JPS629419B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laminate having a single or stacked metal thin film layer based on gold covered on one or both sides by a transparent thin film layer. More specifically, the present invention relates to the above laminate having transparent conductivity and/or selective light transmittance. Transparent conductive coatings are used for applications that utilize their conductivity, such as electrodes for liquid crystal displays, electrodes for electroluminescent materials, electrodes for photoconductive photoreceptors, antistatic layers, heating elements, and other applications in the electronics and electrical fields. It is widely used in The selective light transmitting film is transparent to light in the visible light range, but has the ability to reflect infrared light (including near-infrared light), so it is also useful as a transparent heat insulating film. be. Therefore, it can be used for solar energy collectors (water heaters), solar thermal power generation, greenhouses, windows of buildings, etc. Especially in modern buildings,
Windows occupy a large proportion of the wall surface, and their function as transparent heat-insulating windows that can prevent the use of solar energy and energy dissipation will become increasingly important in the future. Furthermore, it is of great importance as a film for greenhouses, which is necessary for the cultivation of wild vegetables, citrus fruits, etc., and the cultivation of fruits, etc. In this way, transparent conductive films and selective light transmission films are important from the viewpoint of electronics and solar energy utilization, and it is desired by the industry that homogeneous and high-performance films can be supplied industrially at low cost and in large quantities. It was rare. Conventionally known transparent conductive films include metal thin films such as gold, copper, silver, and palladium, compound semiconductor films such as indium oxide, tin oxide, and copper iodide, and gold, copper, silver, and palladium. It is known that a conductive metal film such as the above is made selectively transparent over a certain wavelength range. As a selective transmission film with high infrared light reflecting ability, an indium oxide film or a tin oxide film with a thickness of several thousand angstroms, and a laminated film of a metal film and a transparent conductor film are known. however,
At present, transparent conductive films or selective light transmitting films with excellent performance have not yet been produced industrially at low cost. That is, it is difficult to obtain the above-mentioned metal thin film with high visible light transmittance because metal has high reflective ability or absorbing ability over a wide wavelength range. When visible light transmittance is increased, conductivity or infrared light reflection ability is significantly reduced. To increase conductivity or infrared light reflection ability,
When the thickness of the metal thin film is increased, the visible light transmittance is significantly reduced, and therefore a transparent conductive film or a selective light transmitting film having excellent both properties cannot be obtained. The above compound semiconductor thin film is formed by a thin film forming method in vacuum such as vacuum evaporation method or sputtering method. There are problems such as the fact that the film formation rate is actually slow due to the control, and the size of the evaporation source is limited, which limits its application to large-area substrates.
It lacks industrial productivity and cannot be a cheap product. In order to obtain an excellent transparent conductive or permselective film using a semiconductor such as indium oxide, a film of a semiconductor such as indium oxide with a film thickness of several thousand angstroms has been proposed, but the production rate of the film is extremely slow. Not only this, but also a large amount of valuable resources such as indium are consumed, and as a result, the manufacturing cost of the membrane increases significantly. Furthermore, this film does not have sufficiently high infrared reflectance or conductivity. A typical structure of the above-mentioned transparent conductive film or selective light transmitting film is a laminate in which a metal thin film is sandwiched between transparent high refractive index thin films, such as Bi ₂ O formed by vacuum evaporation, reactive evaporation, or sputtering. ₃ ／Au／
Sandwich-like structured laminates of Bi ₂ O ₃ , ZnS/Ag/ZnS or TiO ₂ /Ag/TiO ₂ have been proposed.
Those using silver or gold as the metal layer have particularly excellent transparency in the visible light region and reflection properties against infrared light due to the optical properties of silver or gold themselves, and also have favorable properties in terms of conductivity. It is particularly excellent as a material because it has . However, a laminate consisting of a silver thin film layer covered by a transparent high refractive index thin film layer has significant environmental stability problems, as its properties deteriorate due to heat, light, gas, and other contaminants. This deterioration is mostly due to silver surface diffusion or corrosion caused by environmental factors. On the other hand, a laminate consisting of a gold thin film layer covered with a transparent high refractive index thin film layer has better stability against heat, light, gas, and other contaminants than the above-mentioned laminate consisting of a silver thin film layer. The golden yellow to light orange color tone of this product was not desirable when applied to windows for general buildings. When looking at the problem of color tone from an environmental engineering or ergonomics perspective, the warm golden to light orange tones of the gold thin film layer give an unstable psychology, and conversely the cool pale blue of the silver thin film layer. is said to have stable psychological effects. Currently, the window area in buildings tends to increase.Color schemes that have a stable psychological effect on floors, ceilings, walls, etc. in living or working environments have been thoroughly studied and are actually being applied. ,
The psychological effects of windows, such as color tones, must also be considered important. The present inventor has been conducting research on laminates having transparent conductivity and/or selective light transmission, and has developed a thin gold film without impairing the chemical or environmental stability of the laminate having a thin gold film layer. As a result of intensive research to improve the color tone of the laminate layer, we found that by using a metal layer whose main component is gold, it is possible to improve the color tone without impairing the properties of gold.
Furthermore, the present invention was achieved based on the knowledge that the effect is particularly large and preferable when the content of silver and copper is in a specific amount. That is, the present invention provides a laminate consisting of a molded substrate and a metal thin film layer (A) covered on one or both sides with a transparent thin film layer (B).
(A) is a single or laminated metal thin film layer containing gold as a main component and silver and copper, and the sum of the weights of silver and copper is 36% by weight relative to the total weight of gold, silver and copper. % to 69% by weight. The present invention will be explained. The molded substrate used in the present invention may be an organic molded substrate, an inorganic molded substrate, or a composite molded substrate thereof, but an organic molded substrate is preferred.
