JPH09331187A - Anti-reflection colored transparent conductive film and cathode ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anti-reflection colored transparent conductive film which is enhanced in antistatic and electromagnetic shielding properties and where a transmission image can be controlled in have by a method wherein the colored transmission conductive film is equipped with a specific transparent conductive layer and a transparent antireflection layer, and one or more of them are made to contain blue, violet or black coloring material. SOLUTION: A colored conductive film 10 composed of a transparent conductive layer 1 and a transparent anti-reflection layer 2 is formed in this sequence on the surface of a transparent substrate 3. The transparent conductive layer 1 contains at least 10wt.% of one or more metal elements including silver. At least, either of the layers 1 and 2 contains one of blue, violet, and black coloring material. With this setup, the transmission spectrum of light can be adjusted without deteriorating antistatic and electromagnetic shielding properties. The hue and the contrast are optimized and the reflection is reduced, so that a transparent image which is sharp and excellent in visibility can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection colored transparent conductive film and a cathode ray tube, and is particularly useful for an image display surface such as a cathode ray tube face panel, which has an excellent antistatic effect, electromagnetic wave shielding effect and antireflection effect. The present invention relates to an antireflection colored transparent conductive film having an effect and having an optimized hue and contrast of a transmitted image, and a cathode ray tube using the same for a face panel.

[0002]

2. Description of the Related Art Generally, a transparent material having a high dielectric constant, such as glass or plastic, is easily charged with static electricity and easily transmits electromagnetic waves. For this reason, a transparent conductive film is attached to a face panel of a cathode ray tube used for a TV Braun tube or a computer display for the purpose of preventing static electricity and / or shielding electromagnetic waves. Further, in a liquid crystal display plate, an electroluminescence display plate, and the like, a transparent conductive film serving as an electrode is formed inside a transparent plate material.

A conventional transparent conductive film is formed by forming a transparent conductive oxide such as indium oxide on a face panel by a sputtering method, a vapor deposition method or the like, and sticking this on the display surface of a cathode ray tube. , A dispersion liquid of antimony-doped tin oxide and a silica sol-based binder is applied to the front surface of the face panel. Also, a transparent conductive film in which at least one transparent antireflection layer is laminated on the upper layer and / or the lower layer of the transparent conductive layer so that the reflected lights on the plurality of laminated thin film surfaces cancel each other by an interference effect. It is used.

As a conventional method for forming a transparent conductive film having high conductivity on the face panel of a cathode ray tube, which not only prevents charging but also shields electromagnetic waves, the face panel is placed in a vapor deposition pot and oxidized. A method for forming an indium compound or a tin oxide compound by vapor deposition (PVD
Method), a method of thermally decomposing an organic compound of indium or tin, a salt solution or the like to form a transparent conductive film on the face panel (CVD method).

[0005]

The transparent conductive film formed by the above-mentioned various methods is sufficiently transparent because it may have a small thickness when used only as an antistatic film, but it is an electromagnetic wave shielding layer. When used as an electrode film or an electrode film, high conductivity is required, so the film thickness must be increased to some extent.
For this reason, there is a problem that the transparency is lowered and the screen is darkened, and the conductive film is colored due to absorption at a specific light wavelength, so that the hue of the transmitted image unnaturally changes. Further, when the PVD method or the CVD method is used, a vacuum or a high temperature is required to form a film, so that a capital investment becomes high when a transparent conductive film is formed on a large area substrate, There was a problem that the efficiency was poor and the manufacturing cost was high.

[0006] In order to suppress the equipment investment and efficiently form the transparent conductive film on a large-sized substrate, a coating method has been proposed. For example, a coating material containing an organic indium compound (see Japanese Patent Application Laid-Open No. 52-1497), a coating material in which an indium salt or tin salt is dissolved in water or an organic solvent (Japanese Patent Application Laid-Open No. 63-
64012, JP-A-55-51737, JP-A-58-82407, and JP-A-57-36714.
Japanese Patent Laid-Open No. 60-220507) and the like have been proposed. However, in order to form a transparent conductive film using these paints, heat treatment at a high temperature of 350 ° C. or higher is required after coating the substrate, so that there is a limit to the material of the substrate that can be used and the manufacturing process. There are also many restrictions on the top.

