JPH09188545A - Electroconductive film, its production and glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electroconductive film enabling the shielding of electromagnetic wave by a low temperature treatment, i.e., applying a coating liquid containing sol prepared by dispersing specific fine particles of electroconductive compound oxide on a base body and curing the coating. SOLUTION: A ruthenium salt and a soluble salt of one element or more selected from Co, Ni, Fe, Zn, Cr, Mn, Cu, Bi, Sb and lanthanoids excluding promethium are hydrolyzed in a medium at pH of 3-13 to obtain a coprecipitate. The obtained coprecipitate is dried and baked at 300-700 deg.C to obtain fine particles of electroconductive compound oxide having an average particle diameter of <=100nm. The fine particles are dispersed in an organic solvent having a permittivity of >=5 and a boiling point of 50-250 deg.C or in water to prepare a coating liquid having a solid concentration of 0.01-10wt.%. This coating liquid is applied on a base body, and the liquid is dried and heated at 100-500 deg.C to cure the coating. Thus, an electroconductive film having a thickness of 50-400nm is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive film, a method for manufacturing the same, and a glass article, for example, a conductive film formed on the surface of a glass substrate such as a cathode ray tube panel, a method for manufacturing the same, and a glass article having the conductive film. .

[0002]

2. Description of the Related Art Conventionally, cathode ray tubes such as cathode ray tubes (CR
T) Since the panel operates at a high voltage, static electricity is induced on the surface of the panel at the time of starting or ending. This static electricity often causes dust to adhere to the surface of the cathode ray tube panel, causing a reduction in the contrast of the display image, or causing discomfort due to a slight electric shock when directly touched by a human hand.

In the past, in order to prevent the above-mentioned matters, many attempts have been made to provide a transparent antistatic film on the surface of the cathode ray tube panel. For example, JP-A-63-7624
No. 7, there is proposed a method in which the surface of a cathode ray tube panel is heated to about 350 ° C. and a translucent conductive oxide layer such as tin oxide and indium oxide is provided by a CVD method.

However, in this method, there is a problem in that in addition to the cost of the apparatus, the phosphor in the cathode ray tube is dropped off because the surface of the cathode ray tube is heated to a high temperature, and the dimensional accuracy is lowered. Further, tin oxide is the most common material used for the conductive layer, but in this case, there is a drawback that it is difficult to obtain a high-performance film by low temperature treatment.

Further, in recent years, radio wave interference to electronic equipment due to electromagnetic wave noise has become a social problem, and standards and regulations are being made to prevent it. Electromagnetic noise may cause skin cancer in human body due to electrostatic charge on CRT, influence of low frequency electric field on fetus, other X-rays,
The harm caused by ultraviolet rays is regarded as a problem in each country. In order to deal with these problems, by interposing a conductive coating film on the surface of the cathode ray tube panel, an electromagnetic wave hits the conductive coating film, induces an eddy current in the coating film, and the electromagnetic wave is reflected by this action. A method has been proposed.

However, in order to obtain such an effect, it is necessary to have a coating film having good conductivity which can withstand high electric field strength.
It was more difficult to obtain a film having such good conductivity by the method using a conductive paint.

In general, a metal or ruthenium oxide or other good conductive material does not have a band gap due to the structure of its orbital electrons, so that absorption occurs in the visible light region and the film is colored. It is difficult to apply as is.

On the other hand, Sb-doped SnO ₂ and F-doped Sn
Semiconductor-type oxides such as O ₂ , ITO, and Al-doped ZnO have a band gap of 3.1 eV or more and are translucent. However, although it has a light-transmitting property, it has been difficult to exhibit conductivity enough to be used for a high-performance electromagnetic wave shield.

Further, the coating method for forming the conductive film and the low-reflection film has been used not only in the field of optical equipment, but also in consumer equipment, especially TV and computer equipment terminals.
Many studies have been made regarding RT. The conventional method is, for example, as described in JP-A-61-118931, in order to have an antiglare effect on the surface of a cathode ray tube panel, a SiO ₂ layer having fine irregularities is attached to the surface or the surface is etched with hydrofluoric acid. Therefore, methods such as providing unevenness have been taken.

However, these methods are called non-glare treatments for scattering external light, and since there is essentially no method of providing a low reflection layer, there is a limit to the reduction of reflectance, and they are applied to panels such as cathode ray tubes. In such a case, it also causes a reduction in the resolution of the display image.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and it is possible to form a high performance conductive film, a low reflection conductive film and films thereof which can be formed by low temperature heat treatment. To provide a glass article having the following.