Examples of materials for the base of organic molded products include polyethylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylic resin, BBS resin, polystyrene resin, polyacetal resin, polyethylene resin, polypropylene resin, polyamide resin, fluorine resin, etc. Plastic resins, thermosetting resins such as epoxy resins, diallyl phthalate resins, silicone resins, unsaturated polyester resins, phenolic resins, urea resins, polyvinyl alcohols, polyacrylonitrile, polyurethanes, aromatic polyamides,
Examples include solvent-soluble resins such as polyimide resins. These may be used alone as homopolymers or copolymers or as a mixture of two or more. These molded products are plate-shaped, sheet-shaped, film-shaped, rod-shaped,
It can be formed into any shape such as thread, block, or pipe, and is not necessarily limited to a flat plate. Depending on the purpose, colored, uncolored, transparent, or opaque materials are selected. Among these, flexible transparent films or sheets are preferred. Among such films, a film having a visible light transmittance of 80% or more and a thickness of 10 to 250 μm is preferred, and a film having the above characteristics of polyethylene terephthalate is particularly preferred. In the laminate of the present invention, the metal thin film layer (A) covered with the transparent thin film layer (B) on one or both sides as described above is provided on the molded substrate. (A) is a single or layered metal thin film whose main component is gold. A single layer refers to a thin metal layer in which gold, silver, and copper atoms coexist; it may be completely uniform, or it may be non-uniform to some extent, but at least a single layer It exists as. Further, in the case of a laminated metal thin film, there are six types of combinations in which three types of metals, gold, silver, and copper are laminated, and any of them can exhibit the expected effects of the present invention. In the stacked metal layers, there is no problem even if the stacked metals form a somewhat uneven mixed layer at the interface between the stacked metals, and the three types of metals used in the present invention are different metals. They exist in contact with each other to form a layer. In addition, when laminating metal thin film layers, a single layer metal thin film is formed in which any two metals coexist among the three metals gold, silver, and copper, and then laminated with one other metal. Even if it is used, the effects of the present invention will not be impaired in any way. For example, a copper layer may be laminated on a single layer of gold and silver, or a single layer of silver and copper may be laminated on a gold layer. Such combinations include the following (a) to (e) (i) Gold layer/silver layer/copper layer (b) Gold layer/copper layer/silver layer (c) Copper layer/gold layer/copper layer (d) Silver Layer/Copper layer/Gold layer (E) Copper layer/Gold layer/Silver layer (F) Copper layer/Silver layer/Gold layer (G) Silver/Copper layer/Gold layer (C) Gold layer/Silver/Copper layer (R) Silver layer/Gold copper layer (N) Gold/Copper layer/Silver layer (R) Copper layer/Gold/Silver layer (E) Gold/Silver layer/Copper layer, among these, (A), (B), (D), ( f)
,
(g), (ch), (l), and (e) are preferred, especially (a) and (b).
,(d),
(F), (G), and (H) are preferred. Furthermore, other components to the extent that they do not impair the desired effects of the present invention (for example, 1% by weight or less for platinum group metals),
For example, aluminum, nickel, iridium, rhodium, palladium, platinum, indium, tin,
There is no problem even if cadmium, germanium, zinc, etc. coexist. The single or stacked metal thin film layers of gold, silver and copper in the object stack of the present invention can be produced in various ways. For example, by performing vacuum deposition or sputtering using an alloy of gold, silver, and copper, it is possible to obtain a single metal thin film layer in which gold, silver, and copper coexist. Alternatively, according to a multi-component evaporation method or a multi-component sputtering method in which gold, silver and copper are vacuum-deposited or sputtered separately, a single metal thin film layer in which gold, silver and copper coexist or a desired order of gold, silver and copper can be formed. It is possible to obtain laminated metal thin film layers. The metal thin film layer created by either method is
The object of the present invention can be achieved by the coexistence of gold, silver and copper. Such coexistence of gold, silver, and copper can improve the drawbacks of forming a metal thin film layer in which only gold, only gold and silver, or only gold and copper coexist. That is, it is possible to change the color tone of the gold thin film layer to a preferable one without impairing the chemical or environmental stability of the gold thin film layer. Generally speaking, it is possible to change the color tone of gold by adding metals with different absorption ranges to gold. For example, if platinum metals such as palladium, iridium, platinum, and rhodium are added to gold, the color tone changes from gray-white to gray-black. In addition, the base metals tin, nickel, chromium, titanium,
If aluminum or the like is added, the color tone will have a large absorption in the visible region and become close to black. The pale blue color tone aimed at by the present invention can be obtained only by adding specific amounts of silver and copper. However, the addition of silver and copper, which are metals less noble than gold, was expected to impair the chemical or environmental stability of gold. Tamman's law for alloys (e.g. Annalen Der
Physik, V Folge, Band1, 1929 page 309−
317), alloys obtained by adding 50 atomic percent or more of a more base metal to a noble metal (for example, an alloy with 32 wt. percent or more of copper added to gold) have poor chemical stability. It is said to be almost equivalent to base metals. Although Tamman's law is an empirical law, it is still widely accepted in metallurgy. According to Tamman's rule, for example, an alloy containing 50 atomic % or more of silver or copper relative to gold (ie, 65 or 68 wt % or more) exhibits chemical stability almost equivalent to that of silver or copper. Furthermore, while Tamman's law applies to fully annealed bulk alloys, thin metal layers such as those used in the present invention require a large increase in surface area and surface defects due to evaporation or sputtering. Due to effects such as uniformity, increased crystallographic defects, and increased activity of new surfaces formed by evaporation or sputtering, even lower amounts of base metals than in the bulk corrosion-resistant alloy described by Tamman's rule are present. It is thought that the presence of metals causes the properties of noble metals to be lost. In other words, in order to maintain the chemical stability of a metal thin film layer containing gold as its main component even when metals less base than gold are mixed in, it is