JPH06278244A - Lamination - Google Patents

Abstract

PURPOSE:To obtain a transparent conductive film or selection beam permeable film with fine durability by laminating at least each one layer of a transparent thin film layer consisting of nitride and/or carbide and substantially light- permeable metallic layer on at least one surface of a transparent substrate. CONSTITUTION:On, at least, one surface of a transparent substrate, there are laminated at least each one layer of a transparent thin film layer consisting of nitride film and/or carbide film and substantially transparent metallic layer. The transparent thin film layer is a transparent laminate being a high refractive transparent thin film consisting of at least a sort of indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, amorphous carbon, and diamond-like carbon. This is also to be a film that is composed of a transparent thin film layer 3 consisting of nitride and/or carbide and substantially transparent precious metal layer 2 laminated on a transparent substrate 1 by at least each one layer, and permitted to be transparent to visible radiation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film used for electrodes for liquid crystal display elements, electromagnetic wave shielding materials, and the like.
Also, the present invention relates to a selective light transmission film used for windows of buildings and refrigerated / frozen showcases.

[0002]

2. Description of the Related Art A transparent conductive film is widely used for applications such as electrodes for liquid crystal display elements, electrodes for electroluminescence, electrodes for electrochromic, transparent heating elements, electromagnetic wave shield materials, etc. by utilizing its transparency and conductivity. In recent years, there has been a strong demand for a transparent conductive film having high transparency and low surface resistance as an electrode for liquid crystal display elements, which is becoming particularly large in size, and a shield material for electromagnetic waves which is said to be generated from OA equipment.

On the other hand, the selective ray transmitting film is used as a transparent heat ray reflecting film because it transmits light in the visible light region sufficiently and has a reflecting function for infrared rays. Therefore, it can be used as a greenhouse, a heat insulating window for a refrigerated showcase, a window of a building, a window of a vehicle such as a train or an automobile. Particularly in recent years, the emission of carbon dioxide gas has become a problem as one of the causes of global warming, and the need for energy saving is increasing more and more. In buildings and automobiles, the proportion of windows is increasing in order to improve comfort and the like. Especially in half-yearly buildings, trains, etc., window openings are occupying a large proportion, and the function as a transparent insulating window that uses sunlight as an indoor proof and blocks heat energy dissipation will become more important in the future. To increase.

For example, in order to save heating costs in winter in cold regions such as Hokkaido, and to reduce cooling costs in summer in regions such as Okinawa where the amount of solar radiation is high, its importance as a selective light transmitting film is great. In this way, the transparent conductive film and the selective light transmitting film are
It is important from the viewpoint of electronics and utilization of solar energy, and it is desired that a large amount of homogeneous and high-performance film be industrially supplied. Conventionally known as transparent conductive films are metal films such as gold and palladium Compound semiconductors such as indium oxide and tin oxide Metal thin films such as gold, silver and palladium are used as titanium oxide, indium oxide and zirconium oxide films. One that is sandwiched between high-refractive index thin films.

In the above, it is not possible to obtain a material having a sufficient visible light transmittance and an excellent conductive property. Examples of the above compound semiconductor include a film forming method in vacuum such as a vacuum vapor deposition method, a sputtering method, an ion plating method, and a thin film forming method by a sol-gel method. Alternatively, a film thickness of about several thousand Å is required to obtain the selective light transmission film, and as a result, the manufacturing cost of the film is significantly increased. As a typical structure of a laminated body in which the metal thin film is sandwiched by high refractive index thin films, a laminated body of a sandwich structure such as TiO ₂ / Ag / TiO ₂ is used, and a silver thin film or silver is used as a metal layer. The one using a thin film made of gold has been used because it is particularly excellent in transparency in the visible light region and reflection characteristics in the infrared ray, and also in conductivity.

The high refractive index thin film of titanium oxide or the like can be provided by a method such as sputtering, ion plating, vacuum deposition, and wet coating. However, when the laminate is formed in a vacuum such as sputtering or ion plating, the silver thin film is oxidized by migration of oxide ions activated by electric discharge, or silver migration occurs, resulting in deterioration of the silver thin film. Therefore, to prevent oxidation of the silver thin film, another type of metal layer is provided in advance, or when a transparent thin film layer is formed on the silver thin film, a reducing gas such as hydrogen is introduced in addition to the oxidizing gas such as oxygen. The laminated body is formed so that silver is not oxidized. When the laminate is formed by wet coating, the transparent thin film layer is formed by hydrolysis, the metal thin film layer is formed by vacuum deposition or sputtering, and further when the transparent thin film is formed by hydrolysis, Attempts to prevent deterioration of the silver thin film layer due to hydrogen ions and impurities by forming sulfides on the metal thin film layer for protection and adjusting the pH of the solution during hydrolysis to a specified range. It was being done. In any of the methods, the condition adjustment during film formation is complicated, or the characteristics of the obtained film are likely to change, and the laminates produced by these methods have performances depending on environmental conditions such as heat, light, oxygen and water. However, there was a problem that deterioration of

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to improve a transparent conductive film or a selective light transmitting film and a method for forming the same, and provide a transparent conductive film or a selective light transmitting film having excellent durability.