A paint in which fine particles or colloid of a transparent conductive oxide such as tin oxide or indium oxide is dispersed in a polymer solution or a binder resin has also been proposed (Japanese Patent Publication No. Sho-3).
JP-A-5-6616, JP-A-57-85866,
JP-A-58-91777, JP-A-62-2787
No. 05 publication). It is said that the transparent conductive film can be formed at a relatively low temperature by using this paint.

However, in any of the above transparent conductive films,
In order to obtain a practical transparency, it is necessary to reduce the thickness of the coating film, and if it is reduced, the conductivity will decrease. It is insufficient for the purpose, and if the film thickness is increased, the transparency is lowered and the screen becomes dark, so that the use is limited.

As a transparent conductive film having an excellent electromagnetic wave shielding effect and an antireflection effect, a transparent conductive layer composed of metal fine particles having an average particle diameter of 2 to 200 nm and a transparent coating film having a refractive index lower than that is proposed. (Japanese Patent Laid-Open No. 8-778
32). Although this transparent conductive film can be expected to have an electromagnetic wave shielding effect, it absorbs at a specific wavelength of transmitted light depending on the light transmission spectrum of metal fine particles, and the conductive film is colored, causing the hue of the transmitted image to change unnaturally. However, the antireflection effect could not be expected.

In addition to the above, for the purpose of simply forming a conductive film, a method of applying a coating material in which reduced metal colloid particles are dispersed in a photosensitive resin (see Japanese Patent Application Laid-Open No. 4-23484), A method of printing by a screen printing method on a dielectric green sheet using a conductive paste (see Japanese Patent Laid-Open No. 4-19609) is also known.
All of these are opaque, and a transparent conductive film cannot be obtained. The present invention has been made in order to solve the above problems, and therefore, the object thereof is that it can be manufactured at low cost, is excellent in antistatic property and electromagnetic wave shielding property, and is transparent in which the hue of a transmitted image is adjusted. It is to provide a conductive film and a cathode ray tube using the same.

[0011]

In order to solve the above problems, the present invention provides a transparent conductive layer according to claim 1 containing at least 10% by weight of at least one metal containing silver. At least one transparent antireflection layer laminated on the upper layer and / or the lower layer of the transparent conductive layer, and at least one layer of these layers is colored with at least one of blue, purple and black. An antireflection colored transparent conductive film containing a material is provided. Hereinafter, the antireflection colored transparent conductive film is simply referred to as “colored conductive film”.

In claim 2, the colored conductive film is
It is preferable that the coloring material is contained in the transparent conductive layer and the content thereof is 20% by weight or less of the content of the metal.

The present invention also provides a cathode ray tube according to claim 3, wherein the colored conductive film according to claim 1 or 2 is formed on the front surface of a face panel.

[0014]

Embodiments of the present invention will be described below in detail. FIG. 1 shows a colored conductive film which is a preferred embodiment of the present invention. In FIG. 1, the colored conductive film 10 is formed on the surface of the transparent substrate 3, and the transparent conductive layer 1 and the transparent antireflection layer 2 are sequentially arranged from the transparent substrate 3 side.
And are stacked.

The transparent conductive layer 1 contains 10% by weight or more of silver and 20% by weight or less of silver, and contains a purple pigment. This silver may be contained in the layer as fine particles, or may be in a thin film state in which the fine particles are melted by heating and fused to the transparent substrate 3. Also,
The antireflection layer 2 in this embodiment is formed mainly of SiO ₂ . In order to obtain the antireflection effect, the antireflection layer 2 has a refractive index different from that of the transparent conductive layer 1.

In the colored conductive film 10 of this embodiment, since the transparent conductive layer 1 contains 10% by weight or more of silver, it has a high conductivity, has an antistatic property, and is harmful to the radiation from a cathode ray tube or the like. It also has the effect of blocking electromagnetic waves. Further, since both the transparent conductive layer 1 and the antireflection layer 2 are transparent, the colored conductive film 10 has a high light transmittance in the visible light range of 400 nm to 800 nm. Furthermore, the antireflection layer 2
Therefore, the reflected light is well suppressed.