necessary to contain gold in an amount considerably greater than, for example, 50 atomic percent. is expected. Furthermore, if the metal thin film layer containing gold as a main component contains a fairly base metal such as copper, it is expected that the amount of gold present will need to be further increased. However, contrary to such expectations, in the laminate of the present invention, the total weight percentage of silver and copper is 36% to 69% by weight based on the total weight of gold, silver, and copper, which are the constituent components of the metal thin film layer. By forming a single or laminated metal thin film layer consisting of gold, silver, and copper that contains 100% of gold, silver, and copper containing The unexpected and surprising result is that the properties of durability, chemical resistance, and corrosion resistance of gold can be sufficiently maintained, and the color tone of the metal thin film layer can be improved to a much more favorable color than that of gold alone. was achieved. To point out the effect of unexpected improvement in corrosion resistance, the laminate of the present invention having a metal thin film layer consisting of gold, silver and copper is almost equivalent to the laminate having a metal thin film layer consisting of only gold, Approximately 5 times or more of a laminate having a metal thin film layer consisting of silver and copper, approximately 7 times or more of a laminate having a metal thin film layer of silver and copper, and approximately 4 times or more of a laminate having a metal thin film layer of silver and gold. It has corrosion resistance. Since the color tone of the laminate changes depending on the amount of silver and copper coexisting with gold, the amounts of silver and copper to be added can be selected depending on the color tone suitable for the application. That is, as the silver content increases, the transmitted color changes from golden to bluish, and when compared at the same film thickness, the visible light transmittance improves as the silver content increases. Furthermore, as the copper content increases, the transmitted color changes from golden to reddish, and when comparing the same thin films, the visible light transmittance decreases as the copper content increases. Furthermore, the environmental stability tends to decrease as the silver content increases, and further decreases as the copper content increases. Therefore, if the content of silver and copper exceeds 69% by weight, the negative effect on environmental stability will be greater than the effect on improving optical properties, which is not preferable. Moreover, if the copper content exceeds 30% by weight, the environmental stability will be significantly lowered and the optical properties will also be lowered, which is not preferable. From these points, the amount of silver contained in the metal thin film layer should not be less than 35.5% by weight and not reach 69.0% by weight, and the amount of copper contained in the metal thin film layer should not be less than 0.5% by weight and not more than 30% by weight. can be,
Moreover, it is preferable that the total amount of silver and copper is from 36% by weight to less than 70% by weight. Furthermore, in order to balance the desired optical properties and environmental stability of the resulting laminate, the total amount of silver and copper is particularly preferably from 45% by weight to 69% by weight. In particular, when emphasis is placed on the chemical resistance and corrosion resistance of the obtained laminate, the content of copper is preferably about 1% to 15% by weight, more preferably 1% to 8% by weight. The thickness of the metal thin film is not particularly limited as long as it has the required characteristics as a transparent conductive film or selective light transmission film, but in order to have infrared light reflective ability or conductivity, it must have at least a certain degree of thickness. It is necessary to have continuity in the area. The film thickness is preferably about 50 Å or more, which gives a continuous structure rather than an island structure, and 500 Å or less from the viewpoint of transparency to solar energy. The thinner the metal thin film layer is, the wider the light transmission area becomes, so to increase transparency it is best to have a film thickness of 250 Å or less, and to have sufficient conductivity or infrared light reflection ability, it should be 70 Å or more. A film thickness of . Even when the metal layer (A) is a laminated metal layer, it is preferable that the total thickness of the laminated metal layers is within the above range, and by controlling the thickness of each metal layer, it is possible to The metal content can be varied. In the present invention, the effects of the component metals as described above are exhibited even without forming an alloy as described above, and effects that are difficult to predict from the effects of adding different metals, which are normally considered in metallurgy. It is assumed that this is expressed. As mentioned above, the method for forming the metal thin film layer (A) includes, for example, vacuum evaporation method, cathode sputtering method,
Chemical plating, electroplating, and a combination of these methods are all possible, but in a laminate using a molded substrate, the sheet as the substrate,
When the surface of the film or the like is smooth, vacuum evaporation is particularly suitable from the viewpoints of uniformity of the formed thin film, ease of production, and film formation speed. In order to keep the composition of gold, silver, and copper in the film as uniform as possible during film formation, alloy or multi-component sputtering methods are suitable, and multi-component sputtering methods or alloy sample and electron beam sputtering methods are also suitable for vacuum evaporation methods. Combinations of heating methods, high-frequency induction heating methods, resistance heating methods, flash vapor deposition methods, etc. are preferred. The metal thin film layer (A) detailed above is covered on one or both sides with a transparent thin film layer (B), and the transparent thin film layer (B) will be explained in detail below. The transparent thin film layer in the present invention is a transparent high refractive index thin film (B-
1) and/or a transparent protective film (B-5). Transparent high refractive index thin film (B-
1) is not particularly limited as long as it has the effect of preventing reflection in the metal layer, but it has a refractive index of 1.6 or more, preferably 1.7 or more for visible light, and a visible light transmittance of 80. % or more, preferably 90% or more. The film thickness is 50 to 1000 Å, preferably 100 to 500 Å. Examples of materials that meet these conditions include thin film layers of titanium dioxide, titanium oxide, zirconium oxide, bismuth oxide, zinc sulfide, tin oxide, and indium oxide. These thin film layers can be provided by methods such as sputtering, ion plating, vacuum deposition, and wet coating. A transparent high refractive index thin film (B-