[0008]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies and as a result, as a result, a transparent thin film layer consisting of a nitride film and / or a carbide film is formed on at least one surface of a transparent substrate. It was found that the above problems can be solved by laminating at least one layer of a light-emitting metal layer, and the present invention has been completed.

That is, the present invention is a transparent laminate in which at least one transparent thin film layer made of a nitride film and / or a carbonized film and at least one substantially transparent metal layer are laminated on at least one surface of a transparent substrate, Alternatively, in a transparent laminate in which a transparent thin film layer made of a nitride film and / or a carbide film and at least one layer of a substantially transparent metal layer are laminated on at least one surface of a transparent substrate, the transparent thin film layer is indium nitride. , Gallium nitride, silicon nitride, tin nitride, boron nitride,
It is a transparent laminated body which is a high refractive index transparent thin film made of at least one of silicon carbide, amorphous carbon and diamond-like carbon, or transparent which is a high refractive index transparent thin film in which the transparent thin film layer is partially oxidized. A laminated body, or a transparent laminated body composed of a high refractive index transparent thin film in which the transparent thin film layer is partially hydrogenated, or
The transparent thin film layer is a transparent laminate comprising a partially hydrogenated high refractive index transparent thin film, or the transparent thin film layer / the metal layer / the transparent thin film layer are laminated in this order on at least one surface of the transparent substrate. The transparent thin film layer / the transparent thin film layer is provided on at least one surface of the transparent substrate.
A transparent laminated body in which the metal layer / the transparent thin film layer / the metal layer / the transparent thin film layer are laminated in this order, or
A transparent laminate in which the transparent thin film layer / the metal layer / the transparent thin film layer / the metal layer / the transparent thin film layer / the metal layer / the transparent thin film layer are laminated in this order on at least one surface of the transparent substrate, Alternatively, the metal layer is a transparent laminate which is a silver thin film, or the metal layer is a transparent laminate which is silver or a thin film layer containing silver as a main component, or the metal layer is silver. It is a transparent laminate in which a thin film layer and a thin film layer containing a metal other than silver as a main component are laminated, or the metal layer is a thin film layer containing silver as a main component and a metal other than silver as a main component. A transparent laminate in which a thin film layer as a component is laminated, or the outermost transparent thin film layer of the transparent thin film layer is a low refractive index layer on the outside and a high refractive index layer on the inside. Or the laminate of the transparent substrates is not laminated A transparent laminated body in which a transparent thin film composed of a high refractive index layer and then a low refractive index layer is formed on a surface of the transparent substrate, or the outermost transparent thin film composed of a high refractive index layer and a low refractive index layer in the transparent thin film layer. Layer or a transparent thin film layer composed of a high refractive index layer and a low refractive index layer laminated on the side where the laminate of the transparent substrate is not laminated, the high refractive index layer is indium nitride, gallium nitride, silicon nitride, tin nitride, A high-refractive-index transparent thin film made of at least one of boron nitride, silicon carbide, amorphous carbon, and diamond-like carbon, or high-refractive index in a transparent thin-film layer made of a high refractive index layer and a low refractive index layer than the transparent substrate. The refractive index layer has a refractive index of 1.6 or more, such as nitrides, carbides, oxides,
A transparent laminate comprising at least one of sulfides, or a transparent thin film layer comprising a layer having a higher refractive index and a layer having a lower refractive index than the transparent substrate, having a refractive index of 1.6 or more, a nitride, a carbide, an oxide. Of the high refractive index layer made of at least one of a sulfide and a sulfide, and having a refractive index of at least 2
It is a transparent laminate which is a laminate of layers or more, or in a transparent thin film layer consisting of a high refractive index layer and then a low refractive index layer than the transparent substrate, the high refractive index layer having a refractive index of 1.6 or more is indium nitride, Gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, amorphous carbon, diamond-like carbon, indium oxynitride, gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride, silicon oxynitride carbide, indium oxide, Tin oxide, indium tin oxide (IT
O), titanium oxide, aluminum oxide, magnesium oxide, thorium oxide, lanthanum oxide, neodymium oxide, zirconium oxide, cerium oxide, bismuth oxide or zinc oxysulfide, or a transparent laminated body of the above or In the thin film layer, the outermost transparent thin film layer consisting of a high refractive index layer and a low refractive index layer or a transparent thin film layer consisting of a high refractive index layer and a low refractive index layer laminated on the side where the laminate of the transparent substrates is not laminated. In the above, the low refractive index layer is a transparent laminated body which is a low refractive index transparent thin film made of at least one kind of oxynitride, fluoride, and oxide having a refractive index of 1.55 or less, or high in the transparent thin film layer. The outermost transparent thin film layer consisting of a refractive index layer and a low refractive index layer or the high refractive index layer and the low refractive index layer laminated on the side where the laminate of the transparent substrate is not laminated. In the transparent thin film layer, wherein the low refractive index layer is a low refractive index transparent thin film made of at least one kind of silicon oxynitride having a refractive index of 1.55 or less, or a high refractive index in the transparent thin film layer. Outermost transparent thin film layer consisting of a refractive index layer and a low refractive index layer or a transparent thin film layer consisting of a high refractive index layer and a low refractive index layer laminated on the side where the laminate of the transparent substrate is not laminated. Is a transparent laminate having a low refractive index transparent thin film made of at least one of silicon oxide, magnesium fluoride, and silicon oxynitride having a refractive index of 1.55 or less.