Further, since the transparent conductive layer 1 contains an appropriate amount of purple pigment, for example, silver alone has a thickness of 400 nm.
There is absorption of short wavelength visible light of 530 nm, and the hue of the transmitted image looks yellowish and unnatural, but it is corrected by the absorption of long wavelength visible light by the violet pigment,
The transmission spectrum of light is flattened over the entire wavelength band of visible light, and the hue of the transmission image is improved to a natural color such as purple.

In the transparent conductive film 10 of the above embodiment, the antireflection layer 2 is laminated on the transparent conductive layer 1, and the antireflection layer 2 is transparent and has a refractive index different from that of the transparent conductive layer 1. Therefore, the light reflected at the interfaces of a plurality of laminated thin films, for example, the interface between the transparent conductive layer 1 and the antireflection layer 2 or the interface between the transparent conductive layer 1 and the transparent substrate 3 cancels each other due to the interference effect, and the transmitted image The external light reflection that causes the deterioration of visibility is effectively suppressed, and the visibility of the transmitted image is enhanced.

Next, the transparent conductive layer 1 used in the present invention will be described in detail. The transparent conductive layer 1 basically contains at least 10% by weight of one or more metals including silver. This metal may be in the form of fine particles, in the form of a thin film, or in the form of a mixture of fine particles and a thin film. This metal may be silver alone, or a combination of silver and gold, copper, platinum, nickel or the like. These metals are
In any case, the wavelength band of visible light is 400 nm to
It should be selected so that it has high transparency in the range of 800 nm, low absorption at a specific wavelength, and good conductivity. When a plurality of metals are used, they may be in an alloy state or may be a state in which a single metal phase is mixed.

The reason for using at least silver in the transparent conductive layer 1 is that silver is relatively easily and inexpensively available as a colloidal dispersion, has high conductivity, and is excellent in antistatic property and electromagnetic wave shielding property. Moreover, a conductive layer having high transparency can be formed. Therefore, silver can be used alone in the transparent conductive layer, but can be used in combination with, for example, gold if necessary from the viewpoint of hue correction.

When silver and gold are used as the metals, the mixing ratio thereof is 99.9: 0.1-0.
It is preferably within the range of 1: 99.9. But,
In order to obtain a more flatly corrected light transmission spectrum and economy, it is more preferable to set the weight of silver: gold within the range of 99: 1 to 50:50.

The reason why the content of the metal in the transparent conductive layer 1 is 10% by weight or more is that if the content is less than 10% by weight, the conductivity is lowered and it becomes difficult to obtain a substantial electromagnetic wave shielding effect. Because.

When the transparent conductive layer 1 contains fine metal particles, the average particle diameter of the fine metal particles is preferably 0.05 μm or less. The reason is that the average particle size is 0.05
This is because if the thickness exceeds μm, absorption of visible light increases when a transparent conductive layer is formed, and it may be difficult to obtain a transparent conductive layer satisfying both transparency and conductivity.

The thickness of the transparent conductive layer 1 is preferably 1 μm or less from the viewpoint of ensuring transparency. In particular, in order to effectively reduce the reflected light by laminating it with the antireflection layer 2, the film thickness is more preferably 0.2 μm or less.

In order to effectively use the transparent conductive layer 1 not only for preventing electrostatic charge but also for shielding electromagnetic waves, it is necessary to design film characteristics corresponding to the frequency of electromagnetic waves to be shielded. Generally, the electromagnetic wave shielding effect is expressed by the following equation (1).

[0026]

[Equation 1]

From the viewpoint of ensuring transparency, the film thickness t is 1 μm.
m (1 × 10 ⁻⁴ cm) or less,
The formula (1) can be approximately represented by the following formula (2).

[0028]

[Equation 2]

That is, it is understood that the smaller the volume specific resistance value (ρ) of the transparent conductive layer 1 is, the greater the shielding effect against electromagnetic waves in a wide range of frequencies. Generally, the electromagnetic wave shielding effect is effective if S> 30 dB,
Further, if S> 60 dB, it is regarded as excellent. The frequency of regulated electromagnetic waves is generally 10 kHz to 1000 M.
In order to obtain a good electromagnetic wave shielding effect with a film thickness of 1 μm or less, it is desirable that the volume resistivity (ρ) of the transparent conductive layer 1 be 10 ³ Ω · cm or less.
This value can be achieved by setting the total content of metals to 10% by weight or more when the transparent conductive layer 1 is formed of, for example, two kinds of silver and gold.

