TW513475B - Transparent conductive layered structure, display in which this transparent conductive layered structure is applied, and coating liquid for forming transparent conductive layer - Google Patents

Abstract

The present invention pertains to a transparent conductive layered structure having a transparent substrate and a transparent 2-layer film consisting of a transparent conductive layer and a transparent coating layer formed in succession on this substrate, that is used for instance, in the front panel of displays, such as CRTs, etc. The above-mentioned transparent conductive layer has as its main components noble metal microparticles with a mean particle diameter of 1 to 100 nm composed of gold and/or platinum and silver and containing 5 to 95 wt% gold and/or platinum, colored pigment microparticles with a mean particle diameter of 5 to 200 nm, and binder matrix. The noble metal microparticles are mixed at a ratio of 1 to 40 parts by weight per 1 part by weight colored pigment microparticles. Moreover, it is characterized in that the transparent 2-layer film has a surface resistance of 10 to 5000 Ω/□, reflectance of 0 to 2.5%, visible light transmittance of 40 to 75%, and standard deviation of transmittance at each wavelength in 5 nm intervals of the visible light wavelength region being 0 to 5%.

Description

513475 Printed clothing A7 B7 of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Field of the invention The present invention relates to a transparent conductive layer structure, which includes a transparent substrate and a transparent conductive layer formed on the substrate in sequence. A transparent 2-layer film composed of a transparent coating. This structure is used as a front panel for displays such as Brown Tubes (Cathode Ray Tubes (CRTs); especially related to a transparent conductive layer structure. Display 'and a coating liquid for forming a transparent conductive layer, wherein the transparent conductive layer structure is to adjust the visible light transmittance of the transparent 2-layer film to within a prescribed range P of 100%, a display, wherein The transparent conductive layer structure is used as well as a coating liquid for forming the transparent conductive layer, and the conductive layer is used in the production of the transparent conductive layer structure. Related Technical Description As a result of office automation in recent years, many OA machines have been used Introducing offices, office environments that today have to face the display of OA machines to complete work are no longer rare. A cathode ray tube of a computer (also referred to as a Brown Tube as described above; CRT) as an example of an OA machine. The requirement when using this CRT is that it can easily see the display screen to prevent visual fatigue. It is also required to be able to avoid the adhesion of dust and the electric shock due to the electrification of the CRT screen. In addition, recently, the harmful effects of low frequency magnetic waves generated by the CRT on the human body have been concerned, and what is desired is to prevent this CRTs leaking to the outside world. In addition, the above electromagnetic waves are generated by deflection coils or flyback transformers, and with the development of larger televisions, the paper size that tends to increase is applicable to Chinese national standards (CNS ) A4 size (210 X 297 mm) _ ^ «like clothing -------- 1T ---------; --¼ (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of the invention (2) Electromagnetic waves leak into the surrounding environment. We can prevent most magnetic field leakage by taking precautionary measures such as changing the shape of the deflection coil. On the other hand, it is also possible to prevent the leakage of the electric field by forming a transparent conductive layer on the surface of the square glass before the CRT s. 'This method of preventing the leakage of the electric field is theoretically the same as the recently used method to prevent charging. However The conductivity of the transparent conductive layer must be much higher than that of the conductive layer formed to prevent charging. That is, although the surface resistance of 108 Ω / 0 (ohms per square) is sufficient to prevent charging, it must be formed. A transparent conductive layer having a low resistance of at least 106Ω / □ or lower, preferably 5 × 103Ω / □ or lower, more preferably 103Ω / □ or lower to prevent electric field leakage (electric field protection effect) . Therefore, several proposals have been made in the past to respond to the above needs, and one of these proposals is to apply and dry a coating liquid for forming a transparent conductive layer on the surface of a square glass in front of CRTs. The system is composed of conductive particles dispersed in a solvent and an organic adhesive such as an alkyl silicate, and then baked at a temperature of about 200 ° C. This is a well-known method that can achieve low surface resistance at low cost. method. • In addition to other methods of forming a transparent conductive layer such as vacuum evaporation and thermal spraying, this method of forming a transparent conductive layer using a coating liquid is much simpler, the manufacturing cost is very low, and It is useful to deal with the electric field protection effect of CRTs. This method uses tin indium oxide (ITO) as the coating liquid for conductive particles. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --- ^ ---- 一 --- --Clothing -------- Order --------- line (please read the precautions on the back before filling this page) 513475 V. Description of Invention (3) for the above transparent conductive layer A known coating liquid. However, since the obtained film has a high surface resistance falling between 104 and 106 Ω / □, a correction circuit for eliminating an electric field is required in order to properly block the electric field leakage phenomenon, and a problem arises that the manufacturing cost will increase accordingly. . On the other hand, the transmittance of a film from a coating liquid for forming a transparent conductive layer using metal powder as the conductive particles is lower than that of a film from a coating liquid using I TO, but the resulting film has Low surface resistance between 102 and 103 Ω / □. Inevitably, because the above-mentioned correction circuit is not necessary, there is a cost advantage, and it is likely to become the mainstream in the future. In addition, the metal particles used for the above-mentioned coating liquid for forming a transparent conductive layer are restricted to precious metals such as silver, gold, platinum, rhodium, palladium that are rarely oxidized in the air, as in Japanese Laid-Open Patent Application No. Hei 8- 77832 and Hei 9-55Π5 as shown. This is because when using metal particles other than precious metals such as iron, nickel, cobalt, etc., an oxide film is always formed on the surface of such metal particles in the atmosphere around the air, and good conductivity cannot be obtained. Transparent conductive layer printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, anti-glare treatment is performed on the surface of the panel to control the reflectivity on the screen, and therefore the display screen is easy to observe. This anti-glare treatment is performed by making fine irregularities on the surface to increase the diffuse reflectance on the surface. However, this method is not the one I really want because it will cause the image quality to decrease due to the decrease in resolution during use. Inevitably, it is better to replace the anti-glare treatment with an interference method. The implementation of this interference method will make the paper transparent. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love).

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i. Description of the Invention (4) The refractive index and film thickness of the film are controlled so that the reflected light will cause damaging interference with the incident light. In order to obtain low reflectivity results by this type of interference method, a 2-layer film is generally used, in which the thickness of the optical film of the film having a high refractive index and the film having a low refractive index are set, respectively. 1 / 4λ and 1 / 4λ (λ is the wavelength) or set to 1/2 λ and 1/4 λ, respectively. At the same time, a thin film composed of the above-mentioned tin indium oxide (ITO) particles is used as such a thin film having a high refractive index type. In addition, compared to materials such as ITO, the metal's optical constant (n-ik; where η: refractive index; i2 = -1; k: dispersion coefficient) is a very small number and k is a very high number, Therefore, even when a transparent conductive layer composed of metal particles is used, the same anti-reflection result as ITO can be obtained by using the interference effect of light on a thin film having a 2-layer structure. As described above, the metal particles used to form the coating liquid for the transparent conductive layer are limited to noble metals such as silver, gold, platinum, rhodium, and palladium, but when comparing their resistances, platinum, rhodium, and The specific resistances of palladium of 10.6, 5.1, and 10.8 microohm · cm are extremely higher than the specific resistances of silver and gold of 1.62 and 2.2 microohm · cm, respectively. Therefore, it is advantageous to use silver particles and gold particles to form a transparent conductive layer having a low surface resistance. However, when silver particles are used, there is a problem of weather resistance due to severe vulcanization and oxidation and the erosion phenomenon caused by salt water and ultraviolet rays. When gold particles are used, there is no such problem with the above. Issues related to climatic resistance, but there are problems with the use of platinum particles-6- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 'J -------------- 11 --------- (Please read the precautions on the back before filling in this page) W3475 A7 ------- B7 _ $, invention description (5), rhodium particles, palladium particles, etc. Cost issue. (Please read the notes on the back before filling this page.) From the viewpoint of this technical background, the inventor of the present invention has previously proposed a coating liquid for forming a transparent conductive layer, and the transparent conductive material made of this coating liquid Layer structure, and display using such a transparent conductive layer structure; wherein the coating liquid is dispersed with precious metal-coated silver particles having an average particle diameter of 1 to 100 nanometers (either gold or copper or gold alone). A compound composed of platinum and platinum is coated on the surface of silver particles) to replace the silver or gold particles. (See specifications in Japanese Published Patent Applications Nos. Hei 11-203943 and Hei 1 1-228872 and Japanese Patent Application Nos. Hei 1 1-366343). In addition, when the surface of the silver particles is coated with gold or platinum alone or a compound composed of gold and platinum, the silver in the silver particles coated with the precious metal is subjected to gold or platinum alone or a compound composed of gold and platinum. Protection, it is expected to improve the weather resistance and chemical resistance. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, it has been confirmed that during the manufacturing process of the transparent conductive layer structure, the above-mentioned average particle diameter is 1 to 100 nanometers. Gold or platinum alone or a compound consisting of gold and platinum is coated on the surface of silver particles) The heat treatment conditions used, part of the silver will diffuse into the coating formed by gold and / or platinum to form an alloy layer and make part The alloy layer is exposed on the surface, resulting in a slight reduction in its weather resistance and chemical resistance. It has also been confirmed that the gold and / or platinum content of the above-mentioned noble metal-coated silver fine particles can be set within a range of 50 to 95% by weight. In addition, it can be formed by the transparent conductive layer whose composition is silver or gold. 7- ^ Paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 513475 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _ 5. The alloy layer obtained by performing the above heat treatment on particles such as the description of the invention (6), and in some cases the composition of the precious metal coating used to coat the surface of the silver particles is not the same as the result of forming this alloy layer Just gold and / or platinum. Therefore, in the specifications of the present invention, the particles in the above-mentioned transparent conductive layer whose composition is silver or gold and the like no longer represent silver particles coated with precious metals but precious metal particles. In addition to the above-mentioned requirements for good conductivity, low reflectivity, weather resistance, chemical resistance, etc., in recent years, there has also been a need to adjust the transmittance of this type of transparent conductive layer structure to less than 100%. (From 40 to 75%) in order to improve the contrast of the image in order to make the display glory easier to observe. • Necessarily, the conventional transparent conductive layer structure disclosed in Japanese published patent applications No. Hei 1 Bu 20 3 943 and Hei 1 1-228872 and Japanese patent application No. Hei Π-366343 exists The problem is that they cannot meet the above needs. Disclosed in the above specifications is a method capable of forming a conventional transparent 2 layer film on the surface of a panel (front panel before CRT) having a low transmittance (for example, 40 to 60%), and a method for enabling a low transmittance The method of forming a transparent 2-layer film on the surface of a panel having a high transmittance is considered in response to such a demand, and the latter is more popular in terms of the fact that the transmittance of the CRT can be controlled according to the demand. In addition, progress has recently been made in flattening the display surface of CRT displays, so that the latter method is also needed in this example to achieve the goal of making the transmittance of the front panel uniform. A brief description of the invention Therefore, one of the objectives of the present invention is to provide a first or second transparent paper that is compliant with China National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back first) (Fill in this page) _Installation ------- Order ---- 513475 Α7 Β7 V. Description of the invention (7) Conductive layer structure, including the transparent conductive layer or transparent coating of the transparent 2-layer film mentioned above It has low transmittance and good conductivity, low reflectivity, climatic resistance, chemical resistance, etc. as in the past. The visible light transmittance of this transparent 2-layer film is adjusted to less than 100% (from 40 to 75%). Another object of the present invention is to provide a display in which the contrast of the display screen is improved and the surface reflectance of the display screen is reduced, and it has a long-term strong electric field protection effect. Another object of the present invention is to provide a coating liquid for forming a transparent conductive layer, which is suitable for manufacturing the above-mentioned first transparent conductive layer structure. That is, the first transparent conductive layer structure according to the present invention is a transparent conductive layer structure including a transparent substrate and a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer sequentially formed on the substrate, wherein