In order to form a transparent conductive film having excellent durability and chemical resistance, the transparent thin film used in the present invention has pH = 5.
Or less, preferably pH = 3 or less, more preferably pH
It is desirable to use a transparent thin film having acid resistance that is insoluble or hardly soluble in an acidic solution of = 1 or less. Thus, by combining the transparent thin film layer having excellent durability and chemical resistance with the metal layer, a transparent conductive film or a selective light transmitting film having excellent durability and chemical resistance is provided. That is, the laminate of the present invention can be used as an electromagnetic shield material or a window heat ray reflective film. When used as a material for electromagnetic wave shielding, it is more effective to provide this laminated body with a ground electrode.

Further specific embodiments of the present invention will be described with reference to FIGS. In each of these transparent laminates, at least one transparent thin film layer 3 made of nitride and / or carbide and at least one light-transmitting metal layer 2 are laminated on the transparent substrate 1. It is transparent to visible light. In the case shown in FIG. 1, the transparent substrate 1
The metal layer 2 and the transparent thin film layer 3 are laminated on the top one by one in this order. In the structure shown in FIG. 2, a transparent thin film layer 3 / a metal layer 2 / a transparent thin film layer 3 is formed on a transparent substrate 1.
A laminated film having a layer structure is provided. In the structure shown in FIG. 3, a 5-layer laminated film composed of transparent thin film layer 3 / metal layer 2 / transparent thin film layer 3 / metal layer 2 / transparent thin film layer 3 is provided on the transparent substrate 1. In the structure shown in FIG. 4, a seven-layer structure composed of transparent thin film layer 3 / metal layer 2 / transparent thin film layer 3 / metal layer 2 / transparent thin film layer 3 / metal layer 2 / transparent thin film layer 3 on transparent substrate 1. Is provided. FIG. 5 shows that the outermost transparent thin film layer of the laminated film is composed of the high refractive index layer 4 and the low refractive index layer 5, and FIG. 6 is a transparent film composed of the high refractive index layer 4 and the low refractive index layer 5 on the transparent substrate. A thin film layer is provided.

The transparent substrate of the present invention has a thickness of 400 nm to
70% light transmittance in the visible region of 800 nm
As described above, more preferably 80% or more of the substrate, a transparent plastic film can be used in addition to glass, and the plastic film is preferable in terms of thinness, flexibility, impact resistance, continuous productivity, and the like. Used. Preferred plastics as the material of the film constituting the transparent substrate are polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides, polyethers, polysulfones, polyethersulfones (PES), polycarbonates, polyarylates, poly Examples of the plastic film include homopolymers or copolymers of ether imide, polyether ether ketone (PEEK), polyimide, aramid and the like.

The thickness of the plastic film used in the present invention is usually 5 to 500 μm, preferably 10 to 20 μm.
It is 0 μm, more preferably 50 to 150 μm. The transparent thin film layer of the present invention is 400 nm to 800 n
It has a light transmittance of at least 60% or more, preferably 70% or more, more preferably 80% or more in the visible light region of m, and pH = 5 or less, preferably pH = 3 or less,
More preferably, any nitride or carbide having an acid resistance that is insoluble or sparingly soluble in an acidic solution having a pH of 1 or less may be used. Examples of preferable nitrides or carbides include indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, amorphous carbon and diamond-like carbon.

In order to improve the visible light transmittance of the transparent laminate, the transparent thin film layer in contact with the metal layer has a refractive index of 1.6 or more, preferably a refractive index of 1.8 or more, more preferably a refractive index of 2.0. A high refractive index transparent thin film made of the above nitrides and / or carbides is preferable. In this case, a part of the transparent thin film layer may be oxidized or hydrogenated.

Examples of the transparent protective layer partially oxidized include indium oxynitride, aluminum oxynitride,
Gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride,
Examples thereof include silicon oxynitride carbide. The nitrogen content in the components of these oxynitrides excluding metal and / or carbon is preferably 30 atomic% or more, more preferably 50 atomic% or more.

Examples of the partially hydrogenated transparent protective layer include, for example, indium hydronitride, gallium hydronitride, silicon hydronitride, tin hydronitride, boron hydronitride, and the like.
Examples thereof include hydrogenated silicon carbide. The nitrogen content in the components of these hydronitrides other than metal and / or carbon is preferably 50 atomic% or more, more preferably 80 atomic% or more. The thickness of these transparent protective layers is usually 1 n.
m to 200 nm, preferably 5 nm to 50 nm,
More preferably, it is 10 nm to 50 nm.

As the method for forming the transparent protective layer of the present invention on the transparent substrate, known methods such as a physical vapor deposition method as well as a spray method and a coating method can be used. Here, the physical vapor deposition method is a method of forming a thin film of metal or the like under reduced pressure or under vacuum, and includes vacuum vapor deposition method, sputtering method, ion plating method, ion beam assisted vapor deposition method, ion cluster beam method. Etc. are illustrated.