[0012]

The present invention provides cobalt, nickel, iron, zinc, chromium, manganese, copper, bismuth,
A substrate is coated with a coating solution containing a sol in which conductive complex oxide fine particles containing ruthenium as a metal component, one or more of antimony and lanthanoid elements (excluding promethium) (hereinafter simply referred to as combination elements) are dispersed. (EN) Provided are a conductive film formed by being applied and cured on the above, a method for producing the conductive film, and a glass article having the conductive film.

When only ruthenium oxide is used as a constituent component of the conductive film, the resulting film exhibits sufficient conductivity, but the visible light absorption of the film may be large and may cause coloration, which is a practical problem. There are cases.

In the present invention, a conductive film formed of conductive composite oxide fine particles is formed by using an oxide of a combined element in addition to ruthenium oxide as a constituent component of the conductive film, thereby exhibiting a predetermined conductivity. A conductive film having a predetermined light-transmitting property can be provided.

The reason why promethium is not used as a concomitant element is that in the lanthanum series, promethium 145 undergoes α-decay and electron capture with a half-life of 17.7 years and is converted to praseodymium and neodymium, respectively, and promethium 147 Β decay occurred with a half-life of 2.62 years,
This is because it has the property of converting to samarium, and therefore promethium does not exist stably in the natural world, and α particles and electron beams are emitted due to radioactive decay, which adversely affects the human body, which is not preferable.

The conductive film according to the present invention may need to change the transmission color tone of the film depending on the purpose of use.
The color tone of the formed film can be changed by combining and combining the oxides of the elements used together. In particular, the effect is remarkable when cobalt is used. Although the composite oxide particles themselves do not have the excellent light-transmitting properties of ITO particles,
By reducing the primary particle size of the above composite oxide particles and making them ultrafine particles, there is also a contribution of quantum size effect etc. even when applied to optical thin films, etc. Was able to improve.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, conductive complex oxide fine particles are prepared by using ruthenium and a concomitant element.
The molar ratio of ruthenium to the combined element is about 99:
It is preferable to use in the range of 1 to about 5:95, and if the amount of ruthenium used is less than the lower limit of the above range, it is not preferable in terms of conductivity of the film, while if it exceeds the upper limit of the above range, Is not preferable in that the translucency is not obtained.

The conductive complex oxide fine particles containing the concomitant element and ruthenium as metal components include, for example, ruthenium salts such as ruthenium chloride and soluble salts of the concomitant element such as cobalt chloride, nickel sulfate and zinc chloride. Can be obtained by simultaneously hydrolyzing the soluble salt of the above in a suitable medium in the range of pH 3 to 13, drying the obtained coprecipitate, and calcining in the range of 300 to 700 ° C. to obtain conductive composite oxide fine particles. preferable.

The firing temperature of the co-precipitate is not preferable because the firing is carried out at a temperature lower than the above temperature range because the fine particles of the conductive complex oxide obtained are amorphous and sufficient conductivity cannot be obtained. In addition, abnormal grain growth or the like occurs in the conductive complex oxide fine particles obtained by firing at a temperature higher than the above temperature range, and appearance defects such as haze when formed into a coating film are unfavorable. If the powder of the conductive complex oxide fine particles composed of the combined element and ruthenium obtained as described above is too large, the particles are difficult to disperse in the dispersion medium, so that the average particle diameter is 10
It is preferably 0 nm or less.

The conductive complex oxide fine particles containing the combination element and ruthenium as metal components are uniformly dispersed in a dispersion medium such as water or alcohol and used as a coating liquid. The solvent that is a dispersion medium is not particularly limited, but when water is used, water is preferable because the dispersibility of the fine particles is particularly improved. When the fine particles are dispersed, it is preferable to carry out stirring in order to facilitate contact between the dispersion medium and the fine particles. A commercially available disperser or crusher such as a colloid mill, a ball mill, a sand mill and a homomixer can be used for this stirring.

When the fine particles are dispersed, 2
It is also possible to heat in the range of 0 to 200 ° C. When stirring above the boiling point of the solvent that is the dispersion medium, pressure is applied so that the liquid layer can be retained. In this way, a sol is obtained in which the conductive complex oxide fine particles containing the combined element and ruthenium as the metal component are dispersed as colloidal particles in the dispersion medium.

The above-mentioned sol in the present invention can be used as it is as a coating solution, but in order to improve the coating property to the substrate,
The fine particles may be dispersed in an organic solvent, or in the case of a dispersion in water, water as a dispersion medium may be replaced with an organic solvent for use.

The organic solvent used as the dispersion medium is preferably an organic solvent having a dielectric constant of 5 or more and a boiling point of 50 ° C. or more and 250 ° C. or less. In the case of an organic solvent having a boiling point of less than 50 ° C., the solvent evaporates quickly when the coating liquid is applied to the substrate, which causes a defect in the appearance of the obtained film. When an organic solvent having a boiling point of more than 250 ° C. is used, the evaporation rate when the coating liquid is applied to the substrate and then dried is extremely slow, and the organic solvent may remain in the film after baking the film, It becomes a factor that deteriorates the characteristics of the film.