the above The main composition of the transparent conductive layer is precious metal particles with an average particle diameter of 1 to 100 nanometers (made of gold and / or platinum and silver and containing 5 to 95% by weight of the above-mentioned gold and / or platinum), average particles The colored pigment particles having a diameter of 5 to 200 nm and the binder matrix are mixed with the precious metal particles in a proportion of 1 to 40 parts by weight of the precious metal particles per part by weight of the colored pigment particles. The transparent 2-layer film contains 10 to With a surface resistance of 5,000 Ω / | □, the transparent 2-layer film has a minimum reflectance of 0 to 2.5% in the reflectance profile in the visible light region. The transparent 2-layer is not included and the transparent 2-layer alone is not included. The visible light transmittance of the film is 40 to 75%, excluding the transparent substrate mentioned above, and the transparent 2-layer film alone is transmitted at each wavelength in the visible wavelength region (380 to 780 nm) at 5 nm intervals. Rate scale-9- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- Line for employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives Printed by Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7___ 5. Description of Invention (8) The standard deviation is 0 to 5%. In addition, the second transparent conductive layer structure according to the present invention is a transparent conductive layer structure including a transparent substrate and a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer sequentially formed on the substrate,-wherein the above transparent The main composition of the conductive layer is precious metal particles with an average particle diameter of 1 to 100 nanometers (made of gold and / or platinum and silver and containing 5 to 95% by weight of the above-mentioned gold and / or molybdenum) and a binder matrix, The main composition of the above-mentioned transparent coating is colored pigment particles with an average particle diameter of 5 to 200 nanometers and a binder matrix. The transparent 2-layer film contains a surface resistance of 10 to 5,000 Ω / □. The transparent 2-layer The minimum reflectance in the visible reflectance profile of the film is 0 to 2.5%, the transparent substrate is not included, and the visible light transmittance of the transparent 2-layer film alone is 40 to 75%, excluding the transparent substrate. The standard deviation of the transmittance of the transparent 2-layer film in the visible wavelength region (380 to 780 nanometers) at every wavelength of 5 nanometers is 0 to 5%. Next, the display according to the invention is characterized in that the display is a display main unit and a front panel disposed above the front of the display main unit, wherein the first or second transparent conductive layer structure is used as the above-mentioned The transparent 2-layer film is disposed on the outer side of the front panel. In addition, the coating liquid for forming a transparent conductive layer used to manufacture the first transparent conductive layer structure according to the present invention is a transparent conductive layer for forming a transparent conductive layer structure. Layer of coating liquid, the transparent conductive layer structure contains a transparent substrate and a transparent conductive layer formed on the substrate in order and transparent -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ） ', -------- Order --------- line # · (Please read the precautions on the back before filling out this page) ^ 3475 Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (9) Transparent 2-layer film composed of bright coating layer, the above-mentioned transparent 2-layer film contains a surface resistance of 10 to 5,000 Ω / □, and the transparent 2-layer film has a reflectance profile in the visible light region. Change into The small reflectance is 0 to 2.5%. The visible light transmittance of the transparent 2-layer film alone is excluding the above transparent substrate and the transparent 2-layer film is not included. The standard deviation of the transmittance at each wavelength in the visible wavelength range (380 to 780 nm) at 5 nm intervals is 0 to 5%, where the main composition of the coating liquid is an average particle diameter of 1 to 1 〇〇NAN and precious metal-coated silver particles containing 5 to 95% by weight of gold and / or platinum (coated with gold or platinum alone or a compound consisting of gold and platinum on the surface of silver particles), average Colored pigment particles having a particle diameter of 5 to 200 nanometers, and a solvent in which such particles are dispersed, and mixed with precious metal in a proportion of 1 to 40 parts by weight of precious metal-coated silver particles per part by weight of colored pigment particles. Coated silver particles. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing a reflectance profile of a transparent conductive layer structure according to Example 1. FIG. FIG. 2 is a graph showing a transmittance profile of a transparent conductive layer structure according to Example 1. FIG. Figure 3 is a graph showing a reflectance contour of a transparent conductive layer structure according to Example 2. FIG. 4 is a graph showing a transmittance profile of a transparent conductive layer structure according to Example 2. FIG. Figure 5 is used to show a -11-I paper size according to Example 3 of the transparent conductive layer structure. Applicable to Chinese national standards (CNSM4 regulations Γ (2) 0 X 297). &Quot; ^ ^ ----- --- Order --------- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of the invention (1G) Graph. Figure 6 is a graph showing the transmittance profile of a transparent conductive layer structure according to Example 3. Figure 7 is a graph showing the reflectance profile of a transparent conductive layer structure according to Example 4. Figure 8 is a graph showing the transmittance profile of the transparent conductive layer structure according to Example 4. Figure 9 is a graph showing the reflectance profile of the transparent conductive layer structure according to Example 5. FIG. 10 is a graph showing a transmittance profile of the transparent conductive layer structure according to Example 5. FIG. 11 is a graph showing a reflectance profile of the transparent conductive layer structure according to Example 6. FIG. Figure 12 is a diagram showing a transmission according to Example 6. A graph showing the transmittance profile of the conductive layer structure. Figure 13 is a graph showing the reflectance profile of a transparent conductive layer structure according to Example 7. Figure 14 is a graph showing a reflectance profile according to Example 7. A graph of the transmittance profile of the transparent conductive layer structure. Fig. 15 is a graph showing the reflectance profile of the transparent conductive layer structure according to Example 11. Fig. 16 is a graph showing the reflectance profile of the transparent conductive layer structure according to Example 11. A graph of the transmittance profile of the transparent conductive layer structure. Figure 17 is used to show a transparent conductive layer structure according to Example 12-12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ 7 clothes -------- order --------- line (please read the precautions on the back before filling this page) 513475 A7 B7 V. Description of the reflectance profile of (11) Graph. Figure 18 is a graph showing the transmittance profile of a transparent conductive layer structure according to Example 12. Figure 19 is a graph showing the reflectance of a transparent conductive layer structure according to Example 12. Contour graph. Figure 20 is used to show a A graph showing the transmittance profile of the transparent conductive layer structure according to Example 13. Figure 21 is a graph showing the reflectance profile of the transparent conductive layer structure according to Comparative Example 1. Figure 22 is for A graph showing a transmittance profile according to the transparent conductive layer structure of Comparative Example 1. Fig. 23 is a graph showing a reflectance profile according to the transparent conductive layer structure of Comparative Example 2. Fig. 24 It is a graph showing a transmittance profile of a transparent conductive layer structure according to Comparative Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail: First, as in Japanese Laid-Open Patent Applications Nos. Hei 1 1-203943 and Hei 1 1-228872, and Japanese Patent Application No. Hei 1bu 366343 Generally disclosed in the document, the present invention is that gold and platinum are chemically stable and have excellent climatic resistance, chemical resistance, oxidation resistance and other properties, and can be composed of gold or platinum alone or composed of gold and platinum. The concept that the compound is coated on the surface of the silver particles to improve the chemical stability of the silver particles. -13- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 513475 A7 _______ B7 V. Description of the invention (12) In addition, as mentioned above, the specific resistance of platinum is more than that of silver and gold. The specific resistance is higher, so from the point of view of the surface resistance of the transparent conductive film, the silver and gold systems are better than the silver-port system and the silver-gold-port system. However, because of the use of gold or lead alone or The compound material composed of gold and platinum is used as the coating on the surface of the above silver particles, so the harm to the good electrical conductivity of silver cannot be lower than the actual application level. In addition, the method of making alloy particles is by The silver and gold or platinum or gold and platinum alloys are made to improve the above-mentioned weather resistance and other properties, and the silver particles coated with gold or platinum alone or a compound composed of gold and platinum are also considered to replace them. However, When using chloroaurate or When an aqueous solution composed of platinum salt and silver salt is used as a starting solution and the above-mentioned alloy particles are produced by a wet method (usually used for preparing particles), there is a problem that when these materials are mixed, slightly soluble Silver chloride. In addition, although the above problems do not occur when sodium cyanide is used as sodium chloroaurate, platinum salt or silver salt, there is a problem that it becomes necessary to process toxic cyanide compounds to produce gold or It is not easy to synthesize alloy particles composed of platinum and silver. Therefore, by using silver particles coated with precious metals (coating gold or platinum alone or a compound composed of gold and platinum on the surface of silver particles), The metal particles used in the coating liquid for forming the transparent conductive layer in the present invention can be expected to make properties of the transparent conductive layer (such as weather resistance and chemical resistance) formed by the coating liquid used to form the transparent conductive layer. Etc.) In addition, the method used in the present invention is to add colored pigment particles to -14- this paper size applies Chinese National Standard (CNS) A4 specification (2.10 X 297 PCT) Shu ·: -------- tr --------- Line (Read the back of the precautions to fill out this page) ^ 3475 A7

5. Description of the invention (13) The transparent conductive layer or transparent coating mentioned above obtains a low transmittance (40 to 75%) transparent 2-layer film for use in a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer. Here, when we add colored pigment particles to the above-mentioned transparent conductive layer, the formation of the network structure in the precious metal particles is somewhat restricted due to the presence of the colored pigment particles (that is, the formation of conductive paths in the precious metal particles will be Banned). Therefore, in the present invention, the amount of the added color pigment particles is set to a small amount so that the formation of conductive paths in the noble metal particles is not prohibited (1 to 40 parts by weight of the color pigment particles per part by weight) Precious metal particles within the range), and obtain a low-transmittance (40 to 75%) transparent 2-layer film whose conductivity is not significantly impaired. Inevitably, it is important that when color pigment particles are added to the above-mentioned transparent conductive layer, the precious metal particles are added at a ratio of 1 to 40 parts by weight of precious metal particles per part by weight of the color pigment particles. On the other hand, when we add colored pigment particles to the transparent conductive layer, the part responsible for conductivity (transparent conductive layer) and the part responsible for low transmittance (transparent coating) are separated, so it can be done without harm. A transparent 2-layer film having a low transmittance (40 to 75%) was obtained under the conductivity of the transparent conductive layer. As mentioned above, since a small amount of colored pigment particles are added to the transparent conductive layer, or the colored pigment particles added to the transparent conductive layer have almost no effect on the conductivity of the transparent conductive layer. It is not always necessary to have conductive color pigment particles, but to be able to use -15- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) -Installation -------- Order --------- ^^ 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by Chuan 475 A7- ------ B7 __ —_ 5. Description of the invention (14) Carbon, titanium dioxide black, titanium oxynitride black 'composite oxide pigment, quinacridine pigment, anthraquinone pigment, perylene pigment, isonitrogen ( (Miscellaneous) Indanone pigment, azo-based pigment, copper phthalocyanine blue pigment, cobalt violet, molybdenum orange, ultramarine blue, Prussian blue, and titanium nitride. However, the particulate material is not limited to these as long as it is colored and its average particle diameter is 5 to 200 nm. In addition, we do not know the optical constants of the above-mentioned color pigments (n_ik; where η: refractive index; = -1; k: dispersion coefficient), but the present invention can be successfully completed because it is found that the first transparent conductive layer structure can be used To obtain good low reflectivity properties, the first transparent conductive layer structure includes a transparent 2-layer film formed on a transparent substrate and composed of a transparent conductive layer and a transparent coating. The main components of the transparent conductive layer are precious metal particles and color Pigment particles, and a binder matrix. The main component of the transparent coating is a binder matrix. The second transparent conductive layer structure includes a transparent 2-layer film formed on a transparent substrate and composed of a transparent conductive layer and a transparent coating. The transparent conductive layer is mainly composed of precious metal particles and a binder matrix, and the transparent coating is mainly composed of colored pigment particles and a binder matrix. In addition, the above-mentioned color pigment particles appear in the transparent conductive layer containing precious metal particles in the first transparent conductive layer structure, and the transparent conductive layer has been adjusted to have a low transmittance. As described above, the formation of network structures within the noble metal particles is somewhat restricted due to the presence of these colored pigment particles. Therefore, the