In the present invention, any metal layer can be used as long as it has excellent transparency in the visible light region, infrared reflection properties, and conductivity, and particularly silver or a thin film containing silver as a main component. Is preferable, and the content of silver in the thin film containing silver as a main component is desirably 3
It is 0% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more, and more preferably 80% by weight or more. Of course, even if it is out of the range described here, it can be used in some cases. In addition, by laminating a thin film layer made of other metal on a thin film layer containing silver or silver as a main component,
It may be a metal layer used here. Further, from the viewpoint of preventing deterioration, the silver thin film may contain a metal such as gold, copper, palladium, platinum, tungsten, nickel or the like within a range not impairing conductivity and transparency. Further, in order to improve the adhesion of the metal layer to the transparent thin film layer, a metal thin film other than silver may be laminated on the thin film layer containing silver or silver as a main component to form the metal layer used here. When gold is added to the silver thin film, the amount of gold contained in the silver thin film is preferably about 3% by weight to 18% by weight. The thickness of these layers is basically 1n
m to 100 nm is preferably 5 nm to 50 nm, and more preferably 10 nm to 30 nm. Examples of the method for forming the metal layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and an ion vapor deposition thin film forming method.

The transparent laminate of the present invention is not limited to one in which one transparent thin film layer made of nitride and / or carbide and one metal layer are laminated on one surface of the selective transparent substrate. For example,
Three-layer laminated film of transparent thin film layer / metal layer / transparent thin film layer deposited on a transparent substrate or transparent thin film layer / metal layer /
7 layers of stacked thin film of transparent thin film layer / metal layer / transparent thin film layer and transparent thin film layer / metal layer / transparent thin film layer / metal layer / transparent thin film layer / metal layer / transparent thin film layer The transparent laminated body of the present invention also includes a laminated film having the constitution.

Further, in the transparent laminated body in which the transparent thin film layer having the low refractive index layer on the outer side and the high refractive index layer on the inner side is provided in the outermost transparent thin film layer, the refractive index is used as the material of the high refractive index layer. Any nitride, carbide, oxynitride, or oxynitride carbide having a refractive index of 1.6 or more, preferably 1.8 or more, more preferably 2.0 or more may be used. Preferred nitrides, carbides, oxynitrides, and oxynitride carbides are indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, silicon nitride, amorphous carbon, diamond-like carbon, silicon carbide nitride, and oxynitride. Examples thereof include indium, gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride, and silicon oxynitride carbide.

Further, in the transparent laminate having the low refractive index layer on the outer side and the transparent thin film layer having the high refractive index layer on the inner side as the outermost transparent thin film layer, an oxide is used as the material of the low refractive index layer. Any fluoride or oxynitride having a refractive index of 1.5 or less may be used. Examples of preferable oxides, fluorides, and oxynitrides having a refractive index of 1.5 or less include silicon oxide, magnesium fluoride, and silicon oxynitride having a refractive index of 1.55 or less.

In the transparent laminate of the present invention, a transparent substrate having no laminate is provided with a transparent thin film composed of a high refractive index layer and a low refractive index layer from the transparent substrate side. The preferred material for the refractive index is 1.6
Any nitride, carbide, oxynitride, oxynitride carbide, oxide, or sulfide having a refractive index of 1.8 or more, and more preferably a refractive index of 2.0 or more may be used. Preferred nitrides, carbides, oxynitrides, oxynitride carbides, oxides, sulfides include indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, amorphous carbon, diamond, diamond-like carbon, and nitrided carbon. Silicon, indium oxynitride, gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride, silicon oxynitride carbide, indium oxide, tin oxide, indium tin oxide (IT
O), titanium oxide, aluminum oxide, magnesium oxide, thorium oxide, lanthanum oxide, neodymium oxide, zirconium oxide, cerium oxide, bismuth oxide, zinc sulfide and the like.

In the transparent laminate of the present invention, a transparent substrate having no laminate is provided with a transparent thin film composed of a high refractive index layer and a low refractive index layer from the transparent substrate side. The material may be any oxide, fluoride or oxynitride having a refractive index of 1.55 or less, preferably 1.4 or less. Preferred oxides, fluorides, and oxynitrides having a refractive index of 1.5 or less are silicon oxide, magnesium fluoride, and a refractive index of 1.55.
The following silicon oxynitride and the like are exemplified.

Of the partially oxidized nitrides, the refractive index of silicon oxynitride can be continuously changed from about 2.2 to about 1.45 according to the component ratio of nitrogen and oxygen. It is useful as a material.

From the laminate of the present invention in which a transparent thin film layer having a low refractive index layer on the outside and a high refractive index layer on the inside is used as the outermost transparent thin film layer of the laminate, an electromagnetic wave shielding material having a higher visible light transmittance or A heat ray reflector can be manufactured. Similarly, a transparent thin film having a low refractive index layer on the outer side and a high refractive index layer on the inner side is provided so that the high refractive index layer is in contact with the surface of the transparent substrate having no laminate of the laminate of the present invention. Similarly, the laminated body also serves as an electromagnetic wave shielding material or a heat ray reflecting material having a high visible light transmittance.