In the colored conductive film of the present invention, the transparent conductive layer 1 includes a visible light wavelength band (400
(nm to 800 nm), and may include inorganic fine particles having transparency. When adding transparent inorganic fine particles,
It is preferable that the transparent conductive layer 1 has conductivity so as not to impair the conductivity. The average particle size of the transparent inorganic fine particles is preferably 0.1 μm or less.

Examples of transparent inorganic fine particles that can be used for this purpose include silicon, aluminum, zirconium,
An oxide, a complex oxide, a nitride, or the like of cerium, titanium, yttrium, zinc, magnesium, indium, tin, antimony, gallium, and the like can be given. In particular, examples of preferable transparent inorganic fine particles having conductivity include oxides such as indium and tin, complex oxides, antimony-doped tin oxide, and the like.

The transparent conductive layer 1 may contain a binder component in order to improve the film strength. Examples of binder components that can be used include, for example, polyester resin, acrylic resin, epoxy resin, melamine resin,
Examples include organic synthetic resins such as urethane resins, butyral resins, and ultraviolet curable resins, hydrolysates of metal alkoxides such as silicon, titanium and zirconium, and organic / inorganic binder components such as silicone monomers and silicone oligomers. .

In order to enhance the affinity between the binder component and the metal, the surface of the metal is coated with a coupling agent such as a silicone coupling agent or a titanate coupling agent, a carboxylate, a polycarboxylate or a phosphate ester. It may be treated with a lipophilic surface treatment agent such as a salt, a sulfonate or a polysulfonate.

The transparent conductive layer 1 can be formed, for example, by the following method. That is, one of them is a colloidal dispersion containing silver fine particles having an average particle diameter of 0.05 μm or less, and optionally other metal fine particles, transparent inorganic fine particles, a binder, a coloring agent, etc., for example, silver colloid. A transparent conductive layer coating material composed of a liquid is prepared, and this is uniformly applied on a substrate 3 such as a cathode ray tube face panel to a thickness such that the ratio of the metal in the dried transparent conductive layer 1 is 10% by weight or more. Is applied, dried, and baked at 150 ° C. for 1 hour, for example.

When the transparent conductive layer 1 contains two or more kinds of metals such as silver and gold, the above-mentioned transparent conductive layer coating material contains fine particles of each metal alone and, if necessary, the above-mentioned fine particles. A plurality of transparent conductive layer paints made of a colloidal dispersion containing transparent inorganic fine particles, a binder, a coloring material, etc. are prepared, and these paints are sequentially applied onto the substrate 3 and each metal in the transparent conductive layer 1 after drying. It can also be formed by a method of uniformly coating, drying, and baking so that the ratio becomes a predetermined value. In this method,
There is no particular restriction on the order of application.

In the above-mentioned forming method, the method for producing the transparent conductive layer coating material to be used is not particularly limited, but for example, a colloidal liquid in which fine metal particles are dispersed may be added, if necessary, to the fine inorganic particles, the binder and the coloring material. It can be produced by a commonly used dispersion technique such as an ultrasonic disperser or a sand mill.

Further, in any of the above methods, the coating can be carried out by using a known thin film coating technique such as spin coating, roll coating, knife coating, bar coating, spray coating, dipping or meniscus coating.

In the colored conductive film of the present invention, at least one transparent antireflection layer 2 is laminated on the upper layer and / or the lower layer of the transparent conductive layer 1. Next, the antireflection layer 2 will be described in detail.

The antireflection layer 2 is made of, for example, a transparent oxide such as silicon, aluminum, zirconium, cerium, titanium, yttrium, zinc, magnesium, indium, tin, antimony or gallium, a complex oxide, or a nitride. A coating material (antireflection coating material) containing an inorganic substance or a precursor capable of producing these by baking as a main component, and optionally other components such as a coloring agent is provided as a lower layer or an upper layer of the transparent conductive layer 1. The transparent conductive layer 1 can be formed at the same time as the transparent conductive layer 1 or separately.