1) is preferably a transparent high refractive index thin film layer made of titanium oxide (B-2), bismuth oxide (B-3) or zinc sulfide (B-4). Further, as the transparent high refractive index thin film layer, a titanium oxide thin film layer (B-2) is particularly preferable because of its excellent optical properties such as visible light refractive index and transparency. It may be either a titanium oxide thin film layer (B-21) formed from a titanate compound or a titanium oxide thin film layer (B-22) formed by vacuum evaporation, sputtering, or the like. The titanium oxide thin film layer (B-22) formed by vacuum deposition or sputtering can be formed by a known method. In the case of sputtering, it can be formed by low-temperature magnetron sputtering, argon gas sputtering of titanium oxide, or reactive sputtering in which oxygen is introduced into metallic titanium. Further, according to the vacuum evaporation method, it is possible to form the titanium oxide thin film layer (B-22) using an electron beam or the like. Further, even if the titanium oxide thin film layer (B-22) formed in this manner contains titanium nitride to the extent that it does not affect the characteristics, there is no problem in achieving the purpose of the present invention. The titanium oxide thin film layer (B-22) containing an organic substance formed from an organic titanate compound can be provided, for example, by using an organic solvent solution of a solute containing an alkyl titanate as a main component. The alkyl titanate has the general formula Ti _l O _n R _o (however,
R is an alkyl group, l, m, and n are positive integers). Among the alkyl titanates represented by the above general formula, especially m=4+(l-1)×3, n=4
+(l-1)×2, where l=1 to 30, is preferably used from the viewpoint of ease of film formation (for example, coating) and properties of the obtained dielectric layer. The value of 1 may not be uniform but may have a distribution, but alkyl titanates in which the distribution of 1 values has a maximum value of 15 or less are particularly preferable in terms of coating solution viscosity and hydrolyzability. In general, an alkyl substituent R having 1 to 20 carbon atoms is preferably used. In particular, those having an alkyl substituent having 2 to 11 carbon atoms are preferably used from the viewpoints of ease of film-forming operations, such as coating, as well as hydrolysis rate, mechanical properties and transparency of the resulting film. Note that a mixture of two or more of the above alkyl titanates may be used. The alkyl titanate is dissolved in an organic solvent to form a solution, and when applied to the surface of the molded product, it is hydrolyzed,
The subsequent condensation reaction results in dealkyl hydroxide formation, forming a network structure. Depending on the coating conditions, alkyl titanates can approach titanium oxide. Examples of the alkyl titanate used in the laminate of the present invention include tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrastearyl titanate, and tetra-2-
Examples include ethylhexyl titanate, diisopropoxy titanium bisacetylacetonate, and particularly tetrabutyl titanate and tetrapropyl titanate are preferably used. These alkyl titanates may be used as is,
Further, precondensed products such as dimers, tetramers, and decamers can also be preferably used. Furthermore, these alkyl titanates may be used after being stabilized with a chelate compound such as acetylacetone. Organic solvents commonly used in the formation of films with alkyl titanates are those that sufficiently dissolve the alkyl titanate and, if a molded substrate is used, have an affinity for the surface of the molded product, making it easy to apply and post-coating. A solvent that dries easily is preferred. Examples of such organic solvents include hexane, cyclohexane, heptane, octane, methylcyclohexane, toluene, benzene, xylene, octene, nonene, solvent naphtha, methanol, ethanol, isopropanol, butanol, pentanol, cyclohexanol, and methylcyclohexanol. , phenol, cresol, ethyl ether, propyl ether, tetrahydrofuran, dioxane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, methyl benzoate, glacial acetic acid, chloroform, Organic solvents such as hydrocarbons such as carbon tetrachloride, trichrene, trichloroethane, chlorobenzene, dibromoethane, methyl cellosolve, cellosolve, and cellosolve acetate, alcohols, ethers, esters, carboxylic acids, and halogen-substituted hydrocarbons can be given. In particular, isopropanol, butanol, n-hexane, toluene, etc. are preferably used. These organic solvents can be used alone or in combination of two or more, if necessary. Furthermore, depending on the case, a water-containing solvent may be used. When forming the thin film layer (B-21) using an alkyl titanate solution, the alkyl titanate is dissolved in an organic solvent to obtain a coating solution. At this time, if necessary, heating may be applied for dissolution within a range that does not impair the intended effects of the present invention.
In order to improve properties such as adhesion, refractive index, color tone, and hardness of the coating film, a small amount of other components soluble in the organic solvent may be added. Examples of such components include solvent-soluble resins such as silicon resins, acrylic acid resins, epoxy resins, and polyurethane resins. The concentration of the organic solvent solution (coating solution) of alkyl titanate is arbitrary, but in particular, in order to uniformly form a thin film layer with a thickness of about several hundred angstroms, it is 0.1 to 30% by weight, preferably 0.5 to 10% by weight. Particularly preferably, the concentration is adjusted to 1 to 7.5% by weight. When applying this solution to the surface of the molded product, for example, methods using a general coating machine such as dipping method, atomization method, spinner method, etc.
i.e. gravure coater, Meyer bar coater,
There is a method of using a reverse roll coater or the like. For example, when coating on a smooth molded substrate such as a film or sheet, it is preferable to use a gravure coater or Mayer bar coater from the viewpoint of control and uniformity of film thickness, and when coating on a non-smooth molded substrate, The muri method is preferably used. At the same time or after applying the solution, the solvent is dried at a temperature higher than room temperature, and if necessary, heat treatment is performed to complete the application. This drying or heat treatment condition is 50~
At a temperature of 200°C, for about 10 seconds to 10 hours. By coating in this manner, the alkyl titanate is hydrolyzed to form a titanium oxide thin film layer (B-21) containing an organic substance. The thin film layer (B-
By adjusting the film forming conditions of 21), the alkyl group can be left in the thin film layer (B-21), and the amount thereof can be 0.1 to 30% by weight, preferably 0.5 to 30% by weight.