The low-refractive index layer and the high-refractive index layer mentioned here are relative to each other, and a medium-refractive index layer is provided between them, or various combinations of the low-refractive index layer, the medium-refractive index layer and the high-refractive index layer are provided. May be. The medium refractive index layer and the high refractive index layer are those having a relatively low refractive index among the high refractive index transparent thin film materials having a refractive index of 1.6 or more as the medium refractive index layer and the high refractive index high refractive index layer. Preferably. Various combinations of the low-refractive index layer, the medium-refractive index layer, and the high-refractive index layer make it possible to produce an electromagnetic wave shielding material and a heat ray reflecting material which have low visible light reflection and little wavelength dependency, and have high light transmittance.

When the laminate of the present invention is used as a selective light transmission film, a film or a hard coat layer may be provided on the laminate for mechanical and chemical protection. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.

[0028]

【Example】

Example 1 Reactive sputtering using DC magnetron sputtering using a film winding type sputtering device having three cathodes (targets) on one surface of polyethylene terephthalate (PET) having a visible light transmittance of 90% and a thickness of 50 μm. Silicon nitride is formed to a thickness of 20 nm in nitrogen gas as a first layer, a silver thin film is formed to a thickness of 10 nm in Ar gas as a second layer, and silicon nitride is formed to a thickness of 20 nm in nitrogen gas as a third layer. did. The visible light transmittance of the obtained laminate was 86%, and the surface resistance was 10 Ω /
□, the infrared reflectance was 90%. The obtained laminate was dipped in a sulfamic acid aqueous solution having a pH of 1.4 for 2 minutes, washed with water and dried, and then the surface resistance was measured and found to be 10 Ω / □, showing no change. In addition, there was no change in appearance such as discoloration.

Example 2 A silicon target and silver were used by using a film winding type sputtering apparatus having three cathodes (targets) on one surface of polyethylene terephthalate (PET) having a visible light transmittance of 90% and a thickness of 50 μm. Use the target, D
C magnetron sputtering was performed. At the time of sputtering the silicon target, a mixed gas of nitrogen: oxygen = 97: 3 was introduced and reactive sputtering was performed to form silicon oxynitride as a first layer with a thickness of 20 nm and a silver thin film as a second layer with a thickness of 10 nm. Then, silicon oxynitride having a thickness of 20 nm was formed as a third layer. The resulting laminate had a visible light transmittance of 86%, a surface resistance of 10Ω / □, and an infrared reflectance of 90%. The obtained laminate was immersed in a hydrochloric acid solution having a pH of 3 for 2 minutes, washed with water and dried, and then the surface was observed. As a result, there was no discoloration on the laminate surface. The surface resistance was measured and found to be 10Ω / □, which was unchanged.

Example 3 Indium nitride having a thickness of 20 nm was formed as a first layer on one side of PET similar to that of Example 1 by reactive DC magnetron sputtering, and a silver thin film was formed as a second layer having a thickness of 12 nm.
nm, and indium nitride with a thickness of 2 as the third layer.
It was formed to 0 nm. Visible light transmittance of the obtained laminate 78
%, The surface resistance was 7Ω / □, and the infrared reflectance was 90%. The obtained laminate was dipped in a hydrochloric acid aqueous solution of pH 3 for 2 minutes, washed with water and dried, and the surface resistance was measured to be 7Ω.
It was / □ and there was no change. Moreover, there was no discoloration on the surface of the laminate.

Example 4 A silver thin film having a thickness of 10 nm was formed on one side of PET having a visible light transmittance of 89% and a thickness of 100 μm by the same method as in Example 1,
Silicon nitride was formed thereon to a thickness of 20 nm. The visible light transmittance of the obtained laminate was 85%, the surface resistance was 10Ω / □,
The infrared reflectance was 90%. PH of the resulting laminate
After dipping in the sulfamic acid aqueous solution of 1.4 for 2 minutes, washing with water and drying, the surface resistance was measured. As a result, there was no change in surface resistance and appearance.

Example 5 A silver thin film having a thickness of 10 nm was formed on one side of PET having a visible light transmittance of 89% and a thickness of 100 μm by the same method as in Example 2.
Silicon oxynitride was formed thereon with a thickness of 20 nm. The resulting laminate has a visible light transmittance of 85% and a surface resistance of 10 Ω /
□, the infrared reflectance was 90%. The obtained laminate was immersed in a sulfamic acid aqueous solution having a pH of 2.0 for 2 minutes, washed with water and dried, and then the surface resistance was measured. As a result, there was no change in surface resistance and appearance.