A transparent hard layer is formed on the transparent conductive layer 1.
A coat layer is formed, and the refractive index of this hard coat layer is transparent.
Antireflection function by making it different from the conductive layer 1
To protect the transparent conductive layer 1 and prevent reflection.
You can also. Form this anti-reflective hard coat layer
As an example of a substance that can be used, for example, the following formula M (OR)_mR_n In the above, M is Si, Ti or Zr, and R is C₁
~ C_FourM is an integer of 1 to 4,
a compound wherein n is an integer of 1 to 3 and m + n is 4
Product, or one or more of its partial hydrolysates
Mention may be made of mixtures. As an example of this compound
Is, for example, tetraethoxysilane (Si (OC
₂H_Five)_Four) Is preferably used. This anti-reflective hard
The coat layer is a metal oxide forming the antireflection layer 2 described above.
Material, complex oxide, or nitride, or by baking
Precursors capable of producing these and / or
May contain a coloring material or the like.

As the antireflection layer 2, a material having a refractive index different from that of the transparent conductive layer 1 is selected, and if the film thicknesses thereof are appropriately adjusted, the interface of the transparent conductive layer 1 and / or the substrate surface can be obtained. The reflected lights from the light sources cancel each other due to the interference effect, and the antireflection effect can be realized.

In general, the antireflection ability of a thin film is determined by the refractive index and film thickness of the film, and in the case of a multilayer film, the number of laminated films. Now, for example, when a transparent conductive layer is used as a lower layer and an antireflection layer having a low refractive index is formed thereon, when the wavelength of the reflected light to be prevented is λ, the transparent conductive layer and the antireflection layer are The optical thickness of each is λ /
Reflection can be effectively prevented by setting λ / 4, λ / 4, or λ / 2, λ / 4. When a transparent conductive layer is used as an upper layer and an antireflection layer having a high refractive index is formed below the transparent conductive layer, when the wavelength of the reflected light to be prevented is λ, the optics of the transparent conductive layer and the antireflection layer are Reflection can be effectively prevented by setting the target film thickness to λ / 4, λ / 4, or λ / 2, λ / 4. In addition, it is possible to effectively prevent reflection by using a three-layer film structure including an antireflection layer, a transparent conductive layer, and an antireflection layer, and setting optical thicknesses of λ / 4, λ / 2, and λ / 4, respectively. can do.

In particular, considering the ease of manufacture and the economical efficiency, the upper layer of the transparent conductive film has a relatively low refractive index,
SiO ₂ (with a refractive index of 1.4
It is preferable to form the film 6) with a film thickness of λ / 4.

In the above embodiment, the transparent conductive layer 1
A purple pigment is contained therein as a coloring material. In the case where silver is used as the metal, for example, when the purple pigment uses silver as a metal, silver absorbs short-wavelength visible light of 400 nm to 530 nm, so that the transparent conductive layer is colored yellowish and the hue of the transmission image looks unnatural. Is corrected to flatten the light transmission spectrum over the entire wavelength band of visible light, thereby improving the hue of the transmitted image.

The coloring material that can be preferably used in the colored conductive film of the present invention is a blue, purple or black coloring material. Among them, the violet pigment and the blue pigment are particularly effective for the toning of the transmitted image, and the black pigment has the effect of toning but also the effect of enhancing the color contrast of the transmitted image. However, the colored conductive film of the present invention may contain a coloring material of another color for the purpose of coloring a specific color.

Examples of suitable coloring agents include phthalocyanine blue, cyanine blue, indanthrone blue, dioxazine violet, aniline black, alkali blue, titanium oxide, and the like.
Organic and inorganic pigments such as chromium oxide, iron black, cobalt blue, cerulean blue, zinc chromate, ultramarine, manganese violet, cobalt violet, dark blue, carbon black, and azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes Examples thereof include quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, perinone dyes, and other blue, purple, or black dyes.

In addition to the above-mentioned usual coloring materials, those having a filter effect of selectively absorbing visible light other than the three primary colors (for example, JP-A-1-320742 and JP-A-3-11532). Japanese Patent Laid-Open No. 3-2540
No. 48, etc.), which obtains a high contrast effect by reducing the transmittance of visible light over the whole (for example, see Japanese Patent Laid-Open No. 6-80903, etc.), minimum reflection in an antireflection film due to interference of a laminate. A material that obtains an antireflection effect by using a coloring material that substantially matches the ratio (see, for example, JP-A-5-203804), or a material that absorbs visible light of a specific wavelength to obtain a natural image that is easy on the eyes ( For example, a coloring material that has been conventionally used or proposed for a transparent conductive film or a face panel of a cathode ray tube such as JP-A-7-151903) can also be used.