conductivity of the transparent conductive layer is somewhat reduced. But * As mentioned above, because a small amount of color pigment particles are added to the transparent conductive layer (each weight part of color pigment particles contains 1 -16- ^ ^ long scale applies Chinese National Standard (CNS) A4 specifications ( 210 x 297 mm) " ^, τ * ^^ pack II --------- line (please read the precautions on the back before filling this page) Printed by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 513475 : A7. B7 V. Description of the invention (15) to 40 parts by weight of precious metal particles), so it does not jeopardize practical applications. In addition, even if the weather resistance of the color pigment particles used is not good, the color pigment particles added in advance will not be caused. The problem of weather resistance arises because these colored pigment particles are protected by a transparent coating layer formed on the transparent conductive layer. On the other hand, a transparent coating layer (which is mainly composed of colored pigment particles and a binder matrix) is formed On the transparent conductive layer (which is mainly composed of precious metal particles and a binder matrix) in the first transparent conductive layer structure, the transparent coating has been adjusted to a low transmittance. Therefore, as described above, the transparent layer The color pigment particles in the coating layer have almost no effect on the conductivity of the transparent conductive layer. In addition, as will be explained later, adding a small amount of color pigment particles to the transparent coating layer is sufficient to achieve the above-mentioned low transmission. (40 to 75%). Therefore, even if the weather resistance of the color pigment particles used is not good, the problem of weather resistance is rarely caused in the added color pigment particles because these color pigment particles are subject to the transparent coating. It is important here that the precious metal particles (precious metal-coated silver particles) and colored pigment particles according to the present invention must have average particle diameters of 1 to 100 nm and 5 to 200 nm, respectively. If The above-mentioned precious metal particles (silver particles coated with precious metals) are less than 1 nm, it is difficult to manufacture the particles and it is difficult to disperse them to make a coating liquid, which makes it impossible to be practically used. In addition, if they are larger than 100 Nanometer, because of the transparent 2-layer film formed, it will increase the scattering of visible light (eventually, it will increase the glare of the film), This makes practical application impossible. This -17- ^ paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '(Please read the precautions on the back before filling this page) Installation --- -Order --------- 513475 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of Invention (16) In addition, the average particle diameter used here represents that observed with a transmission electron microscope The average particle diameter of the particles. It is important for the same reason that the average particle diameter of the above-mentioned color pigment particles must be 5 to 200 nm. Next, the above-mentioned precious metal particles (which are composed of gold and / or platinum and silver) should be included. The transparent conductive layer is formed by applying a coating liquid for forming a transparent conductive layer on a transparent substrate and then performing heat treatment. As a result of performing this heat treatment, as described above, the silver particles partially coated with precious metal will form an alloy, or the silver particles coated with precious metal itself will be separated from the gold or platinum remaining on the surface of the silver particles or The compound consisting of gold and aluminum is combined to produce the above-mentioned precious metal fine particles. The above-mentioned noble metal particles have ideal properties for electric field protection and will eventually result in a transparent 2-layer film having a surface resistance of 10 to 5,000 Ω / □. In addition, the content of gold and / or platinum in the above-mentioned noble metal-coated silver particles falls within a range of 5 to 95% by weight. If the content of gold and / or platinum is less than 5% by weight, the weather resistance of the noble metal particles formed is sometimes poor; if the content is more than 95% by weight, the noble metal-coated silver particles are used. The economic benefits are minimal. In addition, it is preferable that the content of gold and / or platinum in the noble metal-coated silver particles falls within a range of 5 to 95% by weight to avoid the formation of alloys of gold, platinum, silver, and the like, and According to the above heat treatment conditions, the weather resistance and chemical resistance are slightly reduced. If the content of gold and / or platinum in the above-mentioned noble metal-coated silver particles exceeds 50% by weight, the noble metal formed by using the coating liquid for forming a transparent conductive layer will be micro-18. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm), 7 # pack -------- Order --------- (Please read the precautions on the back before filling this page ) 513475 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (17) The weight ratio of silver in the grain is reduced, but because the atomic weight of silver is half of the atomic weight of gold and platinum. In comparison, the reduction of the proportion is not so great when comparing the viewpoint of%, so the influence of silver on the properties of precious metal particles is still maintained. Next, the color pigment particles used are at least one or more types selected from the foregoing materials: carbon, titanium dioxide black, titanium oxynitride black, composite oxide pigments (such as oxide spinel black, titanium nickel oxide, Pigments consisting of titanium antimony nickel oxide, zinc iron oxide, nickel zinc cobalt titanium oxide, cobalt aluminum chromium titanium oxide, cobalt aluminum oxide, copper chromium manganese oxide, etc.), quinacridone pigments (such as quinacridone Red, etc.), anthraquinone pigments (such as anthraquinone red, etc.), perylene pigments, isoaza (hetero) indanone pigments (such as isoaza (hetero) indanone yellow, etc.), azo-based pigments (such as Yonghong 4R, etc.), copper phthalocyanine blue pigments (such as copper phthalocyanine blue, copper phthalocyanine blue, etc.), cobalt violet, molybdenum orange, ultramarine blue, Prussian blue, and titanium nitride. Especially when using titanium nitride particles as color pigment particles, the advantage is that a film with a transmittance is obtained by adding a smaller amount of color pigment particles to the transparent conductive layer or the transparent coating layer. This is because titanium nitride has a better coloring effect on the above-mentioned fine particles such as black titanium oxide, black titanium nitride oxide, and black spinel oxide. The above-mentioned black titanium oxide is a secondary oxide (T i 0 2. x) obtained, for example, by treating thorium oxide (T i 0 2) with large residuals around hydrogen at high temperature, and the isonitrogen titanium oxide is a kind of A nitrogen-containing titanium compound obtained by treating titanium oxide (Ti02) in the atmosphere surrounding ammonia at a high temperature. In addition, oxygen compounds such as iron, manganese, and kiosk are all black spinel oxides. This kind of black spinel oxidation-19 · This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297) (please read the precautions on the back before filling this page). 11 — — — — — ^ · 11 I 11 I--.) 13475 V. Description of the invention of printed clothing for the consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (18: The spinel structure of the material is represented by the chemical formula (C u, Fe, Mn)) ( Fe, Mn) 204 and is made of 33 to 36% by weight of copper oxide, 30 to 51% by weight of manganese oxide, and 13 to 35% by weight of iron oxide. In addition, the above-mentioned black titanium oxide may be an example of Obtained by a method of reacting titanium chloride with nitrogen in a plasma, a method of vaporizing metallic titanium powder and reacting in a plasma under an atmosphere surrounding nitrogen. As for the color transmitted by the film, The fact that a transparent conductive layer or a transparent coating layer coated with carbon particles is opposite and appears light brown. In the case of using both carbon particles and the above-mentioned precious metal particles, the color transmitted by the film is almost colorless. The reason is currently Not terribly, but it looks like because When noble metal particles and carbon particles are used, the optical constant n-ik of the film will have an effect in the desired direction. In addition, examples of the transparent conductive layer using the above-mentioned titanium nitride, black titanium oxide, black titanium nitride, etc. Here, the transmittance profile is similarly flat and the transmitted color is almost colorless. Here, it is also possible to use silicon dioxide-coated color pigment particles coated with silicon dioxide on the surface as such color pigments Particles. When using silicon dioxide-coated color pigment particles in a transparent conductive layer, it is expected to improve the conductivity of the transparent 2-layer film; and when using a silicon dioxide-coated color in a transparent coating layer In the case of pigment particles, it is expected that the mechanical strength of the transparent 2-layer film can be improved. That is, a coating liquid for forming a transparent conductive layer containing color pigment particles is prepared by adding a color pigment particle dispersion, and the dispersion The color pigment is micro-20 using polymer dispersant and surfactant, etc.- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read first Note the surface to fill out this page)

Hi clothing -------- tr --------- ^ 9— Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of the invention (19) The particles are dispersed and coated with precious metals Prepared by colloidal dispersion of silver particles. In addition, this coating liquid for forming a transparent conductive layer is coated on a transparent substrate, and a network structure of the above-mentioned noble metal-coated silver particles (precious metal particles) is formed during the drying process. However, as mentioned earlier, the formation of the network structure in the precious metal particles is somewhat restricted due to the presence of colored pigment particles, and although it has not reached a level that jeopardizes practical applications, in some cases the transparency has increased somewhat 2- Surface resistance of the film. Although the reason is not so clear at present, when the colored pigment particles coated with silica are used in this example, the formation of the above network structure is rarely banned, and even when a very large amount of In the case of silica-coated color pigment particles, the surface resistance of the transparent 2-layer film can be kept very low. When the color pigment particles coated with silicon dioxide are used in the transparent coating layer, the bond between the color pigment particles in the transparent coating layer and the binder matrix is strengthened by the above-mentioned silicon dioxide-coated layer. And, therefore, the mechanical strength of the transparent coating can be improved. It is possible to set the amount of silica to be coated in the above-mentioned silica-coated color pigment particles so as to contain silica in a range of 5 to 100 parts by weight per 100 parts by weight of the color pigment particles. If it contains less than 5 parts by weight of silicon dioxide, a sufficient effect of coating silicon dioxide cannot be obtained. On the other hand, if more than 100 parts by weight of silicon dioxide is used, in some cases the color pigment in the color pigment particles coated with silicon dioxide will be reduced, resulting in the need to add a very large amount of -This paper size applies to China National Standard (CNS) A4 (210 X 297 mm): ---- 7 ----- clothing -------- tT --------- $ · (Please read the precautions on the back before filling this page) 513475 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ______B7 _ 5. Description of the invention (2) Silicon dioxide coated color pigment particles The surface resistance of the transparent 2-layer film is increased. Next, we can prepare a first coating liquid for forming a transparent conductive layer containing silver particles coated with precious metals and color pigment particles (color pigment particles coated with silicon dioxide) by the following methods, and This first coating liquid produces a first transparent conductive layer structure; a second coating liquid for forming a transparent conductive layer containing silver particles coated with precious metal is prepared, and a second transparent conductive layer is manufactured using this second coating liquid Layer structure. First, it is prepared by conventional methods (for example, the Carey-Lea method in the papers of Am. J. Sci., 37, 47 (1 889) and Am, J. Sci., 38 (1889)). Colloidal dispersion of silver particles. I That is, it is prepared by simply adding a mixture of a water-soluble iron (II) sulfide solution and a water-soluble sodium citrate solution and reacting it with a water-soluble silver nitrate solution, filtering and washing the precipitate, and then adding pure water to prepare A colloidal dispersion of silver particles (silver: 0.1 to 10% by weight). This method for preparing a colloidal dispersion of silver particles may be any method without limitation, as long as it can disperse silver particles having an average particle diameter of 1 to 100 nm. The reducing agent is added to the colloidal dispersion of silver particles thus obtained, and then an alkali metal aluminate solution or an alkali metal platinum salt solution is further added to the colloidal dispersion, or an alkali metal aluminate solution and Alkali metal platinate solution or mixed solution of alkali metal aluminate and alkali metal platinate, so that the surface of the silver particles is coated with gold or platinum alone or composed of gold and platinum Compound to obtain a coating coated with precious metal-22- sheet paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) I. ^ ----- pack --------- order --------- (Please read the notes on the back before filling this page) Chuan 475 A7