The dispersion medium used for forming the coating solution is not particularly limited in view of the above points, and examples thereof include alcohols such as methanol, ethanol, propanol and butanol,
Ethers such as ethyl cellosolve, methyl cellosolve, butyl cellosolve and propylene glycol methyl ether, ketones such as 2,4-pentanedione and diacetone alcohol, and esters such as ethyl lactate and methyl lactate are preferable.

Further, in the coating liquid containing the combined element used in the present invention and the conductive complex oxide fine particles containing ruthenium as the metal component, Si (OR) is used from the viewpoint of adjusting the viscosity, surface tension, spreadability and the like of the liquid. ) A silicon compound such as _y · R ′ _4-y (y is 3 or 4, R and R ′ are alkyl groups) can be added.
Further, various surfactants can be added to improve the wettability with the substrate.

The above coating solution is approximately 0.01 to 10% by weight.
It is preferable to adjust so that the solid content of the solid content is less than the lower limit of the above range in terms of the conductivity of the obtained film, while the solid content is the upper limit of the above range. When it exceeds the above range, it is not preferable from the viewpoints of translucency and appearance of the obtained film.

As a method for applying the coating liquid prepared as described above onto a substrate, for example, a spin coating method, a dip coating method, a spray coating method and the like can be preferably adopted. In addition, a conductive film having irregularities on the surface may be formed by using a spray coating method, and the resulting film may have conductivity as well as an antiglare effect, and a hard coat such as a silica coating may be provided thereon. It may be provided. Further, the conductive film of the present invention is formed by either a spin coating method or a spray coating method, and a solution containing Si alkoxide is spray coated thereon to form a non-glare coating of a silica coating having irregularities on the surface. It may be provided.

Since the coating solution containing the conductive complex oxide fine particle sol of the present invention can be provided as a coating solution on a substrate by itself, when a low boiling point solvent is used as a dispersion medium, it can be dried at room temperature. Although a uniform conductive complex oxide film can be obtained, when a medium to high boiling point solvent having a boiling point of 100 ° C. to 250 ° C. is used, heat treatment is performed because the solvent remains in the coating film at room temperature drying. The upper limit of the heat treatment temperature is determined by the softening point of glass, plastic, etc. used for the substrate. Considering this point, the preferable temperature range of the heat treatment is 100 to 500 ° C.

In the present invention, the conductive film can be made into a low reflective film by utilizing the interference effect of light. For example, when the substrate is glass (refractive index n = 1.52), the ratio value of (refractive index of conductive film) / (refractive index of low refractive index film) is about 1.23 on the conductive film. By forming such a low refractive index film, the reflectance of the conductive film can be most reduced. In order to reduce the reflectance, it is preferable to reduce the reflectance of light having a wavelength of 555 nm, particularly in the visible light region, but in practice, it may be appropriately determined in consideration of the reflection appearance and the like. The film thickness of such a low reflection film is preferably about 50 to 400 nm.

The outermost low-refractive-index film of the two-layer low-reflection conductive film is a solution containing MgF ₂ sol or S.
It is formed by using a solution composed of one or more kinds selected from solutions containing i-alkoxide. From the viewpoint of the refractive index, MgF ₂ is the lowest among the materials, and it is preferable to use a solution containing MgF ₂ sol to reduce the reflectance.
From the viewpoint of film hardness and scratch resistance, a film containing SiO ₂ as a main component is preferable.

Various solutions can be used as the solution containing the Si alkoxide for forming the low refractive index film.
R) _y · R ′ _4-y (y is 3 or 4, R and R ′ are alkyl groups), and a liquid containing a Si alkoxide or a partial hydrolyzate thereof can be mentioned. For example, silicon ethoxide, silicon methoxide, silicon isopropoxide,
Monomers such as silicon butoxide or polymers thereof can be preferably used.

The silicon alkoxide may be used by dissolving it in alcohol, ester, ether or the like, or by adding hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, maleic acid, hydrofluoric acid, or aqueous ammonia solution to the solution. You may decompose and use it. The Si alkoxide is preferably contained in the solvent in an amount of 30% by weight or less. If it exceeds 30% by weight, the solid content is large and the storage stability becomes poor.

To this solution, an alkoxide of Zr, Ti, Sn, Al or the like or a partial hydrolyzate thereof is added as a binder for improving the strength of the film, and ZrO is added.
One or more kinds of ₂ , ₂ , TiO ₂ , SnO ₂ , and Al ₂ O ₃ or a composite of two or more kinds may be simultaneously precipitated with MgF ₂ and / or SiO ₂ . The addition amount of these alkoxides and the like to the solution or dispersion is preferably about 0.1 to 10% by weight with respect to the Si alkoxide and / or MgF ₂ . Further, a surfactant may be added to improve wettability with the substrate. Examples of the surfactant to be added include linear sodium alkylbenzene sulfonate, alkyl ether sulfate, and the like.

