JP2000228154A - Colored transparent conductive film and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored transparent conductive film having antistatic effect, electromagnetic wave shield effect, durability such as salt water resistance or abrasion resistance and good visibility of image in using for display surface of a cathode-ray tube and a plasma display, and provide a display which has this colored transparent conductive film formed on the display surface. SOLUTION: This colored transparent conductive film has a transparent conductive layer formed by use of paint for forming the transparent conductive layer including metallic corpuscle as conductive component and not including coloring material and binder component and a transparent color layer formed by use of paint for forming the transparent color layer including coloring material and not including the conductive component and the binder component. Therefore, antistatic effect, electromagnetic wave shield effect, durability represented by salt water resistance or abrasion resistance and god visibility of image are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a colored transparent conductive film,
And a display device in which the colored transparent conductive film is formed on a display surface, and particularly excellent in antistatic effect and electromagnetic wave shielding effect as well as salt water resistance, scratch resistance and the like, which are excellently used for a display surface such as a cathode ray tube or a plasma display. The present invention relates to a colored transparent conductive film which has durability and further has excellent visibility of an image because it contains a coloring material for hue adjustment, and a display device having the colored transparent conductive film formed on a display surface.

[0002]

2. Description of the Related Art A cathode ray tube, which is a kind of display device used as a TV cathode ray tube or a computer display, emits an electron beam onto a phosphor screen which emits red, green, and blue light to display characters and images. Is projected on the display surface, and the static electricity generated on the display surface causes dust to adhere to the display surface, lowering the visibility, and radiating electromagnetic waves to affect the environment. Recently, it has been pointed out that a plasma display, which is being applied to a wall-mounted television or the like, may generate static electricity or emit electromagnetic waves.

In order to solve these problems, for example, a transparent conductive film having an excellent electromagnetic wave shielding effect contains at least 10% by weight of metal fine particles containing at least silver and is colored with an organic or inorganic coloring agent. A colored transparent conductive film having a transparent conductive layer and a transparent anti-reflection layer formed on an upper layer and / or a lower layer of the transparent conductive layer has been proposed.

[0004]

However, these conventional colored transparent conductive films are not sufficient in at least one of an electromagnetic wave shielding effect, visibility, and durability, and further improvement has been demanded. The present invention has been made in order to solve the above-mentioned problems, and therefore, the object is to
A colored transparent conductive film which is not only excellent in electromagnetic wave shielding effect, antistatic effect, durability such as salt water resistance and scratch resistance, but also excellent in image visibility, and this colored transparent conductive film Is to provide a display device formed on a display surface.

[0005]

In order to solve the above-mentioned problems, the present invention provides a paint for forming a transparent conductive layer according to claim 1, which contains metal fine particles as a conductive component and does not contain a coloring material and a binder component. Provided is a colored transparent conductive film having at least a transparent conductive layer formed by using the above, and a transparent colored layer formed using a transparent colored layer forming paint containing a coloring material and not containing a conductive component and a binder component. .
In the colored transparent conductive film, it is preferable that a transparent thin film layer formed using a transparent thin film layer forming paint containing a binder component is formed above the transparent conductive layer and the transparent colored layer. The average particle size of the metal fine particles in the transparent conductive layer forming coating is preferably in the range of 2 nm to 50 nm. The metal fine particles in the transparent conductive layer forming paint are preferably in the form of a chain aggregate. The main component of the metal fine particles is preferably at least one selected from the group consisting of gold, silver, platinum, palladium, ruthenium, rhodium, iridium, osmium, and rhenium.
The transparent coloring layer preferably contains a coloring pigment and silica fine particles. The colored transparent conductive film preferably has a luminous reflectance of 0.8% or less. Furthermore, the present invention provides a display device according to claim 8, wherein any one of the colored transparent conductive films is formed on a display surface.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies on a transparent colored conductive film in order to impart an excellent electromagnetic wave shielding effect, durability and visibility to the display surface of a display device. For the transparent colored layer, use a paint in which the color pigment and silica fine particles are uniformly dispersed and do not contain a binder component. A colored transparent conductive layer formed as a separate layer of a transparent conductive layer that provides a transparent conductive layer and a transparent colored layer that improves visibility is a colored transparent conductive layer having a transparent colored conductive layer having a conventionally known conductive performance and a coloring effect. The present inventors have found that they have higher conductivity than films and exhibit excellent durability and visibility, and have reached the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. In a preferred embodiment of the colored transparent conductive film of the present invention, the transparent conductive layer and the transparent colored layer are laminated as separate layers, and a transparent thin film layer is formed as the outermost layer. In this embodiment, the transparent conductive layer is formed using a transparent conductive layer forming paint that contains metal fine particles as a conductive component and does not contain a coloring material and a binder component. The transparent colored layer is formed using a transparent colored layer forming coating material in which a colored pigment and silica fine particles are uniformly dispersed and do not contain a binder component. Further, the transparent thin film layer is formed using a transparent thin film layer forming paint containing a binder component containing silica as a main component.