V. Description of the invention (21) Colloidal dispersion of coated silver particles. If necessary, a small amount of dispersant will be added to the silver particle colloidal dispersion, alkali metal aluminate solution, alkali metal platinate solution, or alkali metal during the preparation and treatment of the silver particles coated with precious metal. It is contained in at least one of a mixed solution of a gold salt and an alkali metal platinum salt. During the above-mentioned preparation process of the noble metal-coated silver particles, a reaction of coating gold or platinum or a compound composed of gold and platinum on the surface of the silver particles occurs, because when the aurate and platinum salts are reduced, As a result, when platinum and platinum are present, a very large amount of fine silver particles already exist in the liquid, and therefore the growth on the surface will take the silver particles as the nucleation ratio from the viewpoint of energy to nucleate by gold or platinum alone. (Uniform nucleation) under more favorable conditions. Necessarily, because it is speculated that when gold and platinum are produced by reducing aurate and platinate, a very large amount of fine silver particles already exist in the liquid, preferably the preparation of silver particles coated with precious metal During the treatment, the timing of adding the aurate solution or the platinate solution, or the aurate solution and the platinate solution or a mixture thereof, and the above-mentioned reducing agent is adjusted so that the aurate solution or the platinate is added At least the aforementioned reducing agent is added to the solution, or the aluminate solution and the platinate solution or a mixture thereof. In other words, when they are in a mixed state, the reducing agent and the aurate solution or the platinate solution, the reducing agent and the aurate solution and the platinate solution, or the reducing agent and the aurate solution When a mixed solution of P-platinate is added to the silver microparticle colloidal dispersion, in this step, the gold salt solution or lead salt solution, gold salt solution and platinum salt solution, or gold salt and platinum The mixed solution of the acid salt and the above also 23- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ▼ Pack ----- --- Order --------- line ^^-· Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 513475 A7 ______ B7 V. Invention Description (22) Original The agents are mixed to reduce the gold and platinum salts to produce gold and platinum, and the nucleation (uniform nucleation) of gold and platinum occurs separately. Therefore, even if a gold salt solution, a uranate solution, and the like are added to the silver microparticle colloidal dispersion after mixing them with a gold salt solution and a uranium salt solution, the compound of gold or platinum alone does not occur. Reaction coated on the surface of the silver particles. In addition, as the reducing agent, hydrazine [N2H4], borohydride (for example, sodium borohydride [NaBH4], etc.), and formaldehyde can be used. Among them, any reducing agent can be used and is not limited to these reducing agents, as long as the aggregation of silver fine particles does not occur at the time, and gold salts and platinum salts can be reduced to gold and platinum. For example, the reduction reactions of reducing potassium aluminate [KAu (0H) 4] and potassium platinum [K 2 P t (Ο Η) 6] with hydrazine and sodium borohydride are shown by the following chemical formulas: KAu (〇 H) 4 + 3 / 4N2H4- > Au + K〇H + 3H2〇 + 3 / 4N2 K2Pt (〇H) 6 + N2H4- > Pt + 2K〇H + 4H2〇 + N2

KAli (OH) 4 + 3 / 4NaBH4- > Au + K〇H + 3 / 4NaOH + 3 / 4H3B〇3 + 3 / 2H2T K2Pt (〇HU + NaBH4- > Pt + 2K〇H + NaOH + H3B〇 3 + 2H2T When the above-mentioned sodium borohydride is used as a reducing agent, the phenomenon that the electrolyte concentration increases due to the reduction reaction can be determined by the above reaction chemical formula, and therefore it will be described later as will be explained later. It makes the silver particles easily aggregate. Therefore, the inconvenience is that the silver concentration in the colloidal dispersion of the silver particles used cannot be increased because the amount of the reducing agent added is limited. -24- This paper scale applies Chinese national standards (CNS) A4 specification (210 X 297 mm), Z · installation -------- Order --------- (Please read the precautions on the back before filling this page) 513475 A7 _ B7 V. Explanation of the invention (23) On the other hand, when using the above-mentioned hydrazine as a reducing agent, as can be determined by the above reaction chemical formula, a small amount of electrolyte will be generated due to the reduction reaction, so hydrazine is A preferred reducing agent. In addition, in addition to alkali metal aluminate and alkali metal Salts other than acid salts, such as chlorochloric acid [HauC14], platinum chloric acid [H2PtCl6], chloroauric acid salts (such as Ba 11 (: 14 and KivuCl4, etc.), chloroplatinates (Na2PtCl6 & K2PtCl6, etc.) play a role When gold and platinum are coated with starting materials, the reduction reaction due to hydrazine is shown below: XAuC14 + 3 / 4N2H4- > Au + XC1 + 3HC1 + 3 / 4N2 X2PtCl6 + N2H4- > Pt + 2XCl + 4HCl + N2 (X = H, Na, K, etc.) When using chlorochloric acid, etc. in this way, not only the electrolyte concentration is increased due to the reduction reaction, but also when using the aurate and The case of platinum salts also increases the generation of chloride ions when compared. Therefore, these chloride ions will react with the silver particles to produce sparingly soluble silver chloride. As a result, it is difficult to use such materials for forming transparent according to the present invention. The starting material for coating the conductive layer with liquid. It is then preferable to reduce the precious metal-coated silver according to the method described above by desalting methods such as infiltration, electroosmosis, ion exchange, ultrafiltration, etc. The concentration of electrolyte contained in the particulate colloidal dispersion. This is because in general If the electrolyte concentration is not reduced, the colloid will have an aggregation effect with the electrolyte. This phenomenon is well known as the Schlöss-Hadi rule. Next, the desalted colloidal dispersion of silver particles is concentrated to obtain Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling out this page) Installation -------- Order ---%, Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Consumption Cooperative, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Consumption Cooperative, 513475 A7 B7 V. Description of Invention (24) A concentrated dispersion of precious metal-coated silver particles, and then colored pigment particles (coated with silica dioxide) The color pigment particles) dispersion is mixed with a solvent, or an organic binder is further added and mixed to adjust its composition (particle concentration, water concentration, etc.) to obtain a transparent conductive layer used in the method for manufacturing a transparent conductive layer structure. First coating liquid. In addition, the concentrated dispersion of the noble metal-coated silver microparticles is obtained by performing concentration on the desalted colloidal dispersion of the noble metal-coated silver microparticles described above. Then, a single solvent or a solvent containing an inorganic binder is added to the concentrated dispersion of the silver particles coated with precious metals to adjust the composition (particle concentration, water concentration, etc.), so as to obtain a transparent conductive layer structure manufacturing method. A second coating liquid for forming a transparent conductive layer. When ultrafiltration is used as the above-mentioned desalting method, as described later, this kind of ultrafiltration also has a concentration effect, so that it is possible to perform desalting and concentration at the same time. Inevitably, the order in which the colloidal dispersion in which the silver microparticles are dispersed is subjected to decontamination and concentration is selected based on the requirements of the processing method used, and can be simultaneously processed when a method such as ultrafiltration is used. In addition, the above solvents can be replaced with a concentrated dispersion of noble metal-coated silver particles or a color pigment particle (silica dioxide-coated color pigment particle) dispersion contained in the solvent (that is, Said that the use of a single solvent can be omitted). In addition, it is possible to add and mix inorganic binders to the original or concentrated dispersion of silver particles coated with precious metals, or it is possible to add dispersions of colored pigment particles (color pigment particles coated with silica) or It is a solvent containing an inorganic binder. Whichever method is used. -26- Chinese paper standard CNS A4 specification (210 X 297 mm); 7 ------------ Order --------- line (please Read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 ______B7_____ V. Description of the invention (25) In addition, the above-mentioned color pigments can be obtained by mixing color pigment particles with dispersants and solvents. Particle dispersion, using a dispersion device such as a paint agitator, silica mill, ultrasonic spreader, etc. to perform dispersion to a particle diameter of 5 to 200 nanometers, and then reduce the dispersion by means of ion exchange Electrolyte concentration (desalting effect). In addition, the above-mentioned silica-coated color pigment particle dispersion can be obtained by the following method: (1) The silica-coated color pigment particles and dispersant having a surface previously coated with silica. And solvent mixing, using a dispersing device such as a paint agitator, silica mill, ultrasonic disperser to perform the dispersing effect until the particle diameter of 5 to 200 nanometers has been dispersed, and then reducing the dispersion by methods such as ion exchange Electrolyte concentration (desalting effect); (2) mixing the above-mentioned color pigment particles with an alkyl silane such as tetraethoxysilane, or a silica sol of a hydrolyzed alkyl silane, and a solvent, and using the above dispersion The device performs the dispersing effect until the particle diameter of 5 to 200 nanometers has been dispersed, and then performs the desalination function; (3) The color pigment particles are mixed with the dispersant and the solvent, and the dispersing device is used to perform the dispersing effect to achieve the dispersed effect. With a particle diameter of 5 to 200 nanometers, silica sol is added and then coated with silicon dioxide by stirring or ultrasonic treatment , And then go to salt and other effects. In the above coating liquid for forming a transparent conductive layer, the standard for coating the surface of silver particles with gold alone or platinum or a compound consisting of gold and platinum refers to the diameter of the particles coated with gold or lead alone. Or the compound consisting of gold and platinum has not changed significantly before and after, and technically has adopted -27- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ♦: ----- -------- Order --------- ^^ 1 (Please read the precautions on the back before filling this page) 513475 A7 B7 V. Description of the invention (26) Transmission electron microscope ( TEM) and composition analysis (EDX: energy diffusivity X-ray analyzer) to observe the particles, and in addition EXAFS (extended X-ray absorption fine structure) to obtain gold or platinum alone or a compound composed of gold and uranium The number of coordinates is determined, and it is determined that gold or platinum alone or a compound composed of gold and platinum is uniformly dispersed on each particle. In addition, it depends on whether a gold salt solution and a platinum salt solution or a gold salt and platinum are used during the coating process (that is, the preparation process of the noble metal-coated silver particles) during the coating process (that is, the precious metal-coated silver particles). The solution of the acid salt depends on the timing of adding such a solution and the concentration of the aluminate and platinum salt used, and the various coating forms of the compound composed of gold and platinum on the silver particles are considered. That is, it is possible to coat all or part of the surface of the silver particles with gold and coat the entire unit with platinum, or to coat all or part of the surface of the silver particles with platinum and coat the entire unit with gold, Or consider a method in which the entire surface of the silver particles is coated with gold or platinum alone without overlapping or alloying. When the baking is performed during the formation of the transparent conductive layer under a heat treatment condition of, for example, 200 ° C, the conductive particles of the transparent conductive layer formed using the coating liquid for forming a transparent conductive layer as described above can be used as described above. Inside, the alloy layer is formed by the thermal diffusion of gold, platinum, silver, etc., but the details are not neat. Inevitably, as described above, the above-mentioned conductive particles composed of gold, silver, and the like in the transparent conductive layer do not represent silver particles coated with precious metals, but represent precious metal particles in the specifications of the present invention. 'In addition, it can be performed by ordinary methods such as decompression evaporation and exceeding 泸 -28- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling (This page)-installed ---- tT --------- · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 3475 A7 B7 Five Printed and Invention Notes of the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (27 The concentration of the colloidal dispersion of the noble metal-coated silver particles described above. In addition, the water content of the coating liquid used to form the transparent conductive layer should be 1 to 50% by weight. If the water content exceeds 50% by weight, However, there are some examples that can be easily caused by the high surface tension of water during the drying after the coating liquid for forming a transparent conductive layer has been applied to the transparent substrate. The problem of directing can be solved by adding a surfactant to the coating liquid used to form the transparent conductive layer. However, another problem that can occur is that the coating can be quickly generated when the surfactant is added. defect. However, it is preferable that the water content in the coating liquid for forming the transparent conductive layer is 1 to 50% by weight. In addition, the above-mentioned solvent is not particularly limited and is based on the application method and the film manufacturing method It is selected based on the needs. Examples are alcohol solvents such as ethanol, ethanol, isopropanol, butanol, phenethyl alcohol, diacetone alcohol, such as acetone, methyl ethyl ketone (MEK), isobutyl ketone (MIBK), ring Ketone solvents such as hexanone and isophorous boron, for example, diol derivatives such as propylene glycol methyl ether and propylene glycol ether, methylformamide, N-methylformamide, dimethylformamide (DMF), dimethyl Acetylamine, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, etc., but it is not limited to such solvents. Next, it can be used to form a transparent conductive material. The first and second layers are coated with a liquid to obtain the first and second transparent conductive layer structures. Such structures are mainly composed of a transparent substrate and a transparent conductive layer formed on the transparent substrate and the top of the transparent conductive layer. Group of transparent 2-layer film made of transparent coating -29- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm): τ ------------ Order --------- Line ( (Please read the precautions on the back before filling this page) 513475 A7 ____B7_____ 5. Description of the invention (28) The operation of forming the above transparent 2-layer film on the transparent substrate can be performed by the following methods: First, by spraying, for example The coating method, spin coating method, wire rod coating method, scalpel coating method, gravure coating method, and roller coating method will be used to form the first coating liquid for the transparent conductive layer (its main Composition consisting of a solvent, noble metal-coated silver particles having an average particle diameter of 1 to 100 nm, and color pigment particles (silica dioxide-coated color pigment particles) having an average particle diameter of 5 to 200 nm. Dispose on transparent substrates such as glass substrates and plastic substrates, and then dry as needed. The cover is then coated with a coating liquid for forming a transparent conductive layer (its main composition is, for example, silica