The method for producing a low-reflection conductive film (multi-layer conductive film) of the present invention can be applied to a low-reflection conductive film due to the multilayer interference effect. The structure of the multilayer low-reflection film having the antireflection property is as follows. The wavelength of the light to be antireflection is λ, and the high refractive index layer-the low refractive index layer has an optical thickness λ / 2-λ / 4 from the substrate side.
Alternatively, a two-layer low-reflection film formed by λ / 4-λ / 4, a medium-refractive-index layer-a high-refractive-index layer-a low-refractive-index layer having an optical thickness λ
3 / 4- [lambda] / 2- [lambda] / 4, three layers of low reflection film, from the side of the substrate: low refractive index layer-medium refractive index layer-high refractive index layer-low refractive index layer with optical thickness [lambda] 2- [lambda]. A four-layer low-reflection film formed of / 2-? / 2-? / 4 is known as a typical example.

As the substrate for forming the conductive film by the conductive complex oxide fine particles in the present invention, a cathode ray tube panel, a glass plate for a copying machine, a computer panel, a glass for a clean room, a front plate of a display device such as a CRT or LCD, etc. Various glass and plastic substrates can be used. In particular, when the conductive film of the present invention is provided on the glass (panel or the like) for a cathode ray tube, a sufficient electromagnetic wave shielding effect is obtained and the appearance of the coating film is excellent, so that a beautiful image can be obtained, which is preferable.

[0036]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples (Examples 1 to 22) and Comparative Examples (Examples 23 and 24), but the present invention is not limited thereto. The evaluation methods of the films obtained in the following examples and comparative examples are as follows.

(1) Conductivity evaluation: The surface resistance of the film surface was measured with a Loresta resistance measuring instrument (manufactured by Mitsubishi Yuka).

(2) Scratch resistance: Under a load of 1 kg (LIO
After 50 times reciprocating the surface of the membrane with 50-50) manufactured by N, scratches on the surface were visually judged. The evaluation criteria were as follows: が: no scratches were formed, Δ: some scratches were formed, and x: film peeling occurred in part.

(3) Pencil hardness: under a load of 1 kg,
The surface of the film was scanned with a pencil, and the pencil hardness at which scratches on the surface began to be visually observed was judged to be the pencil hardness of the film.

(4) Luminous reflectance: The luminous reflectance of the multilayer film at 400 to 700 nm was measured with a gamma spectroscopic reflectance spectrophotometer.

(5) Luminous transmittance: 380 to 780 nm by spectrophotometer U-3500 manufactured by Hitachi Ltd.
The luminous transmittance was measured. Further, the transmission color tone was qualitatively evaluated from the color coordinate values.

[Example 1] A ruthenium chloride aqueous solution and cobalt chloride were adjusted to pH 10 with aqueous ammonia so that the Ru / Co = 9/1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 12 hours, and then dried in air at 500
The mixture was baked at 3 ° C for 3 hours to obtain Ru-Co composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time is 100 nm.
Met. After that, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution A).

Methyl silicate was dissolved in ethanol, hydrolyzed with an acidic aqueous solution of hydrochloric acid, and adjusted with ethanol so as to be 5% by weight in terms of SiO ₂ (solution A2).

Liquid A: Liquid A2 = 8: 2 (weight ratio), and then the solid content in terms of oxide was 1.0% by weight and the solvent composition was water: EGMBE (ethylene glycol monobutyl ether): NMP. (N-methylpyrrolidone) = 8
It diluted so that it might become a weight ratio of 0: 16: 4 (B liquid).
Liquid B is applied to the surface of a 14-inch cathode ray tube (panel) by spin coating and heated at 180 ° C. for 30 minutes to about 1
A conductive film having a thickness of 00 nm was obtained.

[Example 2] Ethyl silicate was dissolved in ethanol and hydrolyzed with an acidic aqueous solution of hydrochloric acid to obtain 5 in terms of SiO _2.
It was adjusted with ethanol so that it would be wt%. After this, this liquid was diluted to 1.0 wt% with a diluting solvent having a weight ratio of ethyl cellosolve: isopropanol: diacetone alcohol = 5: 4: 1 (Liquid C).

Liquid A in Example 1 had a solid content of 1.0% by weight in terms of oxide and a solvent composition of water: EGMBE: NMP =
After diluting to a weight ratio of 80: 16: 4,
It was applied on the surface of an inch Braun tube by a spin coating method, and then the solution C was applied on the film by a similar spin coating method and heated at 180 ° C. for 10 minutes to obtain a low reflection conductive film having a thickness of about 180 nm.