The colored transparent conductive film of this embodiment exhibits high conductivity, is excellent in salt water resistance and scratch resistance, and is also excellent in image visibility. Although the reason is not always clear, it is considered as follows. That is, the transparent conductive layer contains metal fine particles, does not contain a binder component other than the minimum amount of the binder component permeated during the formation of the transparent thin film layer, and also does not contain a coloring material.
The transparent conductive layer does not substantially contain a component that hinders conductivity, the contact resistance between the metal fine particles is suppressed to a low level, and the surface conductivity is as high as 1 × 10 ⁴ Ω / □ or less. You will gain sex. Since both the transparent conductive layer forming paint and the transparent colored layer forming paint do not contain a binder component, each layer formed using these has a large surface free energy,
The wettability is improved, so that the affinity at the interface between the layers and the adhesion between the layers are improved. As a result, salt water resistance,
The abrasion resistance is improved, and the thickness of each layer is easily controlled, and the antireflection property is also improved. Further, by forming a transparent thin film layer containing a binder component containing silica as a main component on the upper layer, durability such as salt water resistance and scratch resistance is greatly improved, and the luminous reflectance is 0.8%. The following excellent visibility can also be obtained.

As the metal fine particles, noble metal fine particles such as gold, silver, palladium, ruthenium, platinum, rhodium, iridium, osmium and rhenium are effective.
In particular, gold, palladium, and ruthenium provide excellent performance in terms of chemical stability, conductivity, and cost as fine particles, and when these are applied to the display surface of a display device, they exhibit an excellent electric field. Chemical stability represented by shielding properties and salt water resistance can be obtained. The fine particles of gold, palladium, and ruthenium may be used alone or in combination of two or more, and may contain, for example, silver fine particles. Silver fine particles are relatively easily and inexpensively available as a colloidal dispersion, and have high conductivity and excellent antistatic properties and electromagnetic wave shielding properties.
This is particularly effective when it is desired to further reduce the cost of the conductive layer while maintaining the conductivity. Silver fine particles are not durable due to poor salt water resistance when used alone as a conductive material, but gold,
When used as a mixture mainly composed of fine particles of palladium or ruthenium, chemical stability is increased and practically sufficient durability is obtained.

The average particle size of the metal fine particles used is preferably in the range of 2 nm to 50 nm from the relationship between transparency and conductivity. If the particle size of the metal fine particles is less than 2 nm, the properties as a metal are impaired and the conductivity is lowered, which is not preferable.If the particle size exceeds 50 nm, island-like aggregates are easily formed,
It is not preferable because a uniform coating film cannot be formed.

Further, it is particularly preferable that the metal fine particles used form a chain aggregate in the coating material for forming a transparent conductive layer. Here, the chain-like aggregate of metal fine particles refers to a plurality of metal fine particles linked in a chain shape, and may be any of a linear, branched, cyclic, or composite form thereof. When using chain-aggregated metal fine particles, the metal fine particles themselves form a special structure in the transparent conductive layer, that is, a fine network structure in which chain-like aggregates are entangled,
The contact resistance between the particles is more effectively reduced. The length of the chain-like aggregate of the metal fine particles is preferably in the range of 5 nm to 200 nm, and particularly preferably in the range of 10 nm to 100 nm from the viewpoint of transparency. If the length of the chain aggregate is shorter than 5 nm, the resistance between the particles may increase and sufficient conductivity may not be obtained. If the length is longer than 200 nm, the light scattering degree increases and the transparency of the coating film tends to be impaired. .