sol, etc.) by the above mechanism. Next, after the cover is coated, heat treatment is performed at a temperature of, for example, 50 to 350 ° C to ripen the coating liquid for forming a transparent conductive layer and form the above-mentioned transparent 2-layer film. In addition, as mentioned above, the mixing ratio of the color pigment particles (silica dioxide-coated color pigment particles) and the precious metal-coated silver particles in the coating liquid for forming a transparent conductive layer is per weight. The above-mentioned noble metal fine particles are mixed in a proportion of 1 to 40 parts by weight of the noble metal fine particles (parts of the color pigment fine particles (silica dioxide-coated color pigment fine particles)). If the amount of color pigment particles (silica dioxide-coated color pigment particles) added is too small, the transmittance will be too high to adjust it to the above specified range (40 to 75%), and if If the amount added is too large, the transmittance is reduced and the conductivity of the transparent 2-layer film is prohibited for the reasons mentioned above. . On the other hand, by, for example, spray coating method, spin coating method, wire -30- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) '(Please read the precautions on the back first (Fill in this page again)-Install -------- Order --------- Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (29) Mechanisms such as the rod coating method, scalpel coating method, gravure coating method, and roller coating method will be used to form the second coating liquid for the transparent conductive layer (its main composition is a solvent And precious metal-coated silver particles with an average particle diameter of 1 to 100 nanometers) are coated on transparent substrates such as glass substrates and plastic substrates, and then dried as required. Then, the outer cover is coated with a coating liquid (its main composition is, for example, silica sol, etc.) for forming a transparent conductive layer by the above machine. Next, a heat treatment is performed at a temperature of, for example, 50 to 350 ° C after the cover is coated so as to ripen the coating liquid for forming a transparent conductive layer and form the above-mentioned transparent 2-layer film. In addition, it is preferable that a mixing ratio of the color pigment particles (color pigment particles coated with silicon dioxide) and silica sol in the coating liquid for forming a transparent coating layer is silica sol (S i 0 2 ) / Color pigment particles (color pigment particles coated with silica) = 2 to 50 (weight ratio). If the amount of color pigment particles (silica dioxide-coated color pigment particles) added is too small, the transmittance will be too high to adjust it to the above specified range (40 to 75%), and if If the amount added is too large, the transmittance is reduced and the conductivity of the transparent 2-layer film is prohibited for the reasons mentioned above. Although the silver particles coated with precious metals are protected by gold or platinum alone or a compound composed of gold and platinum, there are no problems related to the above heat treatment at 50 to 350 ° C. If the silver particles are not coated, Covered with gold or platinum, its surface resistance will increase due to oxidation and diffusion, and degradation of the film will occur when the temperature exceeds 200t. In addition, when using the first coating liquid form for forming a transparent conductive layer -31- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm); Γ ----- · I.- ----- Order --------- line (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of Invention (3G) When the transparent 2-layer film of the first transparent conductive layer structure is used, the improvement of conductivity, the improvement of strength, and even the improvement of weather resistance can be achieved at the same time, because when the outer cover is coated by the above method for forming transparent When the coating liquid of the conductive layer (its main composition is, for example, silica sol, etc.), the cover silica sol (this silica sol will become the adhesive matrix whose main composition is the silica treated by the above heat treatment) will leak. In the transparent conductive layer formed by coating the coating liquid for forming a transparent conductive layer in advance, the distance between the precious metal-coated silver particles and the color pigment particles (silica dioxide-coated color pigment particles) Within space. In addition, the transparent conductive layer (in which the silver particles coated with noble metal and color pigment particles (color pigment particles coated with silicon dioxide) are dispersed in the above-mentioned adhesive matrix mainly composed of silicon dioxide) The refractive index η in the constant n-ik is not very large, but its dissipation coefficient k is extremely high. Therefore, the transparent 2-layer film structure composed of the transparent conductive layer and the transparent coating layer can significantly reduce the transparent 2 -The reflectivity of the layer film. On the other hand, when a transparent 2-layer film of the second transparent conductive layer structure is formed using a second coating liquid for forming a transparent conductive layer, improvement in strength and even further improvement in weather resistance can be achieved at the same time, because When a coating liquid for forming a transparent conductive layer is coated with an outer cover by the above method (its main composition is color pigment particles having an average particle diameter of 5 to 200 nanometers (color pigment particles coated with silicon dioxide), and For example, silica sol, etc.), containing the color pigment particles (color pigment particles coated with silicon dioxide) and covering the silica sol (this silica sol will become its main composition to include color pigment particles after the above heat treatment). (After 2-32- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) '" " 1 -------- ^ --------- ( Please read the precautions on the back before filling out this page) 513475 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 1. Description of the invention (31) Silica coated color pigment particles) Silica binder matrix) Pervious The noble metal-coated silver fine particle layer was applied in advance to the coating liquid for forming the transparent conductive layers (silver fine particles consisting essentially of a solvent and over a noble metal coating of) the formed. However, the size of the space in the noble metal-coated silver particle layer appears to be the same as the size of the silver particle itself, and it appears to leak to the surface during the coating of the coating liquid for forming the transparent conductive layer. Almost all of the above-mentioned spaces are silica sols with a small particle size, and only a few colored pigment particles (color-coated silica particles coated with silicon dioxide) leak into the space. In addition, the transparent conductive layer, which has been formed by baking the above-mentioned noble metal-coated silver particles (its main composition is the noble metal-coated silver particles with an average particle diameter of 1 to 1000 nanometers and a binder matrix) ) And the refractive index η in the optical constant n-ik of the transparent coating (its main composition is color pigment particles (color pigment particles coated with silicon dioxide) and inorganic binders such as silica sol) However, the transparent 2-layer film structure composed of the transparent conductive layer and the transparent coating layer can significantly reduce the reflectance of the transparent 2-layer film. The silica sols that can be used are: polymers that have undergone hydrolysis and dehydration polymerization by adding water and acidic catalysts to ortho-alkyl silicates, or that have been polymerized into tetramers Polymer and pentamer, etc., are commercially available alkyl silicate solutions that undergo hydrolysis and dehydration polymerization. In addition, when the dehydration polymerization reaction is performed, the viscosity of the solution will increase until it is finally hardened. Therefore, the degree of dehydration polymerization is adjusted so as not to be greater than that which can be coated on a transparent substrate such as a glass substrate or a plastic substrate. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ----- · I ------ Order --------- line (Please read the note on the back first Please fill in this page again for matters) 513475 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs V. Upper limit of viscosity of invention description (32). I have no special restrictions on the degree of dehydration polymerization, as long as the level is not greater than the upper limit of the viscosity, but it is better to make the degree of dehydration polymerization to 500 when considering the film strength and weather resistance. To 3,000 weight average molecular weight. In addition, when the transparent 2-layer film is heated and baked to obtain a hard silicate film (its main composition is silicon dioxide), the dehydration of the hydrolyzed polymer of the alkyl silicate has not been completely completed. Polycondensation reaction. In addition, magnesium fluoride, alumina sol, titania sol, and zirconia sol can be added to adjust the refractive index of the transparent coating and change the reflectance of the transparent 2-layer film. To the silica sol, a hydrogen sulfide-containing compound such as r-hydrosulfopropyldimethoxysilane can also be added. Since the hydrogen-sulfur group (SH group) can form a fairly strong bond with gold, when the precious metal particles containing gold are used, the interface strength between the f metal particles and the binder matrix can be improved and its film can be improved. Strength and weather resistance. • In addition, the above-mentioned first or second coating liquid for forming a transparent conductive layer can also be produced by adding silica sol as an inorganic binder component. The inorganic binder component is averaged in addition to the solvent and dispersed in this solvent. Precious metal-coated silver particles with a particle diameter of 1 to 100 nanometers and colored pigment particles with an average particle diameter of 5 to 200 nanometers, or an average particle diameter of 1 to 100 except for solvents and dispersed in this solvent In addition to the silver-coated silver particles coated with a precious metal, a binder matrix composed of the transparent conductive layer is also included. At the same time, in this example, the same transparent 2-layer film can also be obtained by coating the first or second coating liquid (including silica sol) used to form the transparent conductive layer, and then drying it if necessary -34 -This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)-丨. -------- Order --------- (Please read the note on the back first Please fill in this page again for details) 513475 A7 B7 V. Description of the invention (33) The coating method for forming a transparent conductive layer cover is performed by the above method. Therefore, the first or second transparent conductive layer structure according to the present invention has good conductivity and low reflectance and its visible light transmittance has been adjusted to fall within a specified range (40 to 75%). Therefore, it can be applied to, for example, the above-mentioned Brown Tube (CRT), Plasma Display Panel (PDP), Fluorescent Display Tube (VFD), Field Emission Display (FED), Electro-Luminescence Display (ELD), and Liquid Crystal Display (LCD) ) And other parts of the front panel of the display. In addition, with the display according to the present invention, the first or second transparent conductive layer structure is used as its front panel with its transparent 2-layer film side facing downward, thereby improving its contrast and giving it an antistatic effect. And the effect of electric field protection and the effect of reducing the surface reflection of its display screen. In addition, the coating liquid for forming a transparent conductive layer according to the present invention has the effect of generating a transparent conductive layer structure, and the transparent conductive layer structure has many properties such as good conductivity, low reflectivity, weather, and chemical resistance, and The visible light transmittance of the transparent 2-layer film having this structure is adjusted to be within a prescribed range of less than 100%. Examples of the present invention will now be described in the form of specific items, but the present invention is not limited to these examples. In addition, in addition to "%" in the transmittance, reflectance, and color tone, "%" means "weight%" and "part" means "weight part". [Example 1] A colloidal dispersion of silver fine particles was prepared by the above-mentioned Carey-Lea method. -35- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ▼ Packing --- 1T --------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (34) Specifically, 39 grams of water-based 23% iron sulfide (II) solution and After 48 grams of a 37.5% sodium citrate solution mixture was added to 33 grams of an aqueous 9% silver nitrate solution, the precipitate was filtered and washed, and then pure water was added to prepare a colloidal dispersion of silver particles. (Silver: 0.15%). Next, 8.0 grams of an aqueous 1% hydrazine monohydrate (N2H4 · H20) solution was added to the colloidal dispersion of silver particles, and then 480 grams of an aqueous potassium aluminate [KAu (OH) 4] solution was added. (Gold: 0.075%) and a mixture of 0.2 g of an aqueous 1% polymer dispersant solution and stirred to obtain a colloidal dispersion of gold-coated silver particles coated with gold only. This colloidal dispersion of gold-coated silver particles is desalted with an ion exchange resin (Mitsubishi Chemical Corporation, trade name: DUion SK1B, SA20AP) and then concentrated by ultrafiltration to obtain a concentration of gold-coated silver particles. Dispersion (Liquid A). Next, 5 grams of carbon particles (MA7, Mitsubishi Chemical Corporation) and 0.25 dispersant were mixed with 44.75 grams of water and 50 grams of ethanol, and dispersed with the zirconium beads by a paint shaker. Then, the product was desalted by the above-mentioned ion exchange resin to obtain a carbon fine particle dispersion (Liquid B) having a dispersed particle diameter of 85 nm. The first coating liquid (0.08% silver, 0.32% gold, 0.05% carbon, 11.2% water, 73.3% EA, and 15.0% DAA) used to form the transparent conductive layer was obtained by applying Liquid B, ethanol (EA), and diacetone alcohol (DAA) were added to liquid A. The observation results of the coating liquid used to form the transparent conductive layer were obtained with a transmission electron microscope (TEM). The average particle diameter of the gold-coated silver particles and the carbon particles was -36. National Standard (CNS) A4 Specification (210 X 297 Public Love) (Please read the precautions on the back before filling this page) _Installation -------- Order --------- Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 513475 A7 B7 5. Invention Description (35) are 6.0nm and 34nm respectively. Next, this coating liquid for forming a transparent conductive layer was spin-coated (150 rpm (revolutions per minute), 120 seconds) on a glass substrate (soda-lime glass having a thickness of 3 mm) heated to 40 ° C. ) And then spin-coated (150i * pm, 60 seconds) with silica sol. In addition, the product was matured at 180 ° C for 20 minutes to obtain a glass substrate with a transparent 2-layer film. The transparent 2-layer film is made of transparent conductive material including precious metal particles, color pigment particles, and a silicon dioxide adhesive matrix. Layer and a transparent coating (mainly composed of silicon dioxide) including a silicate film, that is, a transparent conductive layer structure according to Example 1 of the present invention. Here, the above silica sol was obtained by adding 0.02 g of 7-hydrosulfopropyltrimethoxysilane to 100 g of liquid C. The above liquid C is prepared by using 19.6 parts of methyl silicate 51 (trade name,