Example 3 A ruthenium chloride aqueous solution and nickel chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Ni = 9: 1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C. to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 12 hours, and then dried in air at 500
The mixture was baked at 3 ° C for 3 hours to obtain Ru-Ni composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time is 105 nm.
Met. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution D).

Liquid D has a solid content in terms of oxide of 1.0% by weight.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted to give a weight ratio of 4 (solution E). Liquid E 14
It was applied on the surface of an inch cathode ray tube by spin coating, and then C liquid was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes to obtain a low reflection conductive film having a thickness of about 100 nm.

Example 4 A ruthenium chloride aqueous solution and iron chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Fe = 9: 1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C. to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C for 12 hours, and then dried in air at 500 ° C for 3 hours.
Firing was carried out for a period of time to obtain Ru-Fe composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time was 120 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid (F
liquid).

Liquid F has a solid content of 1.0% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It diluted so that it might become the weight ratio of 4 (G liquid). G liquid 14
The solution was applied to the surface of an inch CRT by spin coating, and then the solution C was applied on the film by the same spin coating, and heated at 180 ° C. for 10 minutes to obtain a low-reflection conductive film having a thickness of about 200 nm.

[Example 5] A ruthenium chloride aqueous solution and zinc chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Zn = 9: 1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 12 hours, and then calcined in air at 500 ° C. for 3 hours to obtain Ru—Zn composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time was 130 nm. After that, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid (H
liquid). The solution H was diluted so that the solid content in terms of oxide was 1.0% by weight and the solvent composition was water: EGMBE: NMP = 80: 16: 4 by weight (solution I).

Solution I is applied to the surface of a 14-inch cathode ray tube by spin coating, and then solution C is applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes to form a low-reflection conductive film having a thickness of about 210 nm. Got

Example 6 A ruthenium chloride aqueous solution and chromium chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Cr = 9: 1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C. to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C for 12 hours, and then dried in air at 500 ° C.
And baked for 3 hours to obtain Ru-Cr composite oxide fine particles.
The composite oxide fine particles were pulverized with a sand mill for 2 hours.
The average particle size of the particles in the dispersion liquid at this time was 115 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution J).

Liquid J has a solid content of 1.0% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It diluted so that it might become the weight ratio of 4 (K liquid). K liquid 14
The solution was applied on the surface of an inch CRT by spin coating, and then the solution C was applied on the film by the same spin coating and heated at 180 ° C. for 10 minutes to obtain a low-reflection conductive film having a thickness of about 190 nm.

Example 7 A ruthenium chloride aqueous solution and manganese chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Mn = 9: 1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C. to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 12 hours, and then dried in air at 500
The mixture was baked at 3 ° C for 3 hours to obtain Ru-Mn composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time is 100 nm.
Met. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid (liquid L).

Liquid L has a solid content in terms of oxide of 1.0% by weight.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It diluted so that it might become the weight ratio of 4 (M liquid).

The solution M was applied to the surface of a 14-inch cathode ray tube by spin coating, and then the solution C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes to obtain a low reflection conductive film having a thickness of about 220 nm. A film was obtained.

[Example 8] A ruthenium chloride aqueous solution and copper chloride were adjusted to pH 10 with aqueous ammonia so that the Ru / Cu = 9/1 molar ratio was obtained, and simultaneously added to the solution kept at 50 ° C to precipitate. Co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C for 12 hours, and then dried in air at 500 ° C for 3 hours.
Firing was performed for a period of time to obtain Ru-Cu composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time was 125 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid (N
liquid).

Liquid N has a solid content of 1.0% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It diluted so that it might become the weight ratio of 4 (O liquid).

Liquid O was applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes, and a low-reflection conductive film having a thickness of about 180 nm was applied. Got

Example 9 A ruthenium chloride aqueous solution and lanthanum chloride were adjusted to pH 9.5 with aqueous ammonia so that the Ru: La = 9: 1 molar ratio was obtained, and added simultaneously to the solution kept at 60 ° C. Was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C for 8 hours, and then dried in air at 500 ° C.
And baked for 3 hours to obtain Ru-La composite oxide fine particles.
The composite oxide fine particles were pulverized with a sand mill for 3 hours.
The average particle size of the particles in the dispersion liquid at this time was 105 nm. Then, the mixture was concentrated to obtain a 5 wt% (solid content) sol liquid (P liquid).

The liquid P has a solid content of 1.2% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 230 nm was obtained.