By adjusting the amount to 10% by weight, the thin film layer (B-
21) A transparent conductive coating that improves the adhesion between the metal thin film layer (A) or the surface of a molded product, especially an organic polymer molded substrate, and has excellent transparency and surface conductivity over a wide wavelength range. Alternatively, a selective light transmitting film can be obtained. The titanium oxide thin film layer (B-21) formed from an alkyl titanate compound has a specific amount of alkyl ester groups remaining, so its refractive index is lower than that of titanium oxide obtained by sputtering or vacuum evaporation, and is visible. It is about 1.6 to 2.4 in the optical range. Therefore, the laminate having the titanium oxide thin film layer (B-21) formed from an alkyl titanate compound has (a) uniform light transmittance over a large area; (B)
Excellent adhesion to molded products. (c) It has advantages such as high light transmittance over a wide wavelength range of visible light. The content of organic substances in the titanium oxide thin film layer (B-21) formed from an alkyl titanate compound is
0.1-30% by weight, preferably 0.5-10% by weight
It is. If this amount is less than 0.1% by weight, adhesiveness will be significantly impaired, and if this amount exceeds 30% by weight, transparency will be significantly impaired. The organic substance referred to in the present invention is mainly an alkyl group derived from an alkyl titanate solution when forming the titanium oxide thin film layer (B-21) from an alkyl titanate solution (from the alkyl titanate itself, or from an organic solvent and the alkyl titanate). It may be formed by a reaction with a titanium oxide thin film (B-21), but it may also be a layer in which such an organic substance is contained in another method for forming the titanium oxide thin film (B-21). This organic substance is thought to exist in the titanium oxide thin film layer (B-21) as a bond between titanium and an alkyl ester group, but in the present invention, its content is defined by the amount of alkyl groups. In addition, the content of organic substances derived from alkyl groups contained in the titanium oxide layer can be determined by applying the alkyl titanate compound and drying it in an atmosphere containing appropriate moisture and moisture, preferably in a high temperature and high humidity atmosphere, or in hot water. (For example, relative temperature 80%, temperature 80℃, etc. or 80%
Controlled reduction can be achieved by appropriately contacting it with hot water, etc. By using such a method, it is possible to freely control the refractive index of the titanium oxide layer or the adhesion between the titanium oxide layer and the molded substrate, which is a major feature of forming titanium oxide from an organic titanate compound. It is. Among the transparent high refractive index thin film layers (B-1) described above, the titanium oxide thin film layer (B-2), the titanium oxide thin film layer (B-21) formed from an alkyl titanate compound, and the bismuth oxide thin film layer (B-2) -3) and zinc sulfide thin film layer (B-4) are preferred. Another element that can be a component of the transparent thin film layer (B) of the present invention, that is, the transparent protective film (B-5), mainly improves properties such as surface hardness, weather resistance, corrosion resistance, and stain resistance. In addition to being provided on the surface for the purpose of bonding, it may also be provided directly on the substrate to improve adhesion. Materials used for such a layer include, for example, acrylic ester resins such as polymethyl methacrylate, acrylic resins such as polyacrylonitrile or polymethacrylonitrile, polyolefin resins such as polyethylene or polypropylene, and ethylene silicate. In addition to organic substances such as silicon resins such as polymers, polyester resins, melamine resins, and fluororesins, silicon oxide,
Inorganic substances such as magnesium alumina fluoride can also be applied. Furthermore, the purpose of the present invention may be achieved even if several types of resins or substances from among the above-mentioned compounds are used in a layered manner depending on the purpose. Among such protective layers, when emphasis is placed on low absorption in the infrared region, acrylic resins such as polymethacrylonitrile or polyacrylonitrile, or polyolefin resins such as polyethylene or polypropylene are preferred. These acrylic resin protective layers are preferably coated to a thickness of 0.5μ or less or 1.6μ or more in order to avoid adverse effects due to optical interference effects, and polyolefin resin protective layers are, for example, biaxially stretched. A polyolefin film with a thickness of 12μ or less is suitable. In addition, in order to improve the surface hardness of these protective layers, a UV hardening type surface curing resin such as trimethylolpropane triacrylate or tetramethylolpropane tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) is laminated on the surface. It can be solidified. Furthermore, since an inorganic protective layer has low optical absorption and high surface hardness, silicon oxide, magnesium fluoride, aluminum oxide, etc. are preferably used. More surprising features of the laminate of the present invention are:
The durability is improved by providing such a protective layer. Normally, when a protective layer is provided, it is often thought that durability will be improved in any case, but this is not necessarily the case in the case of a thin film laminate having a special function, which is the object of the present invention. For example, a laminate that uses a silver (Ag) thin film layer as a metal layer and covers both sides with a titanium oxide (TiO ₂ ) thin film layer is provided on a polyester film,
And, for each of the four types of laminates in which the metal layer is a silver-copper (Ag-Cu) metal layer, a gold-silver (An-Ag) layer, or a gold-silver-copper (Au-Ag-Cu) layer, no protective layer is provided. Considering the durability of the installed one,
Example 26 Table 6 shows the results. As described above, the laminate of the present invention having metal thin film layers made of gold, silver and copper covered with transparent thin film layers on both sides has all the required properties such as not only light resistance and corrosion resistance but also heat resistance. In terms of environmental stability, it is possible to achieve previously unimaginable stability due to a combination of effects that cannot be predicted from conventional technology, and it also has favorable optical properties in the pale blue range. It is possible to keep it at . To specifically illustrate the structure of the present invention, (A) a metal thin film layer, (B-1) a transparent high refractive index thin film layer, and a transparent protective thin film layer (B-5) are formed on a molded product substrate as follows. A laminate in which the laminates are sequentially laminated is preferably used. (1) Molded product base/(A)/(B-1) (2) Molded product base/(A)/(B-5) (3) Molded product base/(A)/(B-1)/( B-5) (4) Molded product base/(B-1)/(A)/(B-1) (5) Molded product base/(B-1)/(A)/(B-5) (6 ) Molded product base/(B-1)/(A)/(B-1)/
(B-5) (7) Molded product base/(B-5)/(A)/(B-5) (8) Molded product base/(B-5)/(B-1)/(A)/
(B-5) (9) Molded product base/(B-5)/(B-1)/(A)/
(B-1)/(B-5) Furthermore, when the objective is to obtain a laminate with good visible light transmittance, (1), (3), (4), (6), and (9) are preferably used. In this way, the laminate in which the layers (A) and (B) are provided on the surface of the transparent molded substrate provides electrical energy,
It is also used as an antistatic layer in transparent electrodes that provide optical energy or that provide optical energy and electrical energy. In addition, a laminate provided with the layers (A) and (B), which have particularly excellent selective light transmittance,
It is preferably used as a selectively permeable material for effectively utilizing sunlight and/or as an energy-saving material by utilizing its heat insulating properties. In addition, a laminate using a colored molded product and having the above-mentioned (A) and (B) layers on the surface can impart conductivity without impairing the color of the molded product,
For example, it helps prevent static electricity from forming on molded objects. The above-mentioned coating with excellent infrared light reflectivity is applied to the surface of the colored molding
The laminate provided with the layers (A) and (B) can impart infrared light reflecting ability without impairing the color or pattern of the molded product. In particular, a laminate in which layers (A) and (B) with excellent selective light transmittance are provided on the surface of a molded product colored in a color that absorbs sunlight well, such as black, absorbs sunlight well. , it is effectively used as a selectively absorptive material with little heat radiation. In particular, when such a selectively absorbing material is used as an absorber in a solar water heater that uses sunlight to obtain hot water, the efficiency of utilizing solar heat can be significantly increased. For example, the surface of a molded product that allows water to pass through, such as a pipe, is colored to absorb sunlight well, and the laminate of the present invention having excellent selective light transmittance is formed on this surface. It has a selective absorption effect and is effectively used as a solar heat collector. Because of the advantage that the laminate of the present invention can be formed continuously, a polymer sheet or film is preferably used as the molded product substrate in the laminate of the present invention. In particular, the laminate of the present invention using a transparent polymer sheet or film as a substrate has the advantage of being lightweight, highly flexible, hard to tear, and easy to process. For example, it is preferably used as a transparent electrode for an electroluminescent body, a transparent electrode for a photoconductive photoreceptor, a windowpane of a building, or a heat insulating film installed near a window to prevent heat loss from the window. Furthermore, since the base of the molded product is a sheet or film, continuous production can be easily carried out, the production speed can be greatly increased, and a high quality material can be supplied in large quantities at low cost. The laminate of the present invention has metal thin film layers constituting it.