One or more of the above-mentioned coloring materials may be contained in any one layer or two or more layers of the transparent conductive layer and the antireflection layer, and the two or more coloring materials are different from each other. It may be included in the layer. Generally, it is preferable that the colorant for toning that improves the hue of the transparent conductive layer 1 be contained in the transparent conductive layer 1.

The kinds and amounts of these coloring materials used are
It should be appropriately selected according to the optical film characteristics of the corresponding colored conductive film. In particular, when a coloring material is mixed in the transparent conductive layer 1, it is preferable to select it so as to be 20% by weight or less of the metal content. 20% by weight of metal content
If it exceeds the range, the conductivity may decrease and the electromagnetic wave shielding effect may decrease.

Generally, the absorbance A of a transparent thin film containing a coloring material is represented by the following formula. A = log ₁₀ (I ₀ / I) = εCD (wherein I ₀ is incident light, I is transmitted light, C is color density, D is optical distance, and ε is molar extinction coefficient.)

In the colored conductive film of the present invention, a coloring material having a molar extinction coefficient ε> 10 is generally used. Further, the blending amount of the coloring material varies depending on the absorbance of the coloring material used, but generally, the absorbance A ₁ of the laminated film and the single layer film containing the coloring material is 0.0004 to 3 abs. It is preferable that the amount be within the range. If these conditions are not met, the transparency and / or toning effect will be reduced. In particular, when the above-mentioned coloring material is blended in the transparent conductive layer 1, a great effect is exhibited in adjusting the transmitted color and the reflected color. However, in this case, when the amount of metal added exceeds 10% by weight, a decrease in conductivity is observed, and when it exceeds 20% by weight,
As described above, the electromagnetic wave shielding effect is impaired.

The cathode ray tube of the present invention is one in which the colored conductive film having any of the above structures is formed on the front surface of the face panel. In this cathode ray tube, since the face panel is prevented from being charged, dust or the like does not adhere to the image display surface, electromagnetic waves are shielded, various kinds of electromagnetic interference are prevented, reflected light is reduced, and residual reflected light is reduced. Also has a color tone close to that of natural light, high transparency, haze is removed, and the transmission spectrum is flattened in the visible light band, so the image does not unnaturally color and is excellent in visibility and easy on the eyes. Becomes

[0053]

EXAMPLES The present invention will be described in more detail below with reference to examples. (Preparation of paint) Preparation of silver colloid: sodium citrate dihydrate (1
4 g), 60 g of a solution in which ferrous sulfate (7.5 g) is dissolved
While maintaining at 5 ° C., 25 g of a solution in which silver nitrate (2.5 g) was dissolved was added to form a silver colloid. The obtained silver colloid was washed with water by centrifugation to remove impurities, and then 38.1 g of pure water was added to prepare a silver colloid for paint. The particle size of the obtained silver colloid particles is 0.005.
It was μm to 0.03 μm. Preparation of gold colloid: Tetrachloroauric acid hydrate (2 g)
A potassium colloid solution (4 g) and trisodium citrate dihydrate (0.025 g) were added to the mixture to form a gold colloid. Preparation of antireflection hard coat paint: tetraethoxysilane (0.8 g) and 0. 1N hydrochloric acid (0.8 g) and ethyl alcohol (98.4 g) were mixed to form a uniform solution.

(Example 1) Preparation of transparent conductive paint: Silver colloid 13.5 g Blue pigment (LIONOL BLUE FG-7330 manufactured by Toyo Ink Mfg. Co., Ltd.) 0.05 g Pure water 66.45 g Butyl cellosolve 10.0 g IPA 10. 0 g The above ingredients were blended and dispersed with an ultrasonic disperser (“Sonifer 450” manufactured by Central Scientific Trading Co., Ltd.) to prepare a transparent conductive paint.