Example 10 An aqueous solution of ruthenium chloride and cerium chloride were adjusted to pH 10.5 with aqueous ammonia so that the molar ratio of Ru: Ce was 8: 2, and added simultaneously to a solution kept at 60 ° C. , The precipitate was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then calcined in air at 550 ° C. for 3 hours to obtain Ru—Ce composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 1 hour. The average particle diameter of the particles in the dispersion liquid at this time is 95 n.
m. After that, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution Q).

Liquid Q has a solid content of 1.1% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 190 nm was obtained.

[Example 11] An aqueous solution of ruthenium chloride and praseodymium chloride was adjusted to pH 8.5 with aqueous ammonia so that the molar ratio of Ru: Pr was 9: 1, and the mixture was added at the same time to a solution kept at 60 ° C to cause precipitation. Was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air 4
It was baked at 80 ° C. for 3 hours to obtain Ru—Pr composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2.5 hours. At this time, the average particle size of the particles in the dispersion is 89.
was nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid (R liquid).

Liquid R has a solid content of 1.1% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 180 nm was obtained.

[Example 12] A ruthenium chloride aqueous solution and neodymium chloride were adjusted to pH 10.5 with aqueous ammonia so that the Ru: Nd = 9: 1 molar ratio was obtained, and simultaneously added to a solution kept at 70 ° C to precipitate the solution. Was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 50
The mixture was baked at 0 ° C for 3 hours to obtain Ru-Nd composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 3.0 hours. At this time, the average particle size of the particles in the dispersion is 109
was nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (S solution).

The liquid S has a solid content of 1.1% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 220 nm was obtained.

Example 13 A ruthenium chloride aqueous solution and samarium chloride were adjusted to pH 9.5 with aqueous ammonia so that the Ru: Sm = 9: 1 molar ratio was obtained, and added simultaneously to a solution kept at 65 ° C. Was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 50
The mixture was baked at 0 ° C for 5 hours to obtain Ru-Sm composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2.5 hours. The average particle size of the particles in the dispersion at this time was 119
was nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution T).

The liquid T has a solid content of 1.3% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 230 nm was obtained.

Example 14 A ruthenium chloride aqueous solution and europium chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Eu = 8: 2 molar ratio was obtained, and the mixture was added at the same time to a solution kept at 60 ° C. to precipitate the precipitate. It was deposited. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 50
The mixture was baked at 0 ° C for 2.5 hours to obtain Ru-Eu composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2.5 hours. At this time, the average particle size of the particles in the dispersion is 1
It was 19 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution U).

The liquid U has a solid content of 1.1% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 190 nm was obtained.

Example 15 An aqueous solution of ruthenium chloride and gadolinium chloride were adjusted to pH 9 with ammonia water so that the molar ratio of Ru: Gd was 8: 2 and added simultaneously to a solution kept at 60 ° C. to precipitate the precipitate. It was deposited. This coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 500
Firing at 3.5 ° C. for 3.5 hours gave Ru—Eu composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 2.5 hours. At this time, the average particle size of the particles in the dispersion is 11
It was 9 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol solution (solution V).

Liquid V has a solid content of 1.0% by weight in terms of oxide.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 180 nm was obtained.

Example 16 Aqueous ruthenium chloride and dysprosium chloride were adjusted to pH 9.5 with aqueous ammonia so that the Ru: Dy = 8: 2 molar ratio was obtained, and added simultaneously to the solution kept at 50 ° C. The precipitate was co-precipitated. This coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then calcined in air at 500 ° C. for 2 hours to obtain Ru-Dy composite oxide fine particles. The composite oxide fine particles are 3.5 in a sand mill.
Crushed for hours. The average particle size of the particles in the dispersion liquid at this time was 98 nm. Then, the mixture was concentrated to obtain a 5 wt% (solid content) sol liquid (liquid X).

Liquid X has a solid content in terms of oxide of 1.0% by weight.
And the solvent composition is water: EGMBE: NMP = 80: 16:
It was diluted so as to have a weight ratio of 4 and applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method, and the solution was applied at 180 ° C. for 10 minutes.
After heating for a minute, a low reflective conductive film having a thickness of about 180 nm was obtained.

[Example 17] A ruthenium chloride aqueous solution and holmium chloride were adjusted to pH 10.5 with aqueous ammonia so that the molar ratio of Ru: Ho was 9: 1, and added simultaneously to a solution kept at 70 ° C to precipitate. Was co-precipitated. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 5 ° C.
The mixture was baked at 00 ° C for 3 hours to obtain Ru-Ho composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 4 hours. At this time, the average particle diameter of the particles in the dispersion is 112 n.
m. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

This liquid had a solid content of oxide of 1.3% by weight and a solvent composition of water: EGMBE: NMP = 80: 1.
It was diluted so as to have a weight ratio of 6: 4, and was applied to the surface of a 14-inch cathode ray tube by spin coating, then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low-reflection conductive film having a thickness of about 220 nm was obtained.

