JP3520705B2 - Coating liquid for forming conductive film, conductive film and method for manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive film forming coating solution for forming a conductive film on the surface of a substrate such as a cathode ray tube panel, a conductive film and a method for producing the same.

[0002]

2. Description of the Related Art Since a cathode ray tube operates at a high voltage, static electricity is induced on the surface of the cathode ray tube at the time of starting or ending. Due to this static electricity, dust is often attached to the surface, causing a reduction in image contrast, and often causing discomfort due to a slight electric shock when touched directly.

Further, in recent years, radio wave interference to electronic equipment due to electromagnetic wave noise has become a social problem, and standards and regulations have been made to prevent it. Electromagnetic noise affects the human body, for example, skin cancer due to electrostatic charge on a cathode ray tube (CRT), low frequency electric field (EL).
The effects of F) on the fetus and other harms such as X-rays and ultraviolet rays are regarded as problems in each country.

Electromagnetic noise can be shielded by interposing a conductive coating film on the surface of the cathode ray tube panel, but in order to sufficiently exert the electromagnetic shielding effect, the surface resistance value of the film is less than 1 × 10 ³ Ω / □. I need to be there. However, conventionally, it was difficult to obtain such a good conductive coating film. For example, JP-A-6-234552 describes that an ITO-dispersed silicate film is formed, but the sheet resistance of the film obtained in this case is 1 × 10 ³ Ω / □ or more,
A sufficient electromagnetic wave blocking effect was not obtained.

Further, Japanese Patent Laid-Open No. 6-310058 discloses Ag.
There is a description that a metal film is deposited on the surface of the cathode ray tube using a liquid composed of a salt of a metal such as Cu or Cu and a reducing agent. In this case, the resistance of the film can be reduced, but the obtained film is Ag or C.
a film of a metal u like, essentially inferior in film durability, resistance increase over time or film had practical problems such that discolored. In particular, in the case of a film using Ag, the volume resistance peculiar to the material is the lowest among metals, but the anodic dissolution easily occurs, and the presence of chloride or sulfide accelerates the deterioration of the film. There were many problems and there were many problems for practical use.

When a mixed solution of a metal salt and a reducing agent is applied to a glass substrate to form a film, the formed metal conductive film is in a state of being plated on the glass surface, and the strength of the film is reduced. There is a problem that it is extremely weak and a step of cleaning the conductive film to remove the by-product salt is required. Furthermore, Ag and Cu
Such metals have poor durability and have a problem that they are gradually oxidized even in normal air to increase the resistance of the film and discolor the film.

In addition, the formation of the conductive film and the low-reflection film by the coating method has hitherto been carried out not only in optical devices but also in consumer devices, particularly in cathode ray tubes (CRTs) of TVs and computer terminals. It has been done. The conventional method is disclosed in, for example, JP-A-61-118993.
As described in 1, a method such as attaching a SiO ₂ layer having fine irregularities on the surface to have an antiglare effect on the surface of the cathode ray tube or etching the surface with hydrofluoric acid to provide irregularities on the surface is taken. Came. However, these methods are called non-glare treatment that scatters external light, and there is a limit to the reduction of the reflectance of the film because it is not a method of essentially providing a low reflection layer, and in a cathode ray tube or the like,
It is also a cause of lowering the image resolution.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and has a conductive film having excellent electromagnetic wave shielding properties and film durability, a coating liquid for forming the conductive film, and It is intended to provide a method for manufacturing a conductive film.

[0009]

The present invention provides Ag, Ru,
A coating film for forming a conductive film, which contains an alloy fine particle dispersion containing two or more kinds of metal elements selected from the group consisting of Pt, Pd, Ni, Cu and Au, and a coating solution based on the same.
Conductive film made formed by coating on the body, the coating solution, based on
Provided is a method for producing a conductive film, which comprises applying the composition on a body and curing it to form the conductive film.

The feature of the present invention resides in that the conductive fine particles contained in the coating liquid for forming a conductive film are an alloy and the alloy fine particles are a dispersion in a so-called sol state. As a result, a conductive film having the conductivity required to exhibit the electromagnetic wave shielding property and the durability with no practical problems can be obtained.