Example 6 A PET film having a visible light transmittance of 89% and a thickness of 100 μm and having a thickness of 20 nm was formed as a first layer on one surface of a PET film by reactive sputtering sputtering using DC magnetron sputtering in the same manner as in Example 2. As a second layer, titanium is 1 nm thick in argon gas, and a silver thin film is deposited on top of it.
A metal layer having a thickness of 20 nm was formed, and further, a silicon oxynitride having a thickness of 20 nm was formed as a third layer. The obtained laminate had a visible light transmittance of 65%, a surface resistance of 10Ω / □, and an infrared reflectance of 90%. The obtained laminate was dipped in a hydrochloric acid aqueous solution having a pH of 1.4 for 2 minutes, washed with water and dried, and then the surface resistance was measured to be 10 Ω / □, and the visible light transmittance was 65%. There was no change in transmittance. In addition, there was no change in appearance such as discoloration.

Example 7 A metal layer (thickness 10 nm) made of silicon nitride (thickness 30 nm) / silver + gold 3 wt% by high frequency ion plating on one surface of polyether sulfone (PES) having a visible light transmittance of 89% and a thickness of 50 μm. ) / Silicon nitride (thickness 30n
m) was formed. The resulting laminate had a visible light transmittance of 86%, a surface resistance of 10Ω / □, and an infrared reflectance of 90%. The obtained laminate was dipped in a nitric acid aqueous solution having a pH of 2 for 2 minutes, washed with water and dried, and the surface resistance was measured to be 10 Ω / □, and there was no discoloration.

Example 8 Indium nitride having a thickness of 20 nm was formed as a first layer and a silver thin film was formed as a second layer with a thickness of 12 as a first layer by reactive DC magnetron sputtering on one side of PET similar to that in Example 1.
nm, and silicon nitride having a thickness of 40 nm as the third layer.
Formed. The obtained laminate had a visible light transmittance of 78%, a surface resistance of 7Ω / □, and an infrared reflectance of 90%.
The obtained laminate was dipped in a sulfuric acid aqueous solution having a pH of 1 for 1 minute, washed with water and dried, and the surface resistance was measured and found to be 7Ω / □, which was unchanged. Moreover, there was no discoloration on the surface of the laminate.

Example 9 Visible light transmittance 89%, PET having a thickness of 125 μm was used to form silicon nitride (thickness: 30 n) by high frequency ion plating.
m) / silver (thickness 12 nm) / silicon nitride (thickness 70 nm)
A laminated body composed of / silver (thickness 10 nm) / silicon nitride (thickness 30 nm) was formed. The obtained laminate has a visible light transmittance of 82%, a surface resistance of 6Ω / □, and an infrared reflectance of 95%.
Met. When a grounding electrode was attached to the formed laminate, grounding was performed from the electrode, and the laminate was used as an electromagnetic wave shielding filter, the amount of attenuation was 20 dB or more.

Example 10 Visible light transmittance 88%, 50 μm thick PET on silicon nitride (thickness 30 nm) / silver (thickness 10 nm) / silicon nitride (thickness 60 nm) / silver (thickness 10 nm) / silicon nitride (thickness 60 nm) ) / Silver (thickness 10 nm) / silicon nitride (thickness 3)
(0 nm) was deposited by DC magnetron sputtering to form a transparent conductive film. The resulting laminate has a visible light transmittance of 70% and a surface resistance of 4Ω.
/ □, the infrared reflectance was 96%. The obtained laminated body was sandwiched between two polyvinyl butyral having a thickness of 0.38 mm and sandwiched between two glass plates having a thickness of 3 mm to produce a laminated glass. This laminated glass was treated for 500 hours in an atmosphere of high temperature and high humidity of 60 ° C. and relative humidity of 85%, but there was no abnormality such as whitening of the sputtered layer.

Example 11 Indium nitride having a thickness of 20 nm was formed as a first layer by high frequency ion plating on one side of PET similar to that of Example 1.
Then, a silver thin film having a thickness of 12 nm was formed as a second layer, and further, silicon nitride having a thickness of 40 nm was formed as a third layer. The obtained laminate has a visible light transmittance of 81% and a surface resistance of 7Ω.
/ □, the infrared reflectance was 90%. According to the same method, a silicon nitride film having a thickness of 30 nm was formed on the PET surface on which the laminated body of the laminated body was not laminated, and further 30 silicon oxide was laminated thereon to obtain a laminated body. The resulting laminate had a visible light transmittance of 87%, a surface resistance of 7Ω / □, and an infrared reflectance of 90%. Attach the ground electrode to the obtained laminate,
When grounded from the electrode and used as a filter for electromagnetic wave shielding, the amount of attenuation was 20 dB or more.

Example 12 A silicon oxide film having a thickness of 4 was formed on the outermost silicon nitride layer of the laminate formed in Example 1 by a high frequency magnetron sputtering method.
It was formed to 0 nm. Visible light transmittance of the obtained laminate 90
%, The surface resistance was 10 Ω / □, and the infrared reflectance was 90%.

Comparative Example 1 Indium oxide having a thickness of 20 nm was formed as a first layer on one surface of PET having a visible light transmittance of 89% and a thickness of 100 μm by a reactive sputtering patterner using DC magnetron sputtering as in Example 1. A silver thin film having a thickness of 10 nm was formed as a second layer in argon gas, and indium oxide having a thickness of 20 nm was further formed as a third layer.