Example 18 An aqueous solution of ruthenium chloride and erbium chloride were adjusted to pH 11 with aqueous ammonia so that the molar ratio of Ru: Er was 9: 1 and added simultaneously to a solution kept at 60 ° C. to precipitate the precipitate. It was deposited. This coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 500
Firing at 2.5 ° C. for 2.5 hours gave Ru—Er composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 4 hours. The average particle size of the particles in the dispersion liquid at this time is 95 nm.
Met. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

This liquid has a solid content of 1.2% by weight in terms of oxide and a solvent composition of water: EGMBE: NMP = 80: 1.
It was diluted so as to have a weight ratio of 6: 4, and was applied to the surface of a 14-inch cathode ray tube by spin coating, then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low reflective conductive film having a thickness of about 180 nm was obtained.

Example 19 An aqueous solution of ruthenium chloride and thulium chloride were adjusted to pH 8.5 with ammonia water so that the molar ratio of Ru: Tm was 9: 1 and added simultaneously to a solution kept at 60 ° C. to cause precipitation. Was co-precipitated. This coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then dried in air at 500
The mixture was baked at 3 ° C for 3 hours to obtain Ru-Tm composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 4 hours. The average particle size of the particles in the dispersion liquid at this time is 125 nm.
Met. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

This liquid had a solid content in terms of oxide of 1.1% by weight and a solvent composition of water: EGMBE: NMP = 80: 1.
It was diluted so as to have a weight ratio of 6: 4, and was applied to the surface of a 14-inch cathode ray tube by spin coating, then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low-reflection conductive film having a thickness of about 220 nm was obtained.

[0083] [Example 20] was added to ethanol 50g water 3g, further MgCl ₂ 0.05 mol, BF ₃ · C ₂
After 0.033 mol of H ₅ OH was added and completely dissolved, the mixture was placed in a flask equipped with a reflux condenser and reacted at 85 ° C. for 1 hour to obtain a MgF ₂ sol. This sol was diluted with ethanol so that the solid content in terms of fluoride was 5%, and SiO ₂ :
It was mixed with the A2 solution so that MgF ₂ = 6: 4, and further diluted with a diluting solvent having a weight ratio of ethyl cellosolve: isopropanol: diacetone alcohol = 5: 4: 1 to 1.0% (Y liquid).

A ruthenium chloride aqueous solution and lutetium chloride were adjusted to pH 10 with aqueous ammonia so that the Ru: Lu = 9: 1 molar ratio was obtained, and simultaneously added to a solution kept at 70 ° C. to coprecipitate a precipitate. The coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then calcined in air at 500 ° C. for 4 hours to obtain Ru—Lu composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 4 hours. The average particle size of the particles in the dispersion liquid at this time was 106 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

This liquid had a solid content in terms of oxide of 1.1% by weight and a solvent composition of water: EGMBE: NMP = 80: 1.
The mixture was diluted to a weight ratio of 6: 4, applied on the surface of a 14-inch cathode ray tube by spin coating, and then Y solution was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low-reflection conductive film having a thickness of about 190 nm was obtained.

Example 21 An aqueous solution of ruthenium chloride and antimony pentachloride were adjusted to pH 10 with ammonia water so that the Ru: Sb = 7.5: 2.5 molar ratio was obtained, and added simultaneously to a solution kept at 70 ° C. Was performed and the precipitate was co-precipitated. This coprecipitate was washed and filtered, dried at 100 ° C. for 8 hours, and then calcined in air at 500 ° C. for 1.8 hours to obtain Ru—Sb composite oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 4 hours. The average particle size of the particles in the dispersion liquid at this time was 88 nm. Then concentrated to 5% by weight (solid content)
A sol solution was obtained.

This liquid had a solid content in terms of oxide of 1.1% by weight and a solvent composition of water: EGMBE: NMP = 80: 1.
It was diluted so as to have a weight ratio of 6: 4, and was applied to the surface of a 14-inch cathode ray tube by spin coating, then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low reflective conductive film having a thickness of about 170 nm was obtained.

Example 22 Bismuth nitrate was dissolved in acetylacetone, and Ru: B was added together with an aqueous ruthenium chloride solution.
pH = 10 with ammonia water so that i = 8: 2 molar ratio
And added at the same time to the solution kept at 70 ° C.
The precipitate was co-precipitated. The co-precipitate was washed and filtered to obtain 10
After drying at 0 ° C for 8 hours, baking in air at 500 ° C for 3 hours,
Ru-Bi composite oxide fine particles were obtained. The composite oxide fine particles were pulverized with a sand mill for 2 hours. The average particle size of the particles in the dispersion liquid at this time was 89 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

This liquid had a solid content of 1.2% by weight as oxide and a solvent composition of water: EGMBE: NMP = 80: 1.
It was diluted so as to have a weight ratio of 6: 4, and was applied to the surface of a 14-inch cathode ray tube by spin coating, then liquid C was applied on the film by the same spin coating method, and heated at 180 ° C. for 10 minutes. A low-reflection conductive film having a thickness of about 190 nm was obtained.