Co 1 coat company), 57.8 parts of ethanol, 7.9 parts of an aqueous 1% nitric acid solution, and 14.7 parts of purified water to obtain a substance having a solid concentration of SiO 2 (silicon dioxide) of 10% and a weight-average molecular weight of 1,730 Then, this material is diluted with a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (I PA / NBA = 3/1) to a substance with a final solid concentration of SiO 2 of 0.8%. In addition, the properties of the transparent 2-layer film (visible light transmittance, standard deviation of transmittance, color tone, bottom reflectance / bottom wavelength, surface resistance) formed on the glass substrate are shown in the following table lb. The bottom reflectance refers to the minimum reflectance within the reflectance profile of the transparent conductive layer structure, and the bottom wavelength refers to the wavelength at which the reflectance is the smallest. # -37- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) " " ~~ (Please read the precautions on the back before filling this page) -------- ^ --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of the invention (36) In addition, the reflectance profile of the transparent conductive layer structure according to Example 1 of the present invention is made in The first figure and the transmittance profile are created in the second figure. The transmittance of this transparent 2-layer film without a transparent substrate (glass substrate) at a wavelength of 5 nm in the visible wavelength region (380 to 780 nm) is found as follows . That is, the transmittance (%) of the transparent 2-layer film excluding the transparent substrate = [(transmittance determined by the transparent substrate) / (transmittance of the transparent substrate)] X 100 〇 Unless otherwise specified, Otherwise, the transmittance and transmission profile of the transparent 2-layer film that does not include a transparent substrate are used as the transmittance and transmission profile of the present invention. In addition, in each of the examples and comparative examples, the film thickness of the transparent 2-layer film formed on the glass substrate was measured by observing the cross section of the film with the above-mentioned TEM. It is in the range of 100 to 100 nanometers and falls in the range of 40 to 80 nanometers for each clear coating. In addition, a surface resistance meter (Loresta AP MCP-T400) manufactured by Mitsubishi Chemical Corporation was used to determine the surface resistance of the transparent 2 · layer film. The hue and visible light transmittance were measured using a hue meter (HR-200) manufactured by Murakami Color Research Laboratory. The reflectance and reflection and transmission profiles were measured using a spectrometer (U-4000) manufactured by Hitachi. In addition, the paper size of the gold-coated silver particles is -38- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) * --- J ----- pack ---- ---- Order --------- (Please read the precautions on the back before filling out this page) 513475 A7 B7 V. Description of the invention (37) The particle diameter is made by a transmission electron microscope manufactured by JEOL. Assessed. [Example 2] 10 g of composite oxide particles of iron, manganese, and copper (product of TMB # 3550 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and 0.5 g of dispersant and 89 5 grams of diacetone alcohol are mixed and spread with chromium beads using a paint shaker. Then, the product was desalted with an ion exchange resin to obtain a composite oxide fine particle dispersion (liquid D) of iron, manganese, and copper having a dispersed particle diameter of 98 nm. In addition to using Liquid D instead of Liquid B to obtain a first coating liquid (0.08% silver, 0.32% gold, 0.15% iron oxide bell copper (? 6 ^ 11 彳 11-0), 10.7) for forming a transparent conductive layer, 10.7 % Of water, 73.7% of £ 8, and 15.0% of DAA) and the fact that liquid C is used as the silica sol liquid, has a transparent conductive layer (including precious metal particles, color pigment particles, and The glass substrate of a transparent 2-layer film (that is, the transparent conductive layer structure according to Example 2) composed of a silicon adhesive matrix) and a transparent coating (including a silicate film whose main composition is silicon dioxide) is in accordance with Example 1 Method. In addition, the film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 1b below. In addition, the reflectance profile of the transparent conductive layer structure according to Example 2 of the present invention is made in FIG. 3 and the transmittance profile is made in FIG. 4. [Example 3] f -39- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-Order -------- -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China 513475 A7 B7 V. Description of the invention (38) Hydrolyzing titanium chloride with an alkaline aqueous solution and treating the obtained titanium hydroxide with ammonia at 80 (TC) Titanium oxynitride black with an average particle diameter of 30 nm (15.5% nitrogen) was obtained. 5 grams of such titanium oxynitride black particles and 0.5 grams of a dispersant were mixed with 94.5 grams of ethanol. The paint agitator was used to disperse the beads. Then the product was desalted with ion exchange resin to obtain a nitrogen oxide titanium oxide black with a dispersed particle diameter of 93 nm, a particulate dispersion (liquid E, 5% nitrogen oxidation). Titanium black). In addition to using Liquid E instead of Liquid B to obtain a first coating liquid (0.08% silver, 0.32% gold, 0.1% titanium oxynitride (TixOyNz), and 10 · 7%) for forming a transparent conductive layer. Water, EA of 73 · 8¾, and DAA of 15.0%), liquid C as the silica sol liquid, and the liquid In addition to the fact that it is trans-coated on a glass substrate that has been heated to 351, it has a transparent conductive layer (including precious metal particles, color pigment particles, and a silicon dioxide adhesive matrix) and a transparent coating (including a silicate film, A glass substrate with a transparent 2-layer film (that is, a transparent conductive layer structure according to Example 3) composed of silicon dioxide) was obtained according to the method in Example 1. The transparent 2 film will be formed on the glass substrate. -The film properties of the layer film are shown in Table 1b below. In addition, the reflectance profile of the transparent conductive layer structure according to Example 3 of the present invention is made in Figure 5 and its transmittance profile is made in Figure 6. [Example 4] 4 g of this kind of titanium nitride particles (Net suren company) and 0.2 g of dispersant were mixed with 25 g of water R 10.8 g of ethanol, and spread with cobalt beads using a paint agitator. Then, Based on the above-mentioned ion exchange resin -40- I paper standard common Chinese national standard (CNS) A4 specification (21G X 297 public) (please read the precautions on the back before filling this page) -------- Order -------- Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the Consumer Cooperative Cooperative, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative 513475 A7 — B7 V. Description of the invention (39) Desalting the product to obtain a dispersion of titanium nitride particles with a particle diameter of 80 nm (liquid F) Except the use of a concentrated dispersion of gold-coated silver particles (prepared in the same manner as in Example 1) and liquid F in place of liquid B and addition of acetone, ethanol (EA), and diacetone alcohol (DAA) to obtain The first coating liquid (0.08% silver, 0.32% gold, 0.2% titanium nitride, 10.8% water, 10.0% acetone, 73.6% EA, and 5.0% DAA) to form a transparent conductive layer And a silica sol liquid obtained by adding 0.005 g of r-hydrosulfopropyltrimethoxysilane to 100 g of liquid C-2 (explained below); having a transparent conductive layer ( Including precious metal particles, titanium nitride particles, and silicon dioxide adhesive matrix) and transparent coating (including silicate film, whose main composition is silicon dioxide) is a transparent 2-layer film (that is, according to Example 4) Glass substrate with transparent conductive layer structure) After the method of Example 1 obtained. The above liquid C-2 is prepared by using 19.6 parts of methyl silicate 51 C (trade name Co. Coat), 57.8 parts of ethanol, 7.9 parts of an aqueous 1% nitric acid solution, and 14.7 parts of purified water A substance having a solid concentration of SiO 2 (silicon dioxide) of 10% and a weight-average molecular weight of 1,530 was obtained, and then a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA II) was obtained. 3/1) This substance is diluted to a substance having a solid concentration of SiO 2 of 0.8% in the end. In addition, as a result of observation of the coating liquid for forming a transparent conductive layer, the average particle diameters of the gold-coated silver particles and the titanium nitride particles were 7.0 nm and 20 nm, respectively. • The film properties of the transparent 2-layer film formed on the glass substrate are shown at -41- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ^ "------- ------ tT --------- line (please read the notes on the back before filling this page) 513475 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (40) In the following table 1b. In addition, the reflectance profile of the transparent conductive layer structure according to Example 4 of the present invention is made in Figure 7 and its transmittance profile is made in Figure 8. [Example 5] In addition to using Liquid F and acetone, ethanol (EA), and diacetone alcohol (DAA) were added to a concentrated dispersion of gold-coated silver particles (prepared in the same manner as in Example 1) to obtain a transparent conductive layer. The first coating liquid (0.08% silver, 0.32% gold, 0.15% titanium nitride, 1: 0.8% water, 10.0% acetone, 73.65% of £ 8, and 5.0% of 088), And a silica sol liquid obtained by adding 0.005 g of r-hydrosulfopropyltrimethoxysilane to 100 g of liquid C-2 (explained below) In addition, it has a transparent conductive layer (including precious metal particles, titanium nitride particles, and silicon dioxide adhesive matrix) and a transparent coating (including a silicate film, which is mainly composed of silicon dioxide). The glass substrate of the layer film (that is, the transparent conductive layer structure according to Example 5) was obtained according to the method in Example 1. The film properties of the transparent 2-layer film formed on the glass substrate are shown in the following table lb. In addition, the reflectance profile of the transparent conductive layer structure according to Example 5 of the present invention is made in Figure 9 and its transmittance profile is made in Figure 10. [Example 6] 5 grams of titanium nitride particles ( Netsuren) and 5 grams of silica sol (Liquid C-3) were mixed with 20 grams of purified water and 70 grams of ethanol, and spread with chromium beads using a paint shaker. Paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---- · --- J ----- loading ---- (Please read the precautions on the back before filling this page) tr --------- · 513475 A7 B7 V. Description of the invention (4) Change the resin to its product Desalting to obtain a silicon dioxide-coated titanium nitride microparticle dispersion (liquid G) having a dispersed particle diameter of 90 nm. The TEM observation of the above silicon dioxide-coated titanium nitride microparticles confirmed this. The titanium nitride particles are coated with silicon dioxide. The above silica sol (liquid C-3) is prepared by using 19.6 parts of methyl silicate 51 (trade name, Colcoat), 57.8 parts of ethanol, and 7.9 parts of water A 1% nitric acid solution and 1 4.7 parts of purified water gave a substance having a solid concentration of SiO 2 (silicon dioxide) of 10% and a weight-average molecular weight of 1,840. Next, liquid G and acetone, ethanol (EA), propylene glycol monomethyl ether (PGM), diacetone alcohol (DAA), and formamidine (FA) were added to a concentrated dispersion of gold-coated silver particles ( Prepared in the same way as in Example 1) to obtain a first coating liquid (0.08% silver '0.32% gold, 0.2% titanium nitride, 12.7% water) for forming a transparent conductive layer. 20.0% acetone, 41.5% EA, 20.0% PGM, 5.0% DAA, and 0.1% FA). Observing the obtained coating liquid for forming a transparent conductive layer, the average particle diameters of the gold-coated silver particles and the silicon dioxide-coated titanium nitride particles were 7.5 nm and 30 nanometers. Next, this coating liquid for forming a transparent conductive layer was spin-coated (150 rpm (revolutions per minute), 90 seconds) on a glass substrate (soda-lime glass having a thickness of 3 mm) heated to 40 ° C. ) And then spin-coated (150 rpm, 60 seconds) with silica sol (Liquid C-4). In addition, the product was matured at 180 ° C for 30 minutes to obtain a glass substrate with a transparent 2-layer film. The transparent 2-layer film was composed of precious metal particles and coated with silicon dioxide. -43- This paper is applicable to China National Standard (CNS) A4 Specification (210 x 297 mm) (Please read the precautions on the back before filling this page) Zero ^ 4 -------- Order * -------- · Economic Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives V. Invention Description (42) (Please read the precautions on the back before filling out this page) of titanium nitride particles, and the transparent conductive layer of the silicon dioxide adhesive matrix and including silicic acid The salt film is composed of a transparent coating (its main composition is silicon dioxide), that is, a transparent conductive layer structure according to Example 6 of the present invention. Here, the above silica sol (liquid C-4) was obtained by adding 0.005 g of r-hydrosulfopropyltrimethoxysilica to 100 g of liquid C-2 in Example 4. The film properties of the transparent 2-layer film formed on the glass substrate are shown in the following table lb. In addition, the reflectance profile of the transparent conductive layer structure according to Example 6 of the present invention is made in the first figure and its transmittance profile is made in the twelfth figure. '[Example 7] 5 g of titanium nitride particles (Net suren) and 20 g of the above-mentioned liquid C-3 were mixed with 20 g of purified water and 5 g of ethanol, and spread with cobalt using a paint agitator. Beads. Then, the product was desalted with the above-mentioned ion exchange resin to obtain a silica-coated titanium nitride particulate dispersion (liquid H) having a dispersed particle diameter of 95 nm. TEM observation of the above silicon dioxide-coated titanium nitride particles confirmed that the titanium nitride particles had been coated with silicon dioxide. Next, in addition to replacing liquid G in Example 6 with liquid plutonium, the first coating liquid (0.08% silver, 0.32% gold) was formed by using i to replace liquid G in Example 6. , 0.1 5% titanium nitride, 12.7% water, 20.0% acetone, 41.5% EA, 20.0% PGM, 5.0% DAA, and 0.1% FA) and the above liquid C- 2 In addition to the fact that it is a silica sol liquid, it has a transparent conductive layer (including noble metal particles, coated with silicon dioxide-nitriding-44-) This paper size applies to China National Standard (CNS) A4 (210 X 297 (Mm) 513475 A7 ------- B7___ 