When forming indium oxide on the silver thin film, in order to prevent oxidation and migration of the silver thin film, nitrogen gas and hydrogen gas were introduced in addition to argon and oxygen gas to form a laminate. The resulting laminate had a visible light transmittance of 87%, a surface resistance of 10Ω / □, and an infrared reflectance of 9
It was 0%. The obtained laminate was immersed in a sulfamic acid aqueous solution having a pH of 1.4 for 2 minutes, washed with water and dried, and then the surface resistance was measured. As a result, the resistance increased to 100 Ω / □, and partial discoloration occurred.

Comparative Example 2 Indium oxide (thickness: 30) was formed on one side of PET similar to that of Example 1 by using the reactive sputtering used in Example 1.
nm) / silver thin film (thickness 10 nm) / indium oxide (thickness 70 nm) / silver thin film (thickness 10 nm) / indium oxide (thickness 30 nm). When forming indium oxide on the silver thin film, in order to prevent oxidation and migration of the silver thin film, nitrogen gas and hydrogen gas were introduced in addition to argon and oxygen gas to form a laminate.

The visible light transmittance of the obtained laminate was 84%,
The surface resistance was 7Ω / □ and the infrared reflectance was 95%.
A laminated glass was prepared from the obtained laminate in the same manner as in Example 8, and evaluated by the same method. As a result, whitening occurred from the end face portion, whitening proceeded inside the laminate, and durability was poor.

Comparative Example 3 On a PET film having a visible light transmittance of 88% and a thickness of 50 μm, indium oxide (thickness 30 nm) / silver thin film (thickness 10 nm) / indium oxide (thickness 60 nm) / silver thin film (thickness 10 nm) / oxidation Indium (thickness 60 nm) /
Silver thin film (thickness 10 nm) / indium oxide (thickness 30 n
The transparent conductive film was formed by depositing the laminated body of m) by DC magnetron sputtering. The resulting laminate had a visible light transmittance of 70%, a surface resistance of 4Ω / □ and an infrared reflectance of 96%. The obtained laminate is sandwiched between two polyvinyl butyral having a thickness of 0.38 mm,
It was sandwiched between two glass plates with a thickness of 3 mm to prepare a laminated glass. This laminated glass is 60 ℃, relative humidity 85%
In a high temperature and high humidity atmosphere for 500 hours. Whitening occurred from the end face portion, whitening progressed inside the laminate, and durability was poor.

Comparative Example 4 As a first layer, tetrabutyl titanate prepared by diluting titanium oxide with isopropyl alcohol was applied to one side of the same PET as in Example 1 and heated at 100 ° C. for 5 minutes. Provided. A silver thin film layer (thickness 10 nm) is provided as a second layer on this by DC magnetron sputtering,
Further, as the third layer, titanium oxide (thickness 30
nm) was formed. The resulting laminate had a visible light transmittance of 80%, a surface resistance of 15Ω / □, and an infrared reflectance of 90%. When the obtained laminate was evaluated in the same manner as in Example 8, whitening occurred from the end face portion and the durability was poor.

[0046]

As is apparent from the above examples and comparative examples, the present invention makes it possible to improve the manufacturing process and manufacture a highly reliable transparent conductive film or selective light transmitting film.

[Brief description of drawings]

FIG. 1 is a sectional view showing a preferred structure of the present invention.

FIG. 2 is a sectional view showing a preferred structure of the present invention.

FIG. 3 is a sectional view showing a preferable configuration of the present invention.

FIG. 4 is a sectional view showing a preferred structure of the present invention.

FIG. 5 is a sectional view showing a preferred structure of the present invention.

FIG. 6 is a sectional view showing a preferable structure of the present invention.

[Explanation of symbols]

 1 transparent substrate 2 metal thin film layer 3 transparent thin film layer 4 high refractive index transparent thin film layer 5 low refractive index transparent thin film layer

Claims (24)