The coating solution of the present invention contains fine alloy particles in the form of a sol in advance. When this is applied to a substrate, minute holes are introduced into the conductive film, unlike conventional plating films. Has been done. Furthermore, when a coating solution containing a hydrolyzate of Si alkoxide that forms a silicon oxide compound is applied onto the conductive film, the coating solution penetrates into the pores to significantly improve the film strength of the conductive film. To do.

Further, in the present invention, unlike the above-mentioned conventional method which uses a coating solution composed of a metal salt and a reducing solution, a by-product is not generated during the formation of the conductive film, and the conductive film and the conductive film are formed thereon. The deterioration of the film strength between the film and the formed film does not occur. Therefore, according to the present invention, a conductive film which solves the above-mentioned problems can be formed on a glass substrate such as a cathode ray tube panel surface.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Alloy fine particles used in the present invention are Ag, Ru, Pt, Pd, Ni, Cu and Au.
It is an alloy fine particle composed of two or more kinds of metal elements selected from the group consisting of The method for producing the fine particles is not particularly limited and can be produced by various methods, but it is particularly preferable to produce by mixing a substance capable of reducing metal ions with a metal salt solution. Preferred alloys in the present invention are, for example, A
g-Pd, Ag-Cu-Pd, Ag-Ni, Ru-P
d, Au-Pd, Pt-Pd and the like.

In the present invention, the metal salt used for producing the fine alloy particles by reduction is not particularly limited,
Silver nitrate, silver nitrite, ruthenium nitroso nitrate, ruthenium nitrate, palladium nitrate, nickel nitrate, nitrates such as copper nitrate, ruthenium chloride, ruthenium ammonium chloride,
Ruthenium potassium chloride, Ruthenium sodium chloride,
Gold (I) chloride, Gold (II) chloride, Chloroauric acid, Silver chloride, Platinum chloride, Platinum ammonium chloride, Palladium chloride, Palladium ammonium tetrachloride, Palladium potassium hexachloride, Nickel chloride, Cuprous chloride, Chloride Preferred are chlorides such as cupric acid, ruthenium acetate, silver acetate, silver acetate, palladium acetate, nickel acetate, cobalt acetate, acetate salts such as cupric acetate, and sulfate salts such as palladium sulfate, copper sulfate and nickel sulfate. These metal compounds are preferably dissolved in a solvent such as water and used as they are.

Further, in the present invention, an aqueous solution of two or more kinds of metal salts is used as a mixture in order to produce fine alloy particles.
Due to the different metal species used, their reduction potentials are also different and it is necessary to make the reduction potentials of different metals the same in order to alloy these metal species. Various methods can be considered to make the reduction potentials the same, but it is preferable to add a substance capable of forming a complex with at least one metal ion before the reduction, a solvent capable of being solvated, or the like.

As the substance capable of forming a complex with a metal salt,
Various known substances can be applied to each metal ion, and examples thereof include carboxylic acids such as oxalic acid, citric acid, EDTA and its derivatives, salts thereof, ammonia, triethanolamine and the like. Of these,
A citrate, particularly sodium citrate, is preferable because the obtained alloy fine particles have excellent uniformity.

Further, as the organic solvent which solvates a specific metal ion, a solvent having a particularly high electron donating property is preferable from the viewpoint of affinity for the metal ion, and it is not particularly limited as long as this condition is satisfied, but dimethyl sulfoxide, N- Solvents such as methyl-2-pyrrolidone, tetrahydrofuran, dimethylformamide, acetonitrile and sulfolane are preferred.

The reducing agent capable of reducing a compound such as silver nitrate to precipitate an alloy is not particularly limited, but FeSO ₄ and S
Examples thereof include base metal salts such as nSO ₄ , formalin, glucose, Rossell salt, tartaric acid, sodium thiosulfate, borohydride compounds, hypophosphite, and organic solvents such as ethanol. Among these compounds, it is preferable to use a salt containing a base metal such as FeSO ₄ or SnSO ₄ having a relatively slow reduction rate. FeSO ₄ is particularly preferable because it has a slow reduction rate and can easily form a uniform alloy fine particle dispersion.