Visible light transmittance,
The surface resistance and infrared reflectance can be changed arbitrarily, and the following typical uses are available. (a) Transparent conductive laminates used for antistatic or photoconductive photoreceptor conductive layers (b) Transparent electrodes for solid displays such as liquid crystal electroluminescent bodies and surface illumination bodies (c) Day frost heaters for vehicle windows, etc. Transparent surface heater used as a heating element (d) Transparent heat insulating laminate product applicable to glass parts of building windows, greenhouses, and freezing/refrigerating cases The features of the present invention are summarized as follows. The laminate of the present invention has properties not previously available. That is, (1) instead of the metal film conventionally used as a metal layer, by using a single or laminated metal thin film made of silver, gold, and copper, durability such as heat resistance and light resistance can be improved. In addition, the color tone is greatly improved without impairing environmental stability such as corrosion resistance and stain resistance. (2) The laminate of the present invention has excellent transparency over a wide wavelength range, and has excellent solar energy transmittance, visible light transmittance, near-infrared light transmittance, etc. Hereinafter, a more specific explanation of the present invention will be shown in Examples. In addition, the light transmittance in the examples is a value at a wavelength of 500 nm unless otherwise specified. The infrared reflectance was measured by attaching a reflectance measurement device to a Hitachi EPI-type infrared spectrometer and measuring the reflectance of a slide glass with a sufficiently thick layer of vacuum-deposited silver (approximately 3000 Å) to 100 Å.
Measured as %. The amount of the organic substance contained in the titanium oxide thin film layer (B-21) is determined by forming a molded product of the laminate of the present invention having transparent conductivity or selective light transmission into a piece of about 2 mm in size, and This was immersed in a solution consisting of 1000 parts by weight of water, 20 parts by weight of ethyl alcohol, and 1 part by weight of hydrochloric acid at room temperature for 24 hours to extract the organic components. 9000) and Chromosorb W (60~
30 parts by weight of PEG-20 was filled into a mesh (30 meshes), and the ions were determined by mass fragment graphics method. The elemental composition in the metal thin film layer was determined by quantitative determination using fluorescent X-ray analysis (using a Rigaku fluorescent X-ray analyzer) and atomic absorption spectrometry. Example 1 A biaxially stretched polyethylene terephthalate film with a light transmittance of 86% and a thickness of 75 μm was coated with a titanium oxide thin film layer with a thickness of 300 Å as the first layer, and a titanium oxide thin film layer with a thickness of 300 Å as the second layer.
A thin film layer of 140 Å of gold, silver, and copper (50% by weight of gold, 5% of copper, 45% by weight of silver) and a 300 Å thick titanium oxide thin film layer as the third layer were sequentially laminated,
A laminate having transparent conductivity and selective light transmission was formed on a film. The titanium oxide thin film layer is made of 3 parts of tetrabutyl titanate and isopropyl alcohol.
A solution consisting of 65 parts of normal hexane and 32 parts of normal hexane was applied using a bar coater and heated to 100° C. for 5 minutes. A single thin film layer in which gold, silver and copper coexist is gold-silver-
It was formed using a copper alloy (50% gold, 5% copper, 45% silver) using a low-temperature magnetron sputtering method. The content of butyl groups contained in the first and third titanium oxide thin film layers was 5.5%. (trout
(No. 56 was quantified by mass fragment graphics method) The obtained film had a light transmittance of 73%, a surface resistance of 15Ω/square, and an infrared reflectance of 93%. Further, the color tone of the obtained film had transmitted light with a considerably bluish tinge. The obtained film was irradiated with light for 3000 hours using a carbon arc light resistance tester (Shimadzu CW-DV3), and then its infrared light reflectance was measured. In both cases, when carbon arc light is irradiated from the coating side and when it is irradiated from the substrate polyethylene terephthalate film side, the infrared light reflectance
Retained over 80%. Furthermore, the obtained film was placed in a gear oven tester set at 90°C and the infrared light reflectance was measured after 3000 hours, and the infrared light reflectance remained at 80% or more. Comparative Example 1 A laminated film was prepared in the same manner as in Example 1 except that the second metal thin film layer was formed only of gold (thickness: 100 Å). The obtained film had a golden transmitted light characteristic of gold. Carbon arc light irradiation and thermal deterioration acceleration tests were performed in the same manner as in Example 1, and as a result, the reflectance was maintained at 80% or more even after 3000 hours. Examples 2 to 7 A transparent conductive and selectively transparent layer was prepared in the same manner as in Example 1, except that the composition and thickness of the metal thin film layer were changed to those shown in Table 1. I got the film. The visible light transmittance of each obtained film is 70%
The infrared light reflectance was 90% or more. In addition, all the samples had a preferable color tone as they had a blue-based transmitted light color.