A transparent conductive layer-forming coating material containing the chain aggregate is applied on a substrate, dried and then dried at 100 ° C. to 1000 ° C.
When the film is formed by baking at a temperature within the range described above, the contact resistance between the particles is suppressed to be small, and even if the transparent conductive layer is a thin film having a thickness of 10 nm to 30 nm, the surface resistance value is 5 × 10 ³ Ω / □.
The following high conductivity is obtained, and as a result, particularly excellent antistatic effect and electromagnetic wave shielding effect are obtained.

There are various methods for forming a chain-like aggregate of metal fine particles. For example, a method in which a metal salt aqueous solution is adjusted to a pH of 5 to 7 when a metal aqueous sol is formed, and a reducing agent in a range of 0.5 to 3 molar equivalents to metal ions in the solution is added. Is mentioned. Here, when the pH of the aqueous metal salt solution is greater than 7, or the amount of the reducing agent is more than 3 times the molar equivalent, the grain growth of the metal fine particles themselves proceeds excessively, and precipitation is likely to occur. When the pH of the aqueous metal salt solution is less than 5, or the reducing agent is less than 0.5 times the molar equivalent, monodispersed fine particles are generated,
Alternatively, the reduction reaction does not proceed sufficiently and metal fine particles are not generated. Further, as another method of forming a chain aggregate of metal fine particles, a method of holding the metal fine particle dispersion at a temperature in the range of about 40 ° C. to the boiling point of the dispersion medium or lower for several hours to several tens of hours,
There is a method of controlling the polarity of the dispersion medium by adding an organic compound such as alcohol. Regardless of the method, the optimum conditions for the formation of the chain-like aggregates differ depending on the type of the metal fine particles. Therefore, it is necessary to determine the optimum conditions by preliminary experiments.

As the above-mentioned coloring material, a coloring pigment is preferable from the viewpoint of its ultraviolet resistance and heat resistance. The particle size is 2 nm to 50 from the viewpoint of dispersion stability and coloring performance.
The range of nm is practical, particularly preferably 5 nm to 50 nm.
Excellent dispersion stability, coloring performance and transparency are obtained within the range of nm. Examples of the coloring material used here include monoazo pigment, quinacridone, iron oxide yellow, disazo pigment, phthalocyanine green, phthalocyanine blue, cyanine blue, flavanthrone yellow, dianthraquinolyl red, indanthrone blue, thioindigo bordeaux, Perylene orange, perylene scarlet, perylene red 178, perillylene maroon, dioxazine violet, isoindoline yellow, nickel nitroso yellow, madder lake, copper azomethine yellow, aniline black, alkali blue, zinc white, titanium oxide, red iron oxide, chrome oxide, Iron black, titanium yellow, cobalt blue, cerulean blue, cobalt green, alumina white, viridian, cadmium yellow, cadmium red, Organic and inorganic pigments such as vermilion, lithopone, graphite, molybdate orange, zinc chromate, calcium sulfate, barium sulfate, calcium carbonate, lead white, ultramarine, manganese violet, emerald green, navy blue, carbon black and the like can be mentioned. . These color pigments can be used alone or in combination of two or more to improve visibility.

The type and amount of the coloring pigment to be used should be appropriately selected according to the optical film characteristics of the colored transparent conductive film. The absorbance A of the transparent thin film is generally represented by the following equation. A = log ₁₀ (I ₀ / I) = εCD where I _{0 is} incident light, I is transmitted light, C is color density, D is light distance, ε is molar extinction coefficient. In the colored transparent conductive film of the present invention, a coloring material having a molar absorption coefficient of ε> 10 is generally used. The amount of the coloring material varies depending on the molar extinction coefficient of the coloring material used, but the absorbance A of the laminated film and the single-layer film containing the coloring material is 0.0004 to 0.0969 abs. It is preferable that the amount is within the range of the above. If these conditions are not met, the transparency will decrease.