Further, it is preferable to add a substance that adsorbs to the surface of the produced alloy fine particles to form a so-called protective colloid because the particle diameter of the alloy fine particles in the obtained dispersion becomes uniform. As such a substance, various known substances can be mentioned, and examples thereof include polymeric materials such as PVA, PVP, gelatin, and acrylic resins.

Further, in the present invention, cations such as alkali metal ions, ammonium ions and polyvalent metal ions contained in the alloy fine particle dispersion, inorganic anions such as mineral acids, and organic anions such as acetic acid and formic acid. It is preferable to deionize ions and the like before use. In this case, the amount of ions in the dispersion liquid can be measured by various methods. For example, when the conductivity is measured, the conductivity of the coating liquid is 500 μS / cm or less, and particularly 200 μS / cm or less. Is preferred. If deionization is insufficient and the amount of ions in the liquid increases,
It is not preferable because the alloy fine particles in the liquid aggregate and the conductive film having a predetermined surface resistance cannot be obtained, and the appearance of the obtained film deteriorates.

The deionization method is not particularly limited,
For example, ultrafiltration Filtration, ion exchange or the like can be used. In particular, the method of contacting the obtained alloy fine particle dispersion with the ion exchange resin is preferable because desalting can be performed without impairing the stability of the alloy fine particle dispersion. In the alloy fine particle dispersion obtained by the above method, the average primary particle diameter of the alloy fine particles is preferably 100 nm or less. This has an average primary particle size of 100 nm
This is because when it exceeds the above range, the scattering of visible light increases, the haze value of the film increases, and the resolution of the image display unit decreases. Especially 50
nm or less is preferable.

The alloy fine particle dispersion can be used as it is as a coating liquid for forming a conductive film of the present invention by diluting or substituting it with various solvents. The solvent used in this case is not particularly limited, and various known organic solvents other than water can be applied. For example, methanol, ethanol, propanol,
Alcohols such as butanol, polyhydric alcohols such as ethylene glycol, ethyl cellosolve, methyl cellosolve, butyl cellosolve, ethers such as propylene glycol methyl ether, 2,4-pentanedione, Zia <br/> Seth down ketone alcohol , Esters such as ethyl lactate and methyl lactate, amides such as N-methyl-2-pyrrolidone, and sulfur compounds such as dimethyl sulfoxide and sulfolane.

The concentration of fine alloy particles in the coating liquid for forming a conductive film is preferably adjusted to 0.01 to 5% by weight, particularly 0.05 to 2% by weight. If it exceeds 5% by weight, the transparency of the formed film remarkably decreases, and if it is less than 0.01% by weight, the resistance of the formed film increases, which is not preferable. Further, in order to change the physical properties such as the transmittance or color tone of the film in the coating liquid, Sn, In, Sb, Zn, Al, T
One or more compounds selected from the group consisting of i, Si and Ga can be added. The compound to be used is not particularly limited, but in the case of using Sn-doped In ₂ O ₃ and Sb-doped SnO ₂ , the transmittance can be controlled without increasing the resistance of the formed film. preferable.

Further, it is preferable to use SiO ₂ sol obtained by hydrolyzing SiO ₂ , particularly ethyl silicate or the like, because the coating property of the coating liquid is improved. Also, TiO
_{The use of 2} is also preferable because the coating property of the coating liquid and the color tone of the formed film can be controlled. Particularly, regarding TiO ₂ , fine particles of TiO _x containing nitrogen atoms in an amount of 0.3 to 30% by weight based on the total of titanium atoms and oxygen atoms (2.
When reduced TiO _{2 represented} by 0> x ≧ 1.0) is used, it is effective in improving the light resistance of the obtained film. The nitrogen atom-containing titanium oxide fine particles can be obtained by subjecting titanium oxide fine particles or titanium hydroxide fine particles to heat treatment in an atmosphere containing nitrogen gas or ammonia gas. In this case, the heat treatment temperature at the time of producing particles is appropriately determined in relation to the particle diameter, but is preferably 300 to 850 ° C.

The nitrogen atom content of the nitrogen atom-containing titanium oxide fine particles is preferably in the range of 0.3 to 30% by weight,
If it is less than 0.3% by weight, it is difficult to reduce the production of oxygen radicals during ultraviolet irradiation, and therefore the effect of suppressing the transition of the alloy fine particles to the excited state is small. Further, if it exceeds 30% by weight, the film is easily oxidized and the oxidation resistance of the film itself is deteriorated. The particle size of such nitrogen atom-containing titanium oxide fine particles is generally 100 nm or less, preferably 80 nm.
It is the following.