[Table] *The rest is all gold. Coat the obtained film with acrylate resin (Dyanal LR574, Mitsubishi Rayon Co., Ltd.) using a bar coater and dry it for 3 minutes in a hot air dryer set at 120°C to determine the film thickness. A 2μ thick acrylic protective layer was formed. The visible light transmittance of the obtained film was 63% or more, and the infrared light reflectance was 83% or more. Almost no change in color tone was observed due to the lamination of the protective layer. These films were subjected to carbon arc light irradiation and thermal deterioration acceleration tests in the same manner as described in Example 1, but even after 3000 hours, the infrared light reflectance remained at 80% or more, and no changes in appearance, etc. were observed. was not seen. In addition, a 100 ppm sodium hypochlorite aqueous solution was sprayed onto these films twice a day to test the corrosion resistance of the metal thin film, and the corrosion state after 50 days is summarized in Table 1. Examples 8 to 10 Transparent conductive and selectively transparent films were obtained in the same manner as in Example 1. An acrylate resin or an acrylic resin was coated on each of these films, or a polypropylene film was laminated thereon to obtain a laminate having a protective layer. The resulting laminate had an infrared reflectance of 83% or more and a visible light transmittance of 60% or more. The color tone of the obtained film was pale blue with transmitted light. The acrylate resin was provided in the same manner as in Example 2. The acrylic resin was coated with a solution of polymethacrylonitrile in a mixed solvent of methyl ethyl ketone and cyclohexanone using a bar coater, dried for 2 minutes in a hot air dryer set at 130°C, and provided to a thickness of 2 μm. Polypropylene film laminate is a polypropylene film (thickness 12μ) with adhesive Toagosei.
Co., Ltd. S-1601 was coated with a bar coater and bonded onto the laminate. These obtained films were immersed in a 1N hydrochloric acid solution for 3 hours, but no change occurred. Comparative Examples 2 to 6 Transparent conductive and selectively transparent laminates were prepared in the same manner as in Example 1, except that the composition and thickness of the metal thin film layer were changed to those shown in Table 2. I got the film. The color tone of the obtained films was pale blue in Comparative Examples 3 and 4, and pale blue with a slight yellow tinge in Comparative Examples 5 and 6. A protective layer of acrylic resin was laminated on the obtained film in the same manner as in Example 2, and then a corrosion resistance test was conducted. Corrosion resistance tests were carried out by immersing in a 1N hydrochloric acid aqueous solution for 3 hours, and by spraying the sodium hypochlorite aqueous solution described in Example 2 and observing the condition 60 days later. The results are shown in Table 2.

[Table] * The rest is all gold. Also, the results of conducting the same carbon arc light irradiation test as in Example 1 on transparent conductive and selectively transparent laminates with the same configuration as Comparative Examples 5 and 6.
After 1000 hours, the infrared reflectance remained at 80% or higher, but the color partially changed to purple. As a result of measuring the distribution in the depth direction of the discolored portion using ESCA (JEOL JESCA-4), interdiffusion of gold, silver, and titanium oxide was confirmed. Example 11 A laminate having transparent conductivity and selective light transmittance was formed on the polyethylene terephthalate film used in Example 1 in the same manner as in Example 1, except that a titanium oxide layer was formed by sputtering on the film. I let it happen. The titanium oxide thin film layer was created using a low temperature magnetron sputtering device using a titanium oxide powder sintered body as a target. The sputtering conditions were set to an argon gas pressure of 5×10 ^-3 Torr and a high-frequency input power of 2 W/cm ² to obtain a titanium oxide thin film layer with a thickness of 300 Å. The infrared light reflectance of the obtained laminate was 90%,
The visible light transmittance was 75%. Further, the color tone was almost unchanged from Example 1. Carbon arc light irradiation and thermal deterioration acceleration tests were conducted in the same manner as in Example 1, but the infrared light reflectance remained at 80% or more even after 3000 hours in each case, and no change in appearance was observed. . Examples 12 to 14 Transparent conductivity and selective light transmission were obtained in the same manner as in Example 1, except that the metal thin film layer was composed of metal thin film layers laminated in the order of gold, silver, and copper as shown in Table 3. A laminate with properties was formed on the film. As a method for sequentially laminating gold, silver, and copper, each metal was sequentially evaporated using a multi-source vacuum evaporation method. For example, after a predetermined amount of gold is deposited, silver is successively deposited and then copper is deposited successively to obtain metal thin film layers that are separated from each other to form layers. The color tone of the laminate was almost indistinguishable from that of Example 1. After manufacturing the obtained laminate, ESCA (JEOL Ltd.)
Interdiffusion of the metal layers was observed using JESCA-4), but the metal layers were separated from each other and the degree of interdiffusion was smaller than expected. A protective layer of 2μ of acrylate resin was laminated on the obtained laminate in the same manner as in Example 2, and then carbon arc light irradiation and thermal deterioration acceleration tests were conducted in the same manner as in Example 1, but each time was 2000 hours. Infrared light reflectance remains 80 even after elapsed time
% or more was retained.

[Table] * Examples 15 to 17 in which the rest are all gold The same as Example 1 except that the metal thin film layer is composed of a metal thin film layer formed by laminating a gold thin film on a metal thin film layer consisting of silver and copper. A laminate having transparent conductivity and selective light transmission was formed on a film in a similar manner. The metal thin film layer consisting of silver and copper contains 92% by weight of silver,
A laminated metal thin film layer was obtained by forming the target by magnetron sputtering using a target consisting of 8% by weight of copper, and then vacuum evaporating gold. The optical properties of the resulting laminate are an infrared reflectance of 90%.
The visible light transmittance was 70%. The color tone of the obtained laminate became pale blue with a yellowish tinge as the gold content increased. A 2μ thick polymethacrylonitrile layer was laminated on the obtained laminate as a protective layer, and the layer was soaked in 1N hydrochloric acid solution for 30 minutes.
The results of the soaking time are shown in Table 4.