The above-mentioned paint for forming a transparent conductive layer comprises, in addition to the above-mentioned metal fine particles or agglomerates of chained metal fine particles, a silica fine particle having an average particle diameter of 100 nm or less per metal.
It may be contained in the range of from 60% by weight to 60% by weight. Further, it is preferable that the coating material for forming a transparent coloring layer contains, in addition to the coloring pigment, silica fine particles having an average particle diameter of 100 nm or less in a range of 0.1 to 50 times the amount of the coloring pigment. . . When the coating material for forming a conductive layer and / or the coating material for forming a transparent coloring layer contains silica fine particles, there is an advantage that the wettability with components of other layers is improved, and the adhesion between both layers is improved. Aqueous properties and scratch resistance can be improved. The silica fine particles are more preferably contained in the range of 20% by weight to 40% by weight with respect to the contained metal, from the viewpoint of achieving both improvement in film strength and conductivity with respect to the transparent conductive layer. Is more preferably contained in the range of 1 to 20 times the amount of the contained color pigment from the viewpoint of improvement in film strength and reflection characteristics.

[0017] In addition to the above components, the transparent conductive layer forming paint and the transparent colored layer forming paint may include other components, if necessary, for the purpose of improving film strength, conductivity and reflection characteristics. For example, silicon, aluminum, zirconium, cerium, titanium, yttrium, zinc, magnesium,
Oxides such as indium, tin, antimony and gallium,
Complex oxides or nitrides, particularly oxides of indium or tin, and fine particles of inorganic substances mainly composed of the complex oxides or nitrides may be contained as long as the effects of the present invention are not impaired. The amount of addition at this time is preferably not more than 40% by weight of the conductive material from the viewpoint of suppressing a decrease in conductivity, particularly for the transparent conductive layer forming paint, and particularly preferable for the transparent colored layer forming paint. From the viewpoint of suppressing the deterioration of the film strength, the content is preferably 50% by weight or less of the silica fine particles.

To apply the above-mentioned paint for forming a transparent conductive layer or the above-mentioned paint for forming a transparent colored layer, a spin coating method, a roll coating method, a spray method, a bar coating method, a dipping method,
Any of ordinary thin film coating techniques such as a meniscus coating method and a gravure printing method can be used. Of these, spin coating is a particularly preferred coating method because a thin film having a uniform thickness can be formed in a short time. After the application, the coating film is dried and baked at 100 ° C. to 1000 ° C. to form a transparent conductive layer or a transparent coloring layer on the surface of the substrate.

The conductive performance of the transparent conductive film necessary for exhibiting the electromagnetic wave shielding effect in addition to the antistatic function is represented by the following equation (1). S = 50 + 10 log (1 / ρf) + 1.7t√ (f / ρ) Formula 1 where S (dB); electromagnetic wave shielding effect ρ (Ω-cm); volume resistivity of conductive film f (MHz); Electromagnetic wave frequency t (cm): film thickness of conductive film. Here, the thickness t is 1 μm from the viewpoint of light transmittance.
(1 × 10 ⁻⁴ cm) or less.
If the term including the film thickness t is ignored in Equation 1, the electromagnetic wave shielding effect S can be approximately expressed by Equation 2 below. S = 50 + 10 log (1 / ρf) (2) Here, as the value of S (dB) increases, the electromagnetic wave shielding effect increases.