Example 23 An aqueous ruthenium chloride solution was adjusted to pH 7 with aqueous ammonia and added to the solution kept at 45 ° C. to coprecipitate a precipitate. This coprecipitate was washed and filtered, dried at 100 ° C. for 12 hours, and then calcined in air at 500 ° C. for 3 hours to obtain Ru oxide fine particles. The composite oxide fine particles were pulverized with a sand mill for 0.5 hours. The average particle size of the particles in the dispersion liquid at this time was 118 nm. Then, the solution was concentrated to obtain a 5 wt% (solid content) sol liquid.

Further, the liquid was mixed with the solid content of oxide of 1.0% by weight and the solvent composition was water: EGMBE: NMP =
After diluting to a weight ratio of 80: 16: 4, it was applied on the surface of a 14-inch cathode ray tube by spin coating, and then liquid C was applied on the film by the same spin coating method.
It was heated at 180 ° C. for 10 minutes to obtain a low reflective conductive film having a thickness of about 190 nm.

Example 24 Indium chloride and tin chloride were mixed with I
An aqueous solution prepared to have a molar ratio of n: Sn = 9: 1 was added to a solution adjusted to pH 10 with ammonia to coprecipitate a precipitate. This coprecipitate is washed and filtered and then 100
After being dried at ℃ for 12 hours, it was baked in air at 650 ℃ for 3 hours to obtain Sn-doped In ₂ O ₃ oxide fine particles. The oxide fine particles were pulverized with a sand mill for 1.0 hour. The average particle size of the particles in the dispersion liquid at this time was 120 nm.
Then, the mixture is concentrated to a solid content of 5%, the solid content in terms of oxide is 1.0% by weight, and the solvent composition is water: EGMBE: N.
Dilute so that the weight ratio of MP = 80: 16: 4, and
It was applied on the surface of a 4-inch cathode ray tube by a spin coating method, and then the solution C was applied on the film by a similar spin coating method and heated at 180 ° C. for 10 minutes to obtain a low reflection conductive film having a thickness of about 200 nm.

Various properties of the films obtained in Examples 1 to 24 are shown in Tables 1 and 2 below.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

EFFECTS OF THE INVENTION According to the present invention, it is possible to efficiently provide an excellent conductive film by low-temperature treatment by a simple method such as a spray coating method or a spin coating method. In addition, the present invention can produce a conductive film capable of shielding electromagnetic waves at a relatively low cost, is particularly applicable to a large area substrate such as a panel face surface of a CRT, and can be mass-produced. high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Manami Hirotani, Manami Hiroya 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor, Go Morimoto 1150, Hazawa-machi, Kanagawa-ku, Yokohama Asahi Glass Co., Ltd. Central Research Center

Claims (8)

[Claims] 1. Cobalt, nickel, iron, zinc, chromium,
A conductive film comprising conductive complex oxide fine particles containing ruthenium and at least one element of manganese, copper, bismuth, antimony and lanthanoid elements (excluding promethium) and a ruthenium metal component. 2. A multi-layer conductive film having a low reflectivity, wherein a film having a refractive index lower than that of the conductive film is laminated on the conductive film according to claim 1. 3. Cobalt, nickel, iron, zinc, chromium,
On a substrate, a coating liquid containing a sol in which conductive complex oxide fine particles containing ruthenium as a metal component and one or more elements of manganese, copper, bismuth, antimony and lanthanoid elements (excluding promethium) are dispersed A method for producing a conductive film, which comprises applying the composition to a substrate and curing the composition. 4. The method for producing a conductive film according to claim 3, wherein the coating liquid contains at least one of water or an organic solvent having a dielectric constant of 5 or more and a boiling point of 50 ° C. to 250 ° C. 5. The method for producing a conductive film according to claim 3, wherein the coating liquid contains a silicon compound. 6. Cobalt, nickel, iron, zinc, chromium,
A coating solution containing a sol in which fine particles of a conductive complex oxide containing ruthenium as a metal component and one or more elements of manganese, copper, bismuth, antimony and lanthanoid elements (excluding promethium) are dispersed on the surface. A glass article, characterized by being applied and cured to form a conductive film. 7. The glass article according to claim 6, wherein a film having a refractive index lower than that of the conductive film is laminated on the conductive film to form a multilayer conductive film having low reflectivity. 8. The glass article according to claim 6, which is glass for a cathode ray tube.