[Table] *Example 18 where the rest is gold 250mm thick as the first layer on 2mm thick plain glass
Å thick titanium oxide thin film layer, 150 Å thick as second layer
a thin film layer of silver, gold and copper (50% by weight gold, 5% by weight copper, 45% by weight silver) and a thickness as a third layer.
Titanium oxide thin film layers of 300 Å thick were sequentially laminated to form a laminate having transparent conductivity and selective light transmittance on a glass plate. Each titanium oxide thin film layer was coated by spraying a solution consisting of 5 parts of tetramer of tetra-2-ethylhexyl titanate, 40 parts of n-hexane, 25 parts of toluene, and 30 parts of butanol with compressed nitrogen, and heated at 110°C. was heated for 3 minutes. A single thin film layer in which gold, silver and copper coexist is Example 1.
was formed in the same manner as. The resulting laminate has a transmittance of 70% and a surface resistance of 15
Ω/square, and the infrared light reflectance was 85%. Moreover, the color tone was preferable, with transmitted light having a bluish tinge. Examples 19-25 Example 1 except for changing the composition of the metal thin film layer
A laminate having transparent conductivity and selective light transmittance was formed on the film in the same manner as described above. The color tone of the laminate was preferable, with a bluish tinge compared to gold. The resulting laminate had an infrared reflectance of 88% or more and a visible light transmittance of 70% or more. A conductive protective film made of polymethacrylonitrile and having a thickness of 2 μm was formed on these laminates in the same manner as in Example 9. The obtained laminate was subjected to a carbon arc light irradiation test and a thermal deterioration acceleration test in the same manner as in Example 1, but the infrared light reflectance remained 80% or more even after 3000 hours or more in each case, and the appearance etc. There was no change. Table 5 shows the results of immersing these laminates in 1N hydrochloric acid for 3 hours.

[Table] Example 26 and Comparative Examples 7 to 10 A laminate having transparent conductivity and/or selective light transmission was placed on a film in the same manner as in Example 1 except that the composition and thickness of the metal thin film were changed. was formed. In addition, a 2 μm thick transparent protective film made of polymethacrylonitrile was coated on each of the obtained laminates in the same manner as in Example 9 to form a laminate. By these methods, laminates having the same transparent high refractive index thin film layer and metal thin film layer composition, uncoated laminates and laminates coated with a transparent protective layer were constructed. These laminates were subjected to a 1,000-hour photodegradation acceleration test by irradiation with carbon arc light in the same manner as in Example 1, and the results of immersing each laminate in 1N hydrochloric acid for 1 hour were reported as well as the composition of the metal thin film layer. It is listed in the table.

【table】

[Table] Example 27 A metal thin film layer having a thickness of 150 Å and consisting of 50% by weight of gold, 45% by weight of silver, and 5% by weight of copper was formed by direct magnetron sputtering on the polyethylene terephthalate film used in Example 1. . Furthermore, a titanium oxide layer with a thickness of 350 Å was formed on the obtained metal thin film layer in the same manner as in Example 1. The resulting laminate had a visible light transmittance of 70% and an infrared light reflectance of 90%. Moreover, there was almost no difference in color tone from Example 1. Example 28 On the plain glass used in Example 18, a metal thin film layer and a titanium oxide layer similar to those in Example 31 were formed. The resulting laminate had a visible light transmittance of 65%, a surface resistance of 15 Ω/square, an infrared reflectance of 90%, and a color tone similar to that of Example 31. Example 29 A metal thin film layer having a thickness of 150 Å and consisting of 50% by weight of gold, 45% by weight of silver, and 5% by weight of copper was formed on the polyethylene terephthalate film used in Example 1 by direct magnetron sputtering. Further, on the obtained metal thin film layer, an acrylic protective layer having a thickness of 2 μm was formed using the acrylate resin used in Example 2 in the same manner as in Example 2 to obtain a laminate. The resulting laminate had a visible light transmittance of 45% and an infrared light reflectance of 85%. Moreover, the color tone was favorable. Example 30 A film with a thickness of 300 Å was deposited on the polyethylene terephthalate film used in Example 1 in the same manner as in Example 11.
A titanium oxide layer was formed. On the obtained titanium oxide thin film layer, a metal thin film layer having a thickness of 150 Å consisting of 50% by weight of gold, 45% by weight of silver, and 5% by weight of copper was formed by the same method as in Example 27, and then a metal thin film layer was formed on the obtained titanium oxide thin film layer. A titanium oxide layer with a thickness of 270 Å was formed from an alkyl titanate compound in the same manner as in Example 1,
A transparent conductive and/or selectively transparent laminate was obtained. The visible light transmittance of the obtained laminate was 73%,
The infrared light reflectance was 90%.

Claims (1)

[Claims] 1. A laminate consisting of a molded product substrate and a metal thin film layer (A) covered on one or both sides with a transparent thin film layer (B), wherein the metal thin film layer (A) is coated with gold. A single or laminated metal thin film layer containing silver and copper as main components, and the sum of the weights of silver and copper is 36% to 69% by weight relative to the total weight of gold, silver, and copper. A laminate characterized by: 2 Claim 1 in which at least one of the transparent thin film layers (B) includes a transparent high refractive index thin film layer (B-1)
Laminated body as described in section. 3 At least one of the transparent thin film layers (B) is a titanium oxide thin film layer (B-2) and a bismuth oxide thin film layer (B-
3) or a zinc sulfide thin film layer (B-4). 4 Claims 1 to 3 in which at least one of the transparent thin film layers (B) comprises a titanium oxide thin film layer (B-21) formed from an organic titanate compound.
Any of the laminates listed in section. 5 Claims 1 to 4 in which the transparent thin film layer (B) laminated on the metal thin film layer (A) consists of a transparent high refractive index thin film layer (B-1) and a transparent protective thin film (B-5)
Any of the laminates listed in section. 6 Transparent high refractive index thin film layer (B-
1), metal thin film layer (A), transparent high refractive index thin film layer (B-
1) and the transparent protective thin film (B-5) are laminated in the above order.