Generally, the electromagnetic wave shielding effect is S> 30.
If it is dB, it is regarded as effective, and if S> 60 dB, it is regarded as excellent. In addition, since the frequency of the electromagnetic wave to be regulated is generally in the range of 10 kHz to 1000 MHz, the conductivity of the colored transparent conductive film requires a volume resistivity (ρ) of 10 ³ Ω-cm or less. . That is, the lower the volume specific resistance value (ρ) of the colored transparent conductive film, the more effectively the electromagnetic wave of a wider frequency range can be shielded. In order to satisfy this condition, it is preferable that the thickness of the transparent conductive layer in the colored transparent conductive film is 10 nm or more, and that the metal fine particles are further contained at 10% by weight or more. When the thickness of the transparent conductive layer is less than 10 nm or the content of the metal fine particles is less than 10% by weight, the conductivity is reduced, and it is difficult to obtain a substantial electromagnetic wave shielding effect.

In the colored transparent conductive film of the present invention, it is preferable that at least one transparent thin film layer is formed above the transparent conductive layer and the transparent colored layer. This transparent thin film layer preferably contains silica as a main component. This not only protects the transparent conductive layer and the transparent colored layer, but also effectively removes or reduces external light reflection at the interlayer interface of the obtained colored transparent conductive film. A preferred transparent thin film layer is a SiO ₂ thin film having a high surface hardness and a relatively low refractive index. Examples of a material that can form this SiO ₂ thin film include the following formula: M (OR) _m R _n (where M is Si, R is a C ₁ -C ₄ alkyl group, and m is An integer of 1 to 4, n is an integer of 0 to 3, and m + n is 4.) or a mixture of one or more of partial hydrolysates thereof. As an example of the compound of the above formula, particularly, tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) is suitable from the viewpoints of thin film formation, transparency, bonding with a conductive layer, film strength and antireflection performance. .

The transparent thin film layer has a luminous reflectance of 0.8
%, May contain various resins, metal oxides, composite oxides, nitrides, or the like, or precursors capable of producing these by baking.

The above-mentioned transparent thin film layer is formed by uniformly applying a paint for forming a transparent thin film layer containing the above-mentioned components, similarly to the method used for forming the transparent conductive layer and the transparent colored layer. Can be done by Coating is performed by spin coating, roll coating, spraying, bar coating,
Any of ordinary thin film coating techniques such as a dip method, a meniscus coating method, and a gravure printing method can be used. Of these, spin coating is a particularly preferred coating method because a thin film having a uniform thickness can be formed in a short time.
After application, the coating film is dried and baked in the range of 100 ° C to 1000 ° C to form a transparent thin film layer.

In general, the antireflection performance between layers in a multilayer thin film is determined by the refractive index and thickness of the thin film and the number of laminated thin films. By designing the thicknesses of the transparent conductive layer, the transparent coloring layer and the transparent thin film layer, an effective antireflection effect can be obtained. In the case of a multilayer film having antireflection ability, when the wavelength of reflected light to be prevented is λ, if the antireflection film has a three-layer structure, the medium refractive index layer, the high refractive index layer, and the low refractive index from the substrate side Λ / 4, λ /
An optical film thickness of 2, λ / 4 is effective.

In particular, considering the ease of manufacture and economy, an SiO ₂ film having a relatively low refractive index and having a hard coat property (refractive index: 1.46) is formed on the transparent conductive layer at λ / 4. It is preferable that the film is formed to have a film thickness.

In the colored transparent conductive film of the present invention including the transparent conductive layer, the transparent colored layer, and the transparent thin film layer, the baking of the transparent conductive layer, the transparent colored layer, and the transparent thin film layer may be performed sequentially or simultaneously. Good. For example, a coating material for forming a transparent conductive layer is applied to the display surface of a display device, a coating material for forming a transparent colored layer is applied thereon, and a coating material for forming a transparent thin film layer is further applied thereover. By batch baking at a temperature of ° C., a transparent conductive layer, a transparent colored layer, and a transparent thin film layer can be simultaneously formed, and a colored transparent conductive film can be formed.