Film formation: The above transparent conductive paint is applied on the surface of a cathode ray tube panel using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

(Example 2) Preparation of transparent conductive paint: Silver colloid 13.5 g Purple pigment (LIONOGEN VIOLET R6100 manufactured by Toyo Ink Mfg. Co., Ltd.) 0.05 g Pure water 66.45 g Butyl cellosolve 10.0 g IPA 10.0 g Above The ingredients described above were blended and dispersed with an ultrasonic disperser (“Soniffer 450” manufactured by Central Kagaku Trading Co., Ltd.) to prepare a transparent conductive paint.

Film formation: The above transparent conductive paint is applied to the surface of a cathode ray tube panel by using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

(Example 3) The above components were blended and dispersed with an ultrasonic disperser ("Soniffer 450" manufactured by Central Scientific Trading Co., Ltd.) to prepare a transparent conductive paint.

Film formation: The above transparent conductive paint is applied on the surface of a cathode ray tube panel using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

(Example 4) Preparation of transparent conductive paint: Silver colloid 13.5 g Purple pigment (LIONOGEN VIOLET R6100 manufactured by Toyo Ink Mfg. Co., Ltd.) 0.05 g Gold colloid 6 g Pure water 60.45 g Butyl cellosolve 10.0 g IPA 10.0 g The above components were blended and dispersed with an ultrasonic disperser (“Sonifer 450” manufactured by Central Scientific Trading Co., Ltd.) to prepare a transparent conductive paint.

Film formation: The above transparent conductive paint is applied on the surface of a cathode ray tube panel using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

(Comparative Example 1) Preparation of transparent conductive paint: Silver colloid 15 g Pure water 65 g Butyl cellosolve 10 g IPA 10 g The above ingredients were blended and dispersed with an ultrasonic disperser ("Soniffer 450" manufactured by Central Scientific Trading Co., Ltd.). Then, a transparent conductive paint was prepared.

Film formation: The above transparent conductive paint is applied on the surface of a cathode ray tube panel using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

Comparative Example 2 Preparation of transparent conductive paint: Antimony-doped tin oxide fine powder (Sumitomo Osaka Cement Co., average particle size 0.01 μm) 1.5 g Pure water 78.5 g Butyl cellosolve 10.0 g IPA 10.0 g The above components were blended and dispersed with an ultrasonic disperser ("Soniffer 450" manufactured by Central Scientific Trading Co., Ltd.) to prepare a transparent conductive paint.

Film formation: The above transparent conductive paint is applied to the surface of a cathode ray tube panel using a spin coater, and after drying,
Similarly, the antireflection hard coat paint of 1 was applied using a spin coater, and baked at 150 ° C. for 1 hour in a dryer to form a transparent conductive film, whereby a cathode ray tube having an antireflection / high conductive film was prepared.

For each of the samples of Examples 1 to 4 and Comparative Examples 1 and 2, the conductive film evaluation test was conducted. The evaluation items and the test machine (or test method) are described below. (Membrane evaluation method) Transmittance: "Automatic" manufactured by Tokyo Denshoku Co., Ltd.
Haze meter H III DP ”Haze:“ Automatic Haze meter HI ”manufactured by Tokyo Denshoku Co., Ltd.
II DP "Surface resistance value:" Loresta AP "made by Mitsubishi Petrochemical (4-end needle method) Reflectivity: EG & G GAMMA SCIENTIF
IC "MODELC-11" Reflective color: Minolta Camera "CR-300" Scratch resistance: 1 kg load, eraser film surface 50
After reciprocating once, the state of scratches on the film surface is visually evaluated. ○: No scratches △: Slightly scratches ×: Many scratches Visibility: Comprehensive evaluation including low reflection performance, reflected color, and transmitted color ○: Good △: Slightly bad ×: Poor Transmission spectrum: "U-Best50" manufactured by JASCO Corporation The results of the above evaluation test are shown in Table 1 and FIG.
Shown in (b), (c) and (d).

[0067]

[Table 1]

From Table 1, it can be seen that the sample of Comparative Example 2 containing no silver has a high transmittance but a high surface resistance, and thus a low electromagnetic wave shielding performance. The samples of Examples 1 to 4 and Comparative Example 1 containing silver all have surface resistances in the order of 10 ² Ω / □, and it can be seen that high electromagnetic wave shielding performance is obtained.