5. Description of the invention (43) Titanium particles and silicon dioxide adhesive matrix) and transparent coating (including silicate film, whose main composition is silicon dioxide) The glass substrate of the transparent 2-layer film (that is, the transparent conductive layer structure according to Example 7) was obtained according to the method in Example 6. In addition, the film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 1b below. In addition, the reflectance profile of the transparent conductive layer structure according to Example 7 of the present invention is made in FIG. 13 and the transmittance profile is made in FIG. 14. [Example 8] 10 g of a composite oxide particle of iron, manganese, and copper having an average particle diameter of 30 nanometers and having been coated with silicon dioxide (manufactured by the company Dainichiseika Color & Chemicals Mfg. Co., Ltd. It is a product of TMB # 3 5 50) and 0.5 g of dispersant is mixed with 89.5 g of diacetone alcohol and spread with a paint mixer to sell beads. The product was then desalted with an ion exchange resin to obtain a composite oxide particulate dispersion (liquid I) of iron, manganese, and copper having a dispersed particle diameter of 100 nm. Next, in addition to replacing liquid G in Example 6 with liquid I, a first coating liquid (0.08% silver, 0.32% gold, 15% iron manganese copper (Fe-Mn) -Cu-O), 10.7% water, 53.6% EA, 25.0% PGM, 10.0% DAA, and 0.1% FA) and using the above liquid C-2 as the silica sol liquid In addition, it has a transparent conductive layer (including precious metal particles, silicon dioxide-coated iron, manganese and copper composite oxide particles, and a silicon dioxide adhesive matrix) and a transparent coating (including silicate thin film, Its main composition is silicon dioxide) structure -45- This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling this page) Packing ----- --Order --------- Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7__ 5. Description of the invention (44) Transparent 2-layer The glass substrate of the film (that is, the transparent conductive layer structure according to Example 8) was obtained according to the method in Example 6. In addition, the film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 1b below. [Example 9] Titanium chloride was hydrolyzed with an alkaline aqueous solution and treated with ammonia gas at 800 ° C to obtain titanium oxynitride black with an average particle diameter of 30 nm (15.5 % Nitrogen). 5 g of such titanium oxynitride black particles and 10 g of the above-mentioned liquid C-7 were mixed with 20 g of purified water and 65 g of ethanol, and dispersed with zirconium beads using a paint shaker. Then, the product was desalted with an ion exchange resin to obtain a dispersion of silicon dioxide-coated titanium oxide black particles having a particle diameter of 98 nm (liquid J). In addition, by TEM observation of the above-mentioned silicon dioxide-coated titanium oxynitride black particles, it was confirmed that the titanium oxynitride black particles had been coated with silica. Next, in addition to replacing the liquid G in Example 6 with the above liquid: F to obtain a first coating liquid (0.08% silver, 0.32% gold, 0.2% titanium oxynitride 1 (1 ^ (^ Ever), 12.7% water, 20.0% acetone, 41.5% EA, 20.0% PGM, 5.0% DAA, and 0.1% FA) and use the above liquid C-2 as silica In addition to the fact of a sol liquid, it has a transparent conductive layer (including precious metal particles, silicon dioxide-coated titanium nitride black particles, and a silicon dioxide adhesive matrix) and a transparent coating (including a silicate film. Transparent 2-layer film (mainly composed of silicon dioxide) (that is, the transparent conductive layer structure according to Example 9) -46- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please (Read the notes on the back before filling out this page)

513475 A7 B7 V. The glass substrate of the invention is obtained according to the method in Example 6. In addition, the film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 2b below. [Example 10] 10 g of phthalocyanine pigment particles having an average particle diameter of 20 nanometers (product of Cyanine Blue 5230 manufactured by Daichiniseka Color & Chemicals Mfg. Co., Ltd.) and 2 g The above-mentioned liquid C-3 was mixed with 97 g of ethanol, and dispersed with zirconium beads using a paint agitator. Then, the product was desalted with an ion exchange resin to obtain dispersed silica particles having a diameter of 99 nm. Coated phthalocyanine blue particle dispersion (liquid K). In addition, it was confirmed that the phthalocyanine blue particles were coated with the phthalocyanine blue particles by TEM observation of the above silica-coated phthalocyanine blue particles. Silicon dioxide. Next, in addition to replacing liquid G in Example 6 with liquid K, a first coating liquid (0.08% silver, 0.32% gold, 0.1% phthalocyanine blue) for forming a transparent conductive layer was obtained. , 10.7% water, 20.0% acetone, 28.6% EA, 28.8% PGM, 11.2% DAA, and 0.1% FA) and the fact that the above-mentioned liquid C-2 is used as the silica sol liquid 'has a transparent conductive layer (including Transparent 2-layer film composed of precious metal particles, ugly cyan particles coated with silicon dioxide, and a silicon dioxide adhesive matrix) and a transparent coating (including a oxalate film whose main composition is silicon dioxide) The glass substrate (that is, the transparent conductive layer structure according to Example 10) was obtained according to the method in Example 6. In addition, the film property of the transparent 2-layer film to be formed on the glass substrate was -47- The dimensions are applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) II ϋ · tmmmm «ϋ emmme n ϊ Μ 0 ϋν n · _ϋ H 口 口 线- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by 513475 Α7 Β7 V. Description of the invention (46) is shown in the following table 2b ° [Example 11] Diacetone alcohol (DAA) was added to gold via the method prepared in Example 1. The coated silver microparticles concentrate the dispersion to obtain a second coating liquid (0.08% silver, 0.32% gold, 10.7% water, 73.9% £ 8, and 15.0% 0.8) for forming a transparent conductive layer. 8. The observation result of the coating liquid used to form the transparent conductive layer was obtained by a transmission electron microscope (TEM). The average particle diameter of the gold-coated silver particles was 6.0 nm. Next, a method for preparing a silica sol liquid (liquid L) is to use 19.6 parts of methyl silicate 51 (trade name, Colcoat), 57.8 parts, 7.9 parts of an aqueous 1% nitric acid solution, and 1 4.7 Part of purified water to obtain a substance with a solid concentration of SiO2 (silicon dioxide) of 10% and a weight · average molecular weight of 2,830, followed by a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (I PA / NBA = 3/1) This substance is diluted to a substance having a final SiO2 solid concentration of 0.8%. Next, 2 grams of carbon fine particles (MK7, Mitsubishi Chemical Corporation) with an average particle diameter of 34 nanometers and 0.2 grams of dispersant were mixed with 97.8 grams of propylene glycol monomethyl ether (PGM) and passed through a paint agitator This was dispersed with pin beads to obtain a carbon fine particle dispersion (liquid M) having a dispersed particle diameter of 100 nm. In addition, 9.6 g of liquid L and 0.46 g of liquid M were mixed to obtain a coating liquid for forming a transparent conductive layer. Next, rotate the above-mentioned coating liquid used to form the transparent conductive layer -48- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) Order --------- Line 513475 A7 ---- B7— __ ~ V. Description of the invention (47) Coating (1 50rpm (rev / min), 60 seconds) has been heated to 35 ° C was coated on a glass substrate (sodium lime glass with a thickness of 3 mm) and then spin-coated with H 50r pm for 60 seconds) for the coating liquid for forming a transparent coating, and additionally at 180 ° C. The product was aged for 30 minutes to obtain a glass substrate with a transparent 2-layer film. The transparent 2-layer film was composed of a noble metal particle (which is composed of gold and silver) and a transparent coating including a silicate film (its main composition is Carbon particles and silicon dioxide), that is, the transparent conductive layer structure according to Example 11 of the present invention. The film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 2b below. In addition, the reflectance profile of the transparent conductive layer structure according to Example Π of the present invention is made in FIG. 15 and its transmittance profile is made in FIG. 16. [Example 12] Titanium chloride was hydrolyzed with an alkaline aqueous solution and treated with ammonia gas at 800 ° C to obtain titanium oxynitride black (15. 5 having an average particle diameter of 30 nm). % Nitrogen). 5 grams of this kind of titanium oxynitride black particles i 0.5 grams of dispersant were mixed with 94.5 grams of ethanol and dispersed with chromium beads using a paint agitator to obtain titanium oxynitride black with a dispersed particle diameter of 93 nm Microparticle dispersion (liquid N, 5% titanium oxynitride black, in addition to the fact that '9.6 g of liquid L and 0.4 g of liquid N are used to obtain a coating liquid for forming a transparent conductive layer' has a transparent conductive Layer (including precious metal particles composed of gold and silver) and transparent coating (including silicate thin film, whose main composition is silicon dioxide) is transparent 2- -49- This paper standard applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the notes on the back before filling out this page > -------- Order --------- Line-Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 513475 ·. A7 _ B7 V. Description of the invention (48) The glass substrate of the layer film (that is, the transparent conductive layer structure according to Example 12) was obtained according to the method in Example 11. The glass substrate will be formed on the glass substrate. The film properties of the transparent 2-layer film above are shown in Table 2b below. In addition, the reflectance profile of the transparent conductive layer structure according to Example 12 of the present invention is made in FIG. 17 and its transmittance profile is made in FIG. 18. L Example 13] • 10 g of iron, Composite oxide particles of manganese and copper (product of TMB # 3550 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and 0.5 g of dispersant were mixed with 89.5 g of diacetone alcohol and used paint The agitator was used to disperse the beads to obtain a composite oxide particle dispersion (liquid 0) of iron, manganese, and copper with a diameter of 98 nm. In addition, 9.8 g of liquid L and 0.2 g of liquid 0 were used. In addition to the fact that 2 mg of r-hydrosulfopropyltrimethoxysilane is used to form a coating liquid for forming a conductive layer, it has a transparent conductive layer (including precious metal particles composed of gold and silver) and transparent The glass substrate of the transparent 2-layer film (that is, the transparent conductive layer structure according to Example 13) composed of a coating (including a silicate thin film whose main composition is a complex oxide of iron, manganese and copper and silicon dioxide) is real Obtained by the method in 11. The film properties of the transparent 2-layer film formed on the glass substrate are shown in the following table 2b. In addition, the reflectance profile of the transparent conductive layer structure according to Example 1 3 of the present invention is made in Figure 19 and the transmittance profile are made in Figure 20. -50- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before (Fill in this page) Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 513475 A7 B7 V. Description of the invention (49) [Example 14] 5 grams of Example 9 titanium oxide black And 20 grams of the above-mentioned liquid C-3 was mixed with 20 grams of purified water and 55% grams of ethanol, and spread with a bead using a paint shaker. Then, the product was desalted with a market ion exchange resin to obtain a silica-coated titanium oxide black particulate dispersion (liquid P) having a dispersed particle diameter of 100 nm. In addition, by TEM observation of the above-mentioned silicon dioxide-coated titanium oxynitride black particles, it was confirmed that the silicon oxynitride black particles had been coated with silicon dioxide. Next, in addition to the fact that 9.6 g of liquid L and 0.4 g of the above-mentioned liquid P are used to obtain a coating liquid for forming a transparent conductive layer, there is a transparent conductive layer (including precious metal particles composed of gold and silver) ) And transparent coating (including silicate film, whose main composition is coated with silicon dioxide titanium oxide black particles and silicon dioxide) is a transparent 2-layer film (that is, transparent conductive according to Example 14) Layer structure) The glass substrate was obtained by the method in Example 11. [Comparative Example 1] Ethanol (EA) and diacetone alcohol (DAA) were added to Liquid A of Example 1 to obtain a coating liquid (0.08% silver, 0.32% gold, 10.7) for forming a transparent conductive layer. % Water, 73.9% EA, and 15.0% DAA). In addition, in addition to the fact that the coating liquid used to form the transparent conductive layer in Example 1 was replaced with the coating liquid used to form the transparent conductive layer described above and Liquid C was used as the silica sol liquid, there was a transparent conductive layer ( Including precious metal particles and silicon dioxide adhesive matrix) and transparent coating (including silicate film, whose main composition is silicon dioxide) is a transparent 2-layer film (that is, -51-) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297) (Please read the precautions on the back before filling out this page) Packing -------- Order --------- line. Intellectual property of the Ministry of Economic Affairs 513475 A7 _ B7 printed by the Bureau ’s Consumer Cooperative. V. Description of the Invention (5G) The glass substrate according to the transparent conductive layer structure of Comparative Example 1 was obtained according to the method in Example 1. The film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 2b below. In addition, the reflectance profile of the transparent conductive layer structure of Comparative Example 1 according to the present invention is made in FIG. 21 and the transmittance profile is made in FIG. 22. [Comparative Example 2] In addition to the liquid L (silica sol) in Example Π replacing the coating liquid used to form the transparent conductive layer in Example 11, the transparent conductive layer (including precious metal particles and dioxide A glass substrate with a transparent 2-layer film (that is, a transparent conductive layer structure according to Comparative Example 2 for comparison) composed of a silicon adhesive matrix) and a transparent coating (including a silicate film whose main composition is silicon dioxide) Obtained according to the method in Example 11. The film properties of the transparent 2-layer film formed on the glass substrate are shown in Table 2b below. In addition, the reflectance profile of the transparent conductive layer structure of Comparative Example 2 according to the present invention is made in FIG. 23 and the transmittance profile is made in FIG. 24. (Please read the precautions on the back before filling out this page) Order --------- line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-52- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 513475 A7 B7 V. Description of the invention (51) Table la Transparent 2-layer film structure (conducting layer / coating mixing ratio, precious metal or silicate / pigment) Coating ratio 2 (color pigment / Silicate) Example 1 Ag-Au + carbon / silicon oxide 8/1 Example 2 Ag-Au + Fe-Mn-Cu_〇 / s i1i con oxide 2.7 / 1 Example 3 Ag-Au + T i χΟγΝζ / silicon oxide 4/1 Example 4 Ag-Au + TiN / silicon oxide 2/1 Example 5 蠛 Ag-Au + T i N / silicon oxide 2.7 / 1 Example 6 Ag-Au + T i N / silicon oxide 2/1 100 / 10 Example 7 Ag-Au + Ti N / silicon oxide 2.7 / 1 100/40 Example 8 Ag-Au + Fe-Mn-Cu-0 / s i1i con oxide 2.7 / 1 100/20 1 Noble metal particles or silicon dioxide (Silicate) parts by weight / colored pigment particles by weight (please read the precautions on the back before filling out this page) ------- Order --------- Wisdom Ministry of Economy Printed by the Property Agency Staff Consumer Cooperative 2 Parts of colored pigments in coated colored pigment particles / parts of silicon dioxide coating -53- This paper uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 513475 A7 —_______ Β7 V. Invention Note (52) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1 Introduced light transmittance (%) Standard deviation of transmittance 3 Hue 値 (%) Bottom reflectance / Bottom wavelength year% / Nanometer Surface resistance (Ω / □) Example 1 68.3 1.12 0.2 0.02 / 530 566 Example 2 70.4 2.43 0.6 0.03 / 615 1123 Example 3 74.8 3.59 0.4 0.10 / 535 1362 Example 4 62. 