A transparent layer having irregularities may be separately formed as the outermost layer of the colored transparent conductive film. This uneven layer is
It has the effect of scattering the light reflected on the surface of the colored transparent conductive film and giving the display surface excellent antiglare properties. As the material of the uneven layer,
Silica is preferred from the viewpoints of surface hardness and refractive index. This concavo-convex layer is formed by applying a coating for forming a concavo-convex layer as the outermost layer of the colored transparent conductive film by the above-described various coating methods, and after drying, simultaneously or separately with the transparent conductive layer, the transparent colored layer, and the transparent thin film layer. It can be formed by baking at a temperature in the range of 100C to 1000C. As a method for forming the uneven layer, a spray coating method is particularly preferable.

In the display device of the present invention, any one of the above-mentioned colored transparent conductive films is formed on a display surface. Since this display device is prevented from being charged on the display surface, it does not adhere to the image display surface and shields electromagnetic waves, so that various electromagnetic interferences are prevented, and a color pigment for hue adjustment is included. As a result, the contrast characteristics of the image are excellent, and the salt water resistance is high, so that the durability is high even in an environment exposed to salt fog. In addition, when the above-mentioned uneven layer is formed, an excellent antireflection effect and antiglare effect against external light can be obtained.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The following were prepared or prepared as stock solutions common to the following Examples and Comparative Examples. (Aqueous gold sol) p containing 0.15 mmol / l chloroauric acid
H5.7 in an aqueous solution of H5
The obtained colloidal dispersion was concentrated by mixing with mmol / L sodium borohydride to obtain an aqueous sol containing 0.102 mol / L of chain-like fine gold particle aggregates.

(Silver aqueous sol) Silver nitrate (2.5 g) was dissolved in a 5 ° C. aqueous solution (60 g) in which sodium citrate dihydrate (14 g) and ferrous sulfate (7.5 g) were dissolved. An aqueous solution (25 g) of pH 5.9 was added to obtain a red-brown silver sol. The silver sol was washed with water by centrifugation to remove impurity ions, and pure water was added to obtain an aqueous sol containing 0.185 mol / L of silver fine particles. (Aqueous palladium sol) An aqueous solution of pH 6 containing 0.15 mmol / l of palladium chloride was mixed with an equimolar amount of 0.024 mmol / l of sodium borohydride with respect to palladium to obtain a colloidal solution. Concentrate the dispersion,
An aqueous sol containing 0.189 mol / l of palladium fine particles was obtained.

(Colloidal silica) "Silica Doll 30" (carbon black dispersion) manufactured by Nippon Kagaku Kogyo Co., Ltd. "AMBK-2" (blue pigment dispersion) manufactured by Orient Kagaku Kogyo Co., Ltd. "AMBE-4" manufactured by Orient Kagaku Kogyo Co., Ltd. ( Purple pigment dispersion) "AMVT-2" (silicate solution) manufactured by Orient Chemical Co., Ltd. A mixture of tetraethoxysilane (17.4 g), 0.1 N hydrochloric acid (15.0 g), and ethyl alcohol (67.6 g) is mixed. A homogeneous solution was obtained. (Paint for forming a transparent thin film layer) Tetraethoxysilane (2.
8 g), 0.1 N hydrochloric acid (2.4 g) and ethyl alcohol (94.8 g) were mixed to form a uniform solution.

(Example 1) Preparation of paint for forming transparent conductive layer 7 g of the aqueous palladium sol, 3 g of silver aqueous sol, 0.2 g of colloidal silica, 10 g of isopropyl alcohol,
Ethyl alcohol (79.8 g) was mixed with stirring, and the obtained mixture was dispersed with an ultrasonic dispersing machine (“Sonifire 450” manufactured by BRANSON ULTRASONICS) to prepare a paint for forming a transparent conductive layer. As a result of observation by a transmission electron microscope, palladium fine particles and silver fine particles having an average particle diameter of 5 nm were aggregated in a chain, and the length was 10 nm to 80 nm. Preparation of Transparent Colored Layer Forming Paint 2 g of the carbon black dispersion and 0.6 of the blue pigment dispersion
g, purple pigment dispersion 0.6 g, colloidal silica 3.3 g
, 10 g of isopropyl alcohol, and 83.6 g of ethyl alcohol were mixed with stirring, and the resulting mixture was mixed with an ultrasonic dispersing machine (“SONIFIRE 45 manufactured by BRANSON ULTRASONICS”).
0 ”) to prepare a coating material for forming a transparent colored layer. Film formation The above-mentioned transparent conductive layer forming paint is applied to the display surface of a cathode ray tube using a spin coater, and after drying, the above-mentioned transparent colored layer forming paint is applied to this applied surface similarly using a spin coater. After drying, the coating material for forming a transparent thin film layer is further applied to the application surface using a spin coater, and after drying, the cathode ray tube is put in a drier,
The cathode ray tube of Example 1 having a colored transparent conductive film was produced by baking at 1 ° C. for 1 hour to form a colored conductive film.