In Table 1 and FIG. 2 (a), Example 1 containing silver and a blue pigment is relatively similar to Comparative Example 1 except that it does not contain a blue pigment.
The transmittance of 0 nm to 550 nm is improved, and the yellowish transmitted color is moderated as a whole. Also regarding reflection,
Since the reflectance decreases and the reflected color is close to natural color,
The effect of improving visibility is recognized.

In Table 1 and FIG. 2 (b), Example 2 containing silver and a violet pigment is relatively similar to Comparative Example 1 except that it does not contain a violet pigment, and has a wavelength band of 40%.
The transmittance of 0 nm to 500 nm is improved, and the yellowish transmitted color is moderated as a whole. Also regarding reflection,
Since the reflectance decreases and the reflected color is close to natural color,
A large improvement effect of visibility is recognized.

In Table 1 and FIG. 2 (c), Example 3 containing silver and a black pigment greatly impairs the transmission color and reflectance when compared with Comparative Example 1 which is similar except that it does not contain a black pigment. However, since the reflected color close to natural light is obtained, the effect of improving the visibility is recognized.

In Table 1 and FIG. 2 (d), Example 4 containing silver, gold and a violet pigment is similar to Comparative Example 1 except that gold and violet pigment are not included, and the transmission spectrum of Flattening has been achieved, and the yellow transmission color is largely alleviated as a whole. Also regarding reflection,
Since the reflectance decreases and the reflected color is close to natural color,
A large improvement effect of visibility is recognized.

As described above, in the colored conductive film of the present invention, the light transmission spectrum is flattened over the entire visible light band, the reflected color and the contrast are improved, and the antistatic property and the electromagnetic wave shielding property are excellent. Because
Not only is it suitable for use as a face panel of a cathode ray tube, but it can also be used advantageously for other display plates such as liquid crystal display plates, electroluminescence display plates, plasma display plates, and electroluminescent display plates.

[0074]

The colored transparent conductive film of the present invention has a transparent conductive layer according to claim 1 containing 10% by weight or more of at least one metal containing silver, and an upper layer of the transparent conductive layer and / or Or at least one transparent antireflection layer laminated as a lower layer, and at least one layer of these layers contains at least one colorant of blue, purple and black Therefore, the transmission spectrum of light can be adjusted without impairing the antistatic property and the electromagnetic wave shielding property, and the hue and contrast are optimized, and the clear transmission image with good visibility with reduced reflection is obtained. Will be available.

In the second aspect, when the coloring material is contained in the transparent conductive layer and the content thereof is 20% by weight or less of the metal content, the antistatic property, the electromagnetic wave shielding property and the transparency are impaired. It becomes possible to suitably adjust the hue and the contrast.

In claim 3, the cathode ray tube of the present invention comprises:
Since any one of the above colored conductive films is formed on the front surface of the face panel, it is difficult for dust to adhere to the display surface and harmful electromagnetic interference is prevented, and the hue of the transmitted image is natural and the contrast is good. In addition, the difficulty of viewing due to reflection is reduced, and a clear transmitted image with good visibility can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of a colored conductive film of the present invention.

2 (a), (b), (c), and (d) are Embodiment 1, Embodiment 2, Embodiment 3, and Embodiment 4 of the present invention, respectively.
6 is a graph showing the light transmission spectrum in the visible light band of Comparative Example in comparison with Comparative Example.

[Explanation of symbols]

 1 ... Transparent conductive layer 2 ... Antireflection layer 3 ... Transparent substrate 10 ... Antireflection colored transparent conductive film

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01J 29/88 H04N 5/64 541D H04N 5/64 541 G02B 1/10 A

Claims (3)

[Claims] 1. One or more metals containing at least silver
A transparent conductive layer containing 0% by weight or more, and at least one layer laminated on an upper layer and / or a lower layer of the transparent conductive layer.
A transparent antireflection layer of at least one of these layers, and at least one of these layers is at least one of blue, purple and black.
An antireflective colored transparent conductive film comprising a colorant of one kind. 2. The antireflection colored transparent conductive material according to claim 1, wherein the coloring material is contained in the transparent conductive layer, and the content thereof is 20% by weight or less of the content of the metal. film. 3. A cathode ray tube, comprising the antireflection colored transparent conductive film according to claim 1 or 2 formed on the front surface of a face panel.