These nitrogen atom-containing titanium oxide fine particles can be added to the aforementioned alloy fine particle dispersion liquid in the form of fine particles or a hydrolyzate of alkoxide, and dispersed by a disperser such as an ultrasonic disperser or a sand mill. It can also be added to the coating liquid for forming a conductive film of the present invention as the above liquid. The addition amount of these nitrogen atom-containing titanium oxide fine particles is preferably 0 to 50 parts by weight, and particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the alloy fine particles. Further, various surfactants can be added to the coating film for forming a conductive film of the present invention in order to improve the wettability to the substrate to be coated.

The coating solution of the present invention synthesized above may be applied onto a substrate by spin coating, dip coating,
A method such as spray coating is suitable. Further, a spray coating method may be used to form irregularities on the surface to impart an antiglare effect to the film, and a hard coat such as a silica coating may be provided thereon. Furthermore, the conductive film of the present invention is formed by spin coating or spray coating, and S is formed thereon.
A solution containing i-alkoxide may be spray-coated to provide a non-glare coat of silica coating having irregularities on the surface.

The conductive film-forming coating liquid containing the liquid in which fine alloy particles are dispersed according to the present invention is dried at room temperature when a low boiling point solvent is added in order to serve as a coating liquid on a substrate by itself. A coating film is obtained with a boiling point of 100-
When a medium to high boiling point solvent at 250 ° C. is used, the solvent remains in the coating film when dried at room temperature, and therefore heat treatment is performed.
The upper limit of the heating temperature is determined by the softening point of glass, plastic, etc. used as the substrate. Considering this point, the heating temperature is preferably 100 to 500 ° C.

The thickness of the conductive film of the present invention thus formed varies depending on its use, but is generally 0.01 to
0.3 μm is preferable. If the thickness of the conductive film is less than 0.01 μm, the conductivity is insufficient, and the thickness of the conductive film is 0.3 μm.
If it exceeds m, the optical transmittance and strength of the film are insufficient. A more preferable film thickness is 0.02 to 0.1 μm.

In the present invention, the low reflection conductive film can be formed by utilizing the interference effect of light. For example, when the substrate is glass (refractive index n = 1.52), the ratio of n (conductive film) / n (low refractive index film) on the conductive film is about 1.23. By forming a low refractive index film, the reflectance of the conductive film can be most reduced. In order to reduce the reflectance of the conductive film, it is preferable to reduce the reflectance of 555 nm particularly in the visible light region, but in practice, it is preferable to appropriately determine in consideration of the reflection appearance and the like.

The outermost low refractive index film of the two-layered low reflective conductive film is a solution containing MgF ₂ sol or S.
It can be formed using a solution consisting of one or more kinds selected from solutions containing i-alkoxide. From the viewpoint of the refractive index of the film, MgF ₂ is the lowest among the above materials, and it is preferable to use a solution containing MgF ₂ sol in order to reduce the reflectance, but from the viewpoint of film hardness and scratch resistance, SiO ₂ It is preferable to use a solution containing Si alkoxide capable of forming a film containing as a main component.

Various solutions can be used as the solution containing the Si alkoxide for forming the low refractive index film.
(OR) _y R ′ _4-y (y is 3 or 4, R and R ′ are alkyl groups) and a solution containing a Si alkoxide or a partial hydrolyzate thereof can be mentioned. For example, Si ethoxide, Si methoxide, Si isopropoxide, S
i-Butoxide monomers or polymers are preferred.

The Si alkoxide can be used by dissolving it in alcohol, ester, ether or the like, and in the above solution, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, maleic acid,
It is also possible to add hydrofluoric acid or an aqueous ammonia solution and hydrolyze it before use. The Si alkoxide is preferably contained in the solvent in an amount of 30% by weight or less in terms of solid content. If the solid content is too large, the storage stability will be poor, so such solid content is preferable.