(Example 2) Preparation of paint for forming transparent conductive layer 20 g of the gold aqueous sol, 1 g of the silver aqueous sol, 10 g of isopropyl alcohol, 0.4 g of colloidal silica, and 68.6 g of ethyl alcohol were mixed with stirring. Example 1
In the same manner as described above, a paint for forming a transparent conductive layer was prepared.
As a result of observation by a transmission electron microscope, gold fine particles and silver fine particles having an average particle diameter of 6 nm were aggregated in a chain, and the length was 10 nm.
８０80 nm. The transparent colored layer forming coating material was used deposited first in Example 1 was coated using a spin coater on a display screen of a cathode ray tube, dried, the transparent conductive layer forming coating on the coated surface, similarly spin coater And dried, and then the transparent thin film layer forming paint is further applied to the coated surface using a spin coater, dried, and treated in the same manner as in Example 1 to form a colored transparent conductive film. A cathode ray tube of Example 2 having the same was manufactured.

Comparative Example 1 Preparation of Transparent Colored Layer Forming Paint 2 g of the above carbon black dispersion and 0.6 of the blue pigment dispersion
g, purple pigment dispersion liquid 0.6 g, silicate liquid 20 g, isopropyl alcohol 10 g, ethyl alcohol 66.8.
g was mixed under stirring, and the obtained mixed liquid was dispersed by an ultrasonic dispersing machine (“Sonifire 450” manufactured by BRANSON ULTRASONICS) to prepare a coating material for forming a transparent colored layer containing a binder component (silicate). The coating material for forming the transparent conductive layer used in the film forming example 1 was applied to the display surface of the cathode ray tube using a spin coater, and after drying, the coating material for forming the transparent coloring layer containing the binder component was applied to the application surface. Is applied using a spin coater, and after drying, the coating material for forming a transparent thin film layer is further applied to the application surface.
Similarly, it was applied using a spin coater, dried, and treated in the same manner as in Example 1 to produce a cathode ray tube of Comparative Example 1 having a colored transparent conductive film.

Comparative Example 2 Preparation of Transparent Conductive Layer Forming Paint 7 g of the above aqueous palladium sol, 3 g of silver aqueous sol, 2 g of carbon black dispersion, 0.6 g of blue pigment dispersion, 0.6 g of purple pigment dispersion, colloidal 0.6 g of silica, 10 g of isopropyl alcohol, and 76.2 g of ethyl alcohol were mixed with stirring, and the resulting mixture was mixed with an ultrasonic disperser (BRAN).
SON ULTRASONICS “Sonifire 450”) to prepare a coating for forming a transparent conductive layer. As a result of observation with a transmission electron microscope, palladium fine particles having an average particle diameter of 5 nm, silver fine particles, and a coloring pigment having an average particle diameter of 15 nm were partially aggregated in an island shape. The coating for forming the transparent conductive layer is applied to the display surface of a cathode ray tube using a spin coater, and after drying, the coating for forming the transparent thin film layer is applied to the application surface using a spin coater in the same manner. After drying, the same treatment as in Example 1 was performed to produce a cathode ray tube of Comparative Example 2 having a colored transparent conductive film.

(Comparative Example 3) The coating material for forming the transparent conductive layer used in Film Forming Example 1 was applied to the display surface of a cathode ray tube using a spin coater, dried, and then the transparent surface used in Comparative Example 1 was applied to the coated surface. The coating material for forming a colored layer was similarly applied using a spin coater, dried, and treated in the same manner as in Example 1 to produce a cathode ray tube of Comparative Example 3 having a colored transparent conductive film.