1 3.04 0.7 0.06 / 520 730 Example 5 65 · 1 2.52 0.7 0.08 / 535 659 Example 6 60.5 2.66 0.6 0.02 / 530 398 Example 7 66.6 1 .88 0.5 0.03 / 550 319 Example 8 71.2 2.77 0.7 0.13 / 590 627 3 Does not include the above-mentioned transparent substrate, but the transparent 2-layer film is only in the visible wavelength region (380 to 780 nanometers) The number of transmittances at each nanometer interval of 5 nanometers (%).衣 za Transparent 2-layer film structure (conductive layer / coating (noble metal or silicate / Yan EJ—- coating ratio 2 (color pigment / silicate)) Example 9 Ag-Au + T i χΟγΝχ / silicon oxide 2/1 100/20 Example 10 A g-Au + ph t ha 1ocyan i ne blue / silicon oxide 4/1 100/20 * Example 11 A g-A u + carb ο n + silicon oxide 9.6 / 1 * Example 12 Ag-Au / Ti x〇YNz + si 1 icon oxide 3.8 / 1 Example 13 Ag-Au / Fe-Mn -Cu-0 / s i1 icon oxide 3.9 / 1 Example 14 Ag-Au + T i χΟγΝ ^ + si 1 ic ο n oxide 3.8 / 1 100/40 Comparative Example 1 Ag-Au + / silicon oxide-·-Comparative Example 2 Ag · Au / silicon oxide--54- ---------. — (Please read the precautions on the back before filling out this page) Order ·--· The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 513475 A7 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation of the invention 5. Description of the invention (1 precious metal particles or silicon dioxide (salt salt) parts by weight / parts of colored pigment particles 2 parts by weight of colored pigments in silica-coated color pigment particles / silicon dioxide Coating weight Table 2b Visible light transmittance (%) Standard deviation of transmittance 3 Hue 値 (%) Bottom reflectance / Bottom wavelength (% / nm) Surface resistance (Ω / Π) Example 9 67.2 2.84 0.3 0.07 / 545 505 Example 10 67.6 3.95 0.5 0.55 / 600 695 Example 11 70.0 2.27 0.9 1. 10/670 363 Example 12 66.6 3.25 0.4 10.88 / 595 341 Example 13 71 .4 1 .07 0.3 0.85 / 585 369 Example 14 64.8 3.41 0.5 0.82 / 605 339 Comparative Example 1 81. 1 1.43 0. 1 0. 15/600 191 Comparative Example 2 83.3 1. 20 0 0.37 / 485 274 3 The transparent 2-layer film alone is not included in the visible light wavelength range ( 380 to 780 nanometers) for each wavelength at 5 nanometer intervals 値 (%). [Evaluation] 1. As can be clearly seen from the "surface resistance" results shown in Tables 1b and 2b, it was confirmed that although the transparent conductive layers or transparent coatings in Examples 1 to 14 contained colored pigment particles, However, the surface resistance of the same transparent 2-layer film will fall within an acceptable range (10 to 5000 Ω / port), which will not cause problems in practical applications. 2 In addition, as can be clearly seen from the "bottom reflectance / bottom wavelength" results shown in Tables 1b and 2b, it is also confirmed that the transparent conductive layer structure according to each example has a very good low reflectance . 3 · The results of "visible light transmittance" as shown in Tables 1 b to 2b are OK. (Fill in this page)

Order--丨 Line · 513475 A7 137 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i. Invention Description ("It is clear that it confirms that the visible light transmittance adjustment of the transparent 2-layer film according to each example will be adjusted The fact that it is within the specified range (40 to 75%) Conversely, according to Comparative Examples 1 and 2, the visible light transmittances of the transparent 2-layer films were 81.1 and 83.3%, respectively, and cannot be adjusted to Within the specified range. In addition, the figures 2, 4, 6, 8, 10, 12, 14, 1, 16, 18, and 20 can be clearly seen, which confirms the transparency of each example 2 -The films have low transmittance and flat transmission profile. 4. From the comparison of the surface resistance (Ω / □) in the following examples, it can be confirmed that the color pigment particles in the transparent conductive layer structure have been significantly Improved the conductivity of its transparent 2-layer film, in which colored pigment particles are added to a transparent conductive layer with silicon dioxide. That is, this can be done from Examples 2 and 8 to the surface resistance (1, 123 and 627 Ω / port) comparison results, Example 3 and Example 9 for surface resistance (1, 362 and 5 05 Ω / Ο) comparison results, Example 4 and Example 6 on the surface resistance (730 and 398 Ω / Ε]), and Example 5 and Example 7 on the surface resistance (659 and 319 Ω / 匚)) The results are confirmed. 5. In addition, it can be confirmed from the comparison results of Example 12 and Example 14 on the mechanical strength (to be discussed below) that the transparent 2-layer film can be further improved by the colored pigment particles in the transparent conductive layer structure. Mechanical strength, in which colored pigment particles are added to a transparent conductive layer with silicon dioxide. That is, in the pencil hardness test, 4 or 5H is obtained in Example 12 and 6H (in Example 14) Under the load of 1 kg, there is Η -56- (Please read the precautions on the back before filling in this page) • a-cloth. 丨 line · This paper size applies to China National Standard (CNS) A · 彳 specifications (210 X 297 mm) 513475 A7 B7 i. Description of the invention ("9-9H pencils are evaluated by drawing line segments on the surface of the transparent 2-layer film). 6. In addition, the transparent conductive layers according to the examples of the present invention are also described as follows. Structurally perform "climate resistance test" That is, the transparent conductive layer structure according to each example was immersed in an aqueous 10% saline solution, an aqueous 50% citric acid solution, and an aqueous 5% ammonia solution for 24 hours, and the transparent 2-layer on the glass substrate was studied The surface resistance and appearance of the film, but except for the slight change in the reflected color of the appearance of the film immersed in an aqueous 5% ammonia solution, no change was observed. Therefore, it was confirmed that the structure of the transparent conductive layer according to each example was also Has the same weather resistance and chemical resistance as in the past. 7. In addition, although gold-coated silver particles are used in each example and each comparative example, we also use platinum-coated silver particles and gold. Tests were performed on precious metal-coated silver particles of compounds of platinum and platinum. In addition, it was confirmed that when such fine particles were used, they all showed the same tendency as the above-mentioned examples and comparative examples. (Please read the notes on the back before filling out this page)-Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs t

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

513475 ^ VI. Patent Application No. 89 124369 "Transparent conductive layer structure, display using this transparent conductive layer structure, and coating liquid for forming transparent conductive layer" patent (Amended on September 20, 91) Scope of patent application: 1. A transparent conductive layer structure having a transparent substrate and a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer sequentially formed on the substrate; wherein the main component of the transparent conductive layer is Precious metal particles with an average particle diameter of 1 to 100 nanometers (composed of gold and / or platinum and silver and containing 5 to 95% by weight of the above gold and / or platinum), and an average particle diameter of 5 to 200 nanometers Colored pigment particles and binder matrix; the precious metal particles are mixed in a proportion of 1 to 40 parts by weight of precious metal particles per part by weight of colored pigment particles; the transparent 2-layer film contains 10 to 5,000 Ω / □ Surface resistance; The transparent 2-layer film has a minimum reflectance of 0 to 2.5% in the reflectance profile in the visible light region; the transparent substrate is not included, and the transparent 2-layer film alone See the light transmittance of 40 to 75%, without the transparent substrate mentioned above, but the transmission of the transparent 2-layer film in the visible wavelength region (380 to 7 80 nm) at each wavelength of 5 nm interval The standard deviation of the rate is 0 to 5%. 2. A type of transparent conductive layer structure, which has a transparent substrate and a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer formed on the substrate in the order of 513475 VI. Patent application; wherein the transparent conductive layer The main composition is precious metal particles with an average particle diameter of 1 to 100 nanometers (composed of gold and / or platinum and silver and containing 5 to 95% of the above-mentioned gold and / or uranium) and a binder matrix; wherein the transparent The main composition of the coating is colored pigment particles with an average particle diameter of 5 to 200 nanometers and a binder matrix; the transparent 2-layer film contains a surface resistance of 10 to 5,000 Ω / □; the transparent 2-layer film is visible light The smallest reflectance in the reflectance profile in the region is 0 to 2.5%; the transparent light-transmittance of the transparent 2-layer film alone is not included, and the visible light transmittance of the transparent 2-layer film is not included. The transparent 2-layer film alone has a standard deviation of transmittance at a wavelength of 5 nm in the visible light wavelength range (380 to 780 nm) at a wavelength of 0 to 5%. 3. The transparent conductive layer structure according to item 1 or 2 of the patent application scope, wherein the precious metal particles contain 50 to 95% by weight of gold and / or platinum. 4. The transparent conductive layer structure according to item 1 or 2 of the scope of the patent application, wherein the composition of the colored pigment particles is selected from carbon, black dioxide, titanium oxynitride black, composite oxide pigments, quinacridone pigments, and green onions. Vinegar pigment, perylene pigment, isoaza (hetero) indanone pigment, azo-based pigment, copper phthalocyanine blue pigment, cobalt violet, molybdenum orange, ultramarine blue, Prussian blue, titanium nitride One or more types of 513475 Six, the scope of patent application. 5. The transparent conductive layer structure according to item 1 or 2 of the scope of the patent application, wherein the color pigment particles are silicon dioxide-coated color pigment particles having sand dioxide coated thereon. 6. The transparent conductive layer structure according to item 5 of the scope of patent application, wherein the amount of silicon dioxide on the color pigment particles coated with the silicon dioxide is set to 5 to parts by weight per 100 parts by weight of the color pigment particles. Within the range of silicon dioxide. 7. The transparent conductive layer structure according to item 1 or 2 of the patent application scope, wherein the silicon dioxide is the main component of the transparent conductive layer and the adhesive matrix in the transparent coating. 8. A display device comprising a display main unit and a front panel arranged on the front side of the display main unit, wherein a transparent conductive layer structure such as the scope of claims 1 to 7 is used as the front panel and the The transparent 2-layer film side is arranged on the outside. 9. A coating liquid for forming a transparent conductive layer, the transparent conductive layer belongs to a transparent conductive layer having a transparent substrate and a transparent 2-layer film composed of a transparent conductive layer and a transparent coating layer sequentially formed on the substrate. Layer structure, the transparent 2-layer film has a surface resistance of 10 to 5,000 Ω / □, and the transparent 2-layer film has a minimum reflectance of 0 to 2 · 5% in the reflectance profile in the visible light region, The visible light transmittance of the transparent 2-layer film alone is not included in the above transparent substrate 513475 6. Apply for a patent ranging from 40 to 75%, excluding the above-mentioned transparent substrate, but the transparent 2-layer film alone at each wavelength in the visible wavelength region (380 to 780 nm) at 5 nm intervals. The standard deviation of the transmittance is 0 to 5%; wherein the main composition of the coating liquid is a precious metal-coated silver having an average particle diameter of 1 to 100 nm and containing 5 to 95% by weight of gold and / or platinum Fine particles whose surface is coated with gold or platinum alone or a compound consisting of gold and platinum; colored pigment particles having an average particle diameter of 5 to 200 nanometers; and a solvent in which such particles are dispersed; and The noble metal particles are mixed in a proportion of 1 to 40 parts by weight of the noble metal particles per part by weight of the color pigment particles. i 〇 • The coating liquid for forming a transparent conductive layer according to item 9 of the patent application fence, wherein the noble metal-coated silver particles contain 5 to 95% by weight of gold and / or platinum. i 1. The coating liquid for forming a transparent conductive layer according to item 9 or 10 of the scope of patent application, wherein the composition of the colored pigment particles is selected from the group consisting of carbon, titanium dioxide black, titanium nitride black, composite oxide pigment, Quinacridone pigment, anthraquinone pigment, perylene pigment, isoaza (hetero) indanone pigment, azo-based pigment, copper phthalocyanine blue pigment, cobalt violet, molybdenum orange, ultramarine blue, Prussian blue, nitriding One or more types of particles made of titanium. 1 2 · The coating liquid for forming a transparent conductive layer as described in the patent application No. 9 or 10, wherein the colored pigment particles are a kind of surface -4- 513475 VI. Silicon dioxide-coated color pigments coated with silicon dioxide on the scope of the patent application 1 3. For the coating liquid used to form a transparent conductive layer in the scope of the patent application item 12 The amount of silica on the silica-coated color pigment particles is set within a range of 5 to 100 parts by weight of silicon dioxide per 100 parts by weight of the color pigment particles. 14. The coating liquid for forming a transparent conductive layer according to item 9 or 10 of the scope of patent application, which contains an inorganic binder.