[Claims] 1. A laminate, wherein at least one transparent thin film layer made of nitride and / or carbide and at least one substantially translucent metal layer are laminated on at least one surface of a transparent substrate. 2. The transparent thin film layer is a high refractive index transparent thin film made of at least one of indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide, amorphous carbon, and diamond-like carbon.
The transparent laminate according to claim 1. 3. The transparent laminate according to claim 1, wherein the transparent thin film layer is a partially-oxidized high refractive index transparent thin film. 4. The transparent laminate according to claim 1, wherein the transparent thin film layer is a partially hydrogenated high refractive index transparent thin film. 5. The transparent laminate according to claim 1, wherein the transparent thin film layer / the metal layer / the transparent thin film layer are laminated in this order on at least one surface of the transparent substrate. 6. The transparent thin film layer / the metal layer / the transparent thin film layer / the metal layer / on at least one surface of the transparent substrate.
The transparent laminate according to claim 1, wherein the transparent thin film layers are laminated in this order. 7. The transparent thin film layer / the metal layer / the transparent thin film layer / the metal layer / on at least one surface of the transparent substrate.
The transparent laminate according to claim 1, wherein the transparent thin film layer / the metal layer / the transparent thin film layer are laminated in this order. 8. The transparent laminate according to claim 1, wherein the metal layer is silver or a thin film layer containing silver as a main component. 9. The metal layer according to claim 1, wherein the metal layer is formed by laminating a silver thin film layer and a thin film layer containing a metal other than silver as a main component. Transparent laminate. 10. The metal layer according to claim 1, wherein the metal layer is formed by laminating a thin film layer containing silver as a main component and a thin film layer containing a metal other than silver as a main component. The transparent laminate according to item 1. 11. The transparent laminate according to claim 1, wherein the outermost transparent thin film layer of the transparent thin film layer comprises a low refractive index layer on the outer side and a high refractive index layer on the inner side. body. 12. A transparent laminate in which the outermost transparent thin film layer in the transparent thin film layer comprises a high refractive index layer and a low refractive index layer, and the low refractive index layer is provided on the outermost side, the high refractive index The transparent laminate according to claim 11, wherein the layer is made of a nitride, a carbide, an oxynitride, or an oxynitride having a high refractive index of 1.6 or more. 13. A transparent laminated body in which the outermost transparent thin film layer in the transparent thin film layer is composed of a high refractive index layer and a low refractive index layer, and the low refractive index layer is provided on the outermost side, in which the high refractive index layer is provided. Is indium nitride, gallium nitride, silicon nitride, tin nitride,
The transparent laminated body according to claim 13, comprising at least one of boron nitride, silicon carbide, amorphous carbon and diamond-like carbon. 14. A transparent laminate in which the outermost transparent thin film layer in the transparent thin film layer comprises a high refractive index layer and a low refractive index layer, and the low refractive index layer is provided on the outermost side, in which the low refractive index layer is provided. The transparent laminate according to claim 11, wherein the transparent laminate comprises at least one of an oxynitride, a fluoride, and an oxide having a refractive index of 1.55 or less. 15. A transparent laminated body in which the outermost transparent thin film layer in the transparent thin film layer comprises a high refractive index layer and a low refractive index layer, and the low refractive index layer is provided on the outermost side, in which the low refractive index layer is provided. 15. At least one selected from the group consisting of silicon oxide, magnesium fluoride, and silicon oxynitride having a refractive index of 1.55 or less.
The transparent laminate according to item. 16. A laminate in which at least one transparent thin film layer made of nitride and / or carbide and at least one substantially transparent metal layer are laminated on one surface of the transparent substrate, or on at least one surface of the transparent substrate. A laminated body in which transparent thin film layer / metal layer / transparent thin film layer are laminated in this order, or a transparent laminated body in which transparent thin film layer / metal layer / transparent thin film layer / metal layer / transparent thin film layer is laminated on one surface of a transparent substrate, or transparent No transparent laminate is laminated on any one of the transparent laminates of transparent thin film layer / metal layer / transparent thin film layer / metal layer / transparent thin film layer / metal layer / transparent thin film layer laminated in this order on one surface of the substrate. A transparent laminated body, wherein a transparent thin film layer comprising a high refractive index layer and a low refractive index layer is formed on the transparent substrate surface than the transparent substrate. 17. A transparent thin film layer comprising a high refractive index layer and then a low refractive index layer of the laminate, wherein the high refractive index layer has at least one of nitride, carbide, oxide or sulfide having a refractive index of 1.6 or more. The transparent laminate according to claim 16, which comprises a seed. 18. A transparent thin film layer comprising a high refractive index layer and a low refractive index layer of the laminate, wherein the high refractive index layer has at least one of nitride, carbide, oxide or sulfide having a refractive index of 1.6 or more. A transparent thin film layer having a different refractive index selected from the species is included in at least two layers.
The transparent laminate according to any one of 6 and 17. 19. A transparent thin film layer comprising a high refractive index layer and a low refractive index layer of the laminate, wherein the high refractive index layer is indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, silicon carbide or amorphous carbon. , Diamond-like carbon, indium oxynitride, gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride, silicon oxynitride carbide, indium oxide, tin oxide, indium tin oxide (IT
O), titanium oxide, aluminum oxide, magnesium oxide, thorium oxide, lanthanum oxide, neodymium oxide, zirconium oxide, cerium oxide, bismuth oxide or zinc oxysulfide.
Or the transparent laminated body as described in any one of 18 above. 20. A transparent thin layer comprising a high refractive index layer and a low refractive index layer of the laminate, wherein the low refractive index layer is at least one of oxide, fluoride or oxynitride having a refractive index of 1.55 or less. The transparent laminate according to claim 16, which comprises: 21. A transparent thin layer comprising a high refractive index layer and a low refractive index layer of the laminate, wherein the low refractive index layer is silicon oxide,
21. At least one selected from the group consisting of silicon, magnesium fluoride, and silicon oxynitride having a refractive index of 1.55 or less.
The transparent laminate according to item. 22. The transparent laminate according to claim 16, wherein the metal layer is silver or a thin film layer containing silver as a main component. 23. The transparent laminate according to claim 16, wherein the metal layer is a laminate of a silver thin film layer and a thin film layer containing a metal other than silver as a main component. 24. The transparent laminate according to claim 16, wherein the metal layer is a laminate of a thin film layer containing silver as a main component and a thin film layer containing a metal other than silver as a main component.