Examples 1 and 2 and Comparative Examples 1 to
The film configuration of the colored transparent conductive film of Comparative Example 3 is shown in Table 1 below.

[0038]

[Table 1]

(Evaluation Measurement) The performance of the colored transparent conductive film formed on each of the cathode ray tubes of Examples 1, 2 and Comparative Examples 1 to 3 was measured by the following apparatus or method. Surface resistance: "Loresta AP" (manufactured by Mitsubishi Chemical Corporation) (4-terminal method) Electromagnetic wave shielding property: Calculated by the above formula 1 based on 0.5 MHz Salt water resistance: 0.5 MHz after 3 days of salt water immersion Electromagnetic wave shielding effect Transmittance: Tokyo Denshoku Automatic Haze Met
er H〓 DP ”Luminous reflectance: EG & G GAMMASCIENTIFIC“ MODEL
C-11 "Scratch resistance: A load of 1 kg was rubbed with an eraser 30 times, and the degree of scratching was visually evaluated. : No scratches Δ: slight scratches ×: scratches The results of the above evaluation tests are shown in Table 2.

[0040]

[Table 2]

From the results shown in Table 2, it was found that the transparent conductive layer for providing an electromagnetic wave shielding effect and the transparent colored layer for improving the visibility were separated into layers, and these layers were formed such that each layer did not substantially contain a binder component. The transparent conductive film (Examples 1 and 2) has a colored conductive film (Comparative Examples 1 and 3) having a second transparent colored film containing a binder component, and also has both conductive performance and a coloring effect. The conductive performance is higher than that of the colored transparent conductive film having the colored transparent conductive layer (Comparative Example 2),
In addition, it has been found that it has excellent salt water resistance, scratch resistance and visibility.

[0042]

The colored transparent conductive film according to the first aspect of the present invention is a transparent conductive film formed by using a transparent conductive layer forming paint containing metal fine particles as a conductive component and not containing a coloring material and a binder component. Layer, and a transparent colored layer formed using a transparent colored layer forming paint that contains a coloring material and does not contain a conductive component (metal fine particles) and a binder component. Not only is it excellent in prevention effect, durability such as salt water resistance and scratch resistance, but also excellent in image visibility. Further, in the display device according to claim 8 of the present invention, since the colored transparent conductive film is formed on the display surface, the display device has an excellent electromagnetic wave shielding effect and an antistatic effect, prevents electromagnetic wave interference, and displays the image. It is difficult for dust and the like to adhere to the surface, and the hue of the transmitted image is natural, so that a clear image with good visibility can be obtained.

Claims (8)

[Claims] 1. A transparent conductive layer formed using a transparent conductive layer forming paint containing metal fine particles as a conductive component and not containing a coloring material and a binder component, a conductive component containing a coloring material, and a binder component. And a transparent colored layer formed by using a transparent colored layer forming paint containing no. 2. A transparent thin film layer formed by using a transparent thin film layer forming paint containing a binder component is formed above the transparent conductive layer and the transparent colored layer. 2. The colored transparent conductive film according to 1. 3. An average particle diameter of said metal fine particles is 2 nm to 50 nm.
The colored transparent conductive film according to claim 1, wherein the thickness is in the range of nm. 4. The colored transparent conductive film according to claim 1, wherein said metal fine particles are a chain aggregate. 5. The main component of the metal fine particles is gold, silver, platinum, palladium, ruthenium, rhodium, iridium,
The colored transparent conductive film according to claim 1, wherein the transparent conductive film is at least one selected from the group consisting of osmium and rhenium. 6. The colored transparent conductive film according to claim 1, wherein said transparent colored layer contains a colored pigment and silica fine particles. 7. The colored transparent conductive film according to claim 1, wherein the luminous reflectance is 0.8% or less. 8. A display device comprising the colored transparent conductive film according to claim 1 formed on a display surface.