The film thickness of the low refractive index film thus formed is
Generally, 0.02 to 0.
The thickness is 2 μm, and the predetermined optical characteristics (low reflectivity) cannot be obtained even when the film thickness of the low refractive index film is less than 0.02 μm or more than 0.2 μm . More preferable film thickness is 0.04 to 0.1 μm
Is.

To this solution, alkoxides such as Zr, Ti, Sn and Al, and their partial hydrolysates were added as a binder to improve the strength of the film, and ZrO ₂ and T were added.
One or more selected from iO ₂ , SnO ₂ and Al ₂ O ₃ may be simultaneously deposited with MgF ₂ or SiO ₂ . A surfactant may be added to improve the wettability with the substrate. Examples of the surfactant to be added include linear sodium alkylbenzene sulfonate and alkyl ether sulfate.

The method of manufacturing a conductive film of the present invention can be applied to a low reflective conductive film due to the multilayer interference effect. The structure of the multilayer low-reflection film having antireflection properties is as follows: the wavelength of the light to be antireflection is λ, and the high refractive index layer-low refractive index layer has an optical thickness of λ / 2-λ / 4 from the base side. Or λ / 4-λ /
2 layer of low reflection film formed in 4, the medium refractive index layer from the substrate side-
High Refractive Index Layer-Low Refractive Index Layer with Optical Thickness λ / 4-λ / 2-λ
The three-layer low-reflection film formed by / 4, and the optical thickness λ /
A four-layer low-reflection film formed of 2-λ / 2-λ / 2-λ / 4 and the like are known as typical examples. The conductive film of the present invention can be used as the medium refractive index layer or the high refractive index layer.

Further, a display device, particularly a display device using a cathode ray tube such as a TV display or a computer display displays an image with the three primary colors (RGB) of light, but the respective emission spectra of RGB are not completely independent. Overlap occurs in some wavelength regions.

Since the film containing the alloy fine particles of the present invention absorbs light in the entire visible light region, it also absorbs the overlapping portion of the emission spectra of RGB itself, and the light in the overlapping wavelength region of RGB does not pass therethrough, thus improving the contrast. It also contributes to and has excellent low reflectivity.

As the substrate for forming the low-reflection conductive film comprising the conductive film of the present invention containing fine alloy particles and the film containing a silicon compound as the main component formed thereon, a cathode ray tube panel, a glass plate for a copying machine, Examples thereof include computer panels, clean room glass, various glasses such as front plates of display devices such as CRTs and LCDs, and plastic substrates.

[0040]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto . In Examples and Comparative Examples below, the evaluation method of the film obtained are as follows.

1) Conductivity: The surface resistance of the film surface was measured with a Loresta resistance measuring instrument (manufactured by Mitsubishi Yuka). 2) Luminous reflectance: The luminous reflectance of the multilayer film at 400 to 700 nm was measured by a GAMMA spectral reflectance spectrophotometer.

3) Luminous transmittance: The luminous transmittance at 380 to 780 nm was measured with a spectrophotometer U-3500 manufactured by Hitachi Ltd. 4) Scratch resistance: Under 1kg load (LION eraser 5
0-50), the film surface was reciprocated 50 times, and the degree of scratches on the surface was visually evaluated. The evaluation criteria are: ○: no scratches at all, Δ: some scratches, ×: film peeling occurs in part
And

5) Weather resistance: The surface resistance value of the film was measured with a photo dry cleaner PL7-200 manufactured by Sen Engineering after irradiating with ultraviolet rays having a main wavelength of 254 nm for 100 hours. 6) Chemical resistance: The surface resistance value of the film after being immersed in a 5% NaCl solution for 100 hours was measured.

The average primary particle diameter of the particles in the obtained sol is measured by a transmission electron microscope, and the aggregate particle diameter is LPA-31, a laser diffraction particle size analyzer manufactured by Otsuka Electronics.
00 was measured.

(Example 1) "Preparation of Ag-Pd alloy fine particle dispersion" (1-1) N was added to 7.5 g of a 5 wt% palladium nitrate aqueous solution.
- methyl-2-pyrrolidone down 3. After adding 5 g , the mixture was stirred for 15 minutes. After adding 20 g of a 10 wt% silver nitrate aqueous solution to this solution, the solution was stirred for 15 minutes. (1-2) 35 wt% in 20 g of 30 wt% iron sulfate aqueous solution
35 g of a trisodium citrate aqueous solution was added, and the liquid obtained in (1-1) above was further added to this liquid. (1-3) The liquid obtained in (1-2) above was subjected to solid-liquid separation by centrifugation, 30 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation for 10 minutes in this solution was added 30 wt% trisodium citrate aqueous solution 3 0 g.

