtering) were laminated in this order to produce a transparent conductor 121.

(Formation of first high refractive index layer (ZnSnO))
Using an Anelva L-430S-FHS sputtering apparatus, ZnSnO (Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.), formation rate 0.15 nm / s, and layer thickness 40 nm. Zinc / tin oxide) was DC pulse sputtered. The target-substrate distance was 86 mm.

(Formation of transparent metal layer (Ag))
Using an Anelva L-430S-FHS sputtering system, Ar is 20 sccm, sputtering pressure is 0.25 Pa, back pressure is 5 × 10 ⁻⁴ Pa, room temperature (25 ° C.), and the layer thickness of Ag is 0.7 nm / s. DC sputtering was performed so that the thickness was 10 nm to form a transparent metal layer. The target-substrate distance was 86 mm.

(Formation of Second High Refractive Index Layer (ZnSnO))
Using an Anelva L-430S-FHS sputtering apparatus, ZnSnO so as to have a layer thickness of 40 nm at a formation rate of 0.15 nm / sec under Ar 20 sccm, O _{2 2} sccm, sputtering pressure 0.25 Pa, room temperature (25 ° C.). Was DC pulse sputtered. The deposited film had a target-substrate distance of 86 mm.

  The transparent conductor 121 was produced as described above.

  Tables 1 and 2 show the structures of the produced transparent conductors 101 to 121.

<< Evaluation of each characteristic >>
[Evaluation of production efficiency]
The total film formation time (seconds / 100 cm ² ) required for production of each transparent conductor per unit area was calculated.

Next, a relative production time (seconds / 100 cm ² ) was obtained with the time required for production of the transparent conductor 119 being 100, and production efficiency was evaluated according to the following criteria.

A: Relative production time is less than 20 (seconds / 100 cm ² ) O: Relative production time is 20 (seconds / 100 cm ² ) or more and less than 50 (seconds / 100 cm ² ) Δ: Relative production time is 50 (seconds / 100 cm ² ) or more and less than 100 (seconds / 100 cm ² ) ×: Relative production time is 100 (minutes / 100 cm ² ) or more [Evaluation of light transmittance]
About each produced transparent conductor, the average light transmittance was measured in accordance with the following method.

  Matching oil (refractive index = 1.515 manufactured by Nikon) is applied to the surface of each transparent conductor on the second refractive index adjustment layer group side, and the transparent conductor and a non-alkali glass substrate (EAGLE XG (thickness) manufactured by Corning) In this state, the average light transmittance (%) in the wavelength range of 450 to 800 nm of the transparent conductor was measured from the alkali-free glass substrate side. Measuring light was incident from an angle inclined by 5 ° with respect to the normal of the surface of the alkali-free glass substrate, and transmittance at each wavelength was measured with a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.

  Subsequently, the measured average transmittance was ranked according to the following evaluation criteria to evaluate light transmittance.

◎: Average light transmittance is 88% or more ○: Average light transmittance is 85% or more and less than 88% △: Average light transmittance is 83% or more and less than 85% ×: Average Light transmittance is less than 83% [Durability Evaluation]
Each of the produced transparent conductors was subjected to a forced deterioration treatment that was stored in an environment of 85 ° C. and 85% RH for 500 hours, and thereafter, an area of 30 mm × 30 mm was observed using a magnifying glass. The number of occurrences of corrosion spots (white spot failure) having a size of 20 μm or more was measured, and durability was evaluated according to the following evaluation criteria.

◎: No occurrence of corrosion spots (white spot failure) with a size of 20 μm or more ○: The number of occurrences of corrosion spots (white spot failure) with a size of 20 μm or more is 1 or more and less than 5 △: The number of occurrences of corrosion spots (white spot failure) with a size of 20 μm or more is 5 or more and less than 10 ×: The occurrence number of corrosion spots (white spot failure) with a size of 20 μm or more is 10 or more Table 3 shows the evaluation results obtained by the above.

  As is clear from the results shown in Table 3, the transparent conductor produced by the production method of the present invention is more productive, light transmissive, and in a high temperature and high humidity environment than the transparent conductor of the comparative example. It can be seen that it has excellent durability when stored.

1, 1A, 1B Transparent conductor 2, 2-1, 2-2 Transparent substrate 3D, 21 First high refractive index layer (evaporation method)
4D transparent metal layer (deposition method)
5D second high refractive index layer (evaporation method)
6D intermediate layer (deposition method)
7 Adhesion layer 8D Third high refractive index layer (evaporation method)
DESCRIPTION OF SYMBOLS 10 Ion-plating apparatus 11 Vacuum container 12 Board | substrate holding stand 13 Resin board | substrate 14 Heating boat 15 Film-forming substance 16 High frequency power supply 17 Plasma formation part 18 Plasma discharge space 19 Applied power supply 20 Film-forming substance particle 22 Touch panel 23 Front plate EU-1, EU-2 Transparent electrode unit OCA1, OCA2 OCA sheet

Claims (7)

A method for producing a transparent conductor, comprising forming at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on a transparent substrate,
The first high refractive index layer contains sulfide, the second high refractive index layer contains metal oxide,
And all the layers of the said 1st high refractive index layer, a transparent metal layer, and a 2nd high refractive index layer are formed by a vapor deposition method, The manufacturing method of the transparent conductor characterized by the above-mentioned.   The method for producing a transparent conductor according to claim 1, wherein an intermediate layer containing tin oxide is formed between the transparent metal layer and the second high refractive index layer by a vapor deposition method.   The method for producing a transparent conductor according to claim 1, wherein tin oxide is contained in the second high refractive index layer.   The method for producing a transparent conductor according to any one of claims 1 to 3, wherein zinc sulfide is contained as the sulfide in the first high refractive index layer.   The method for producing a transparent conductor according to any one of claims 1 to 4, wherein an adhesion layer is formed between the transparent substrate and the first high refractive index layer.   The transparent conductor according to any one of claims 1 to 5, wherein an indium tin oxide layer (ITO layer) is formed on the second high refractive index layer by a vapor deposition method. Manufacturing method.   The method for producing a transparent conductor according to any one of claims 1 to 6, wherein a silver thin film layer is formed of silver or an alloy containing silver as a main component as the transparent metal layer.

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