(1-4) After repeating the above step (1-3) twice, solid-liquid separation was carried out by centrifugation, 35 g of pure water was added, and ultrasonic irradiation was further carried out for 20 minutes. (1-5) The cation exchange resin was added to the liquid obtained in the above (1-4), and the mixture was stirred for 15 minutes, then the cation exchange resin was filtered off, and the anion exchange resin was added to give 18 After stirring for a minute, the anion exchange resin was filtered off to obtain a Ag-Pd alloy fine particle dispersion liquid. The average primary particle size of the Ag-Pd alloy fine particles in this dispersion was 8 nm, the aggregate particle size in the liquid was 60 nm, and the solid content concentration was 3.5% by weight (A
1 solution).

"Preparation of coating liquid for conductive film" (1-6) A1 liquid was diluted with ethanol and water and adjusted to 80 % by weight of ethanol and 0.27 % by weight of solid content. (A2 liquid). "Preparation of Liquid Containing Silicon Compound" (1-7) 50 g of ethyl silicate was dissolved in 200 g of ethanol, a mixed solution of 1.5 g of concentrated nitric acid and 33 g of pure water was added dropwise under stirring, and the mixture was stirred at room temperature for 2 hours. SiO ₂ concentration 4.
A 9% by weight liquid was obtained (B1 liquid). The B1 liquid, propylene glycol monomethyl ether / isopropyl Piruaru
Co Lumpur / diacetone alcohol = 50: 40: 10 SiO ₂ solid with a mixed solvent (weight ratio) was diluted to 0.70 wt% (B2 solution).

"Coating and Curing" (1-8) 25 g of A2 solution was spin-coated on the surface of a 14-inch (type) CRT panel heated to a surface temperature of 48 ° C. by a spin coating method so that the film thickness at the time of curing would be 40 nm. 100 rp
m2 for 60 seconds, and then apply 20g of B2 solution to A2
The glass for a cathode ray tube with a conductive film of the present invention was obtained by applying a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when the liquid was applied, and then heating at 160 ° C. for 30 minutes. The conductive film is a low reflective conductive film having low reflectivity.

(Example 2) "Preparation of Ag-Cu-Pd alloy fine particle dispersion liquid" (2-1) N was added to 7.5 g of a 5 wt% palladium nitrate aqueous solution.
- methyl-2-pyrrolidone down 3. After adding 5 g , the mixture was stirred for 15 minutes. 10 g of an 8 wt% copper nitrate aqueous solution was added to this liquid and then stirred for 15 minutes, and further 15 g of a 10 wt% silver nitrate aqueous solution was added to this liquid and then stirred for 15 minutes. (2-2) 35 wt% in 20 g of 30 wt% iron sulfate aqueous solution
35 g of a trisodium citrate aqueous solution was added, and the liquid obtained in (2-1) above was further added to this liquid. (2-3) The liquid obtained in (2-2) above was subjected to solid-liquid separation by centrifugation, 20 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation of this solution for 15 minutes, 25 g of a 30% by weight aqueous solution of trisodium citrate was added.

(2-4) After repeating the above step (2-3) three times, solid-liquid separation was carried out by centrifugation, 30 g of pure water was added, and ultrasonic irradiation was further carried out for 30 minutes. (2-5) To the liquid obtained in (2-4) above, a cation exchange resin was added and stirred for 8 minutes, then the cation exchange resin was filtered off, and an anion exchange resin was added to obtain 8 After stirring for minutes, the anion exchange resin was filtered off and the Ag-Cu-Pd
An alloy fine particle dispersion was obtained. Ag-Cu-P of this dispersion
The average primary particle diameter of the d-alloy fine particles was 10 nm, the aggregate particle diameter in the liquid was 98 nm, and the solid content concentration was 2.5% by weight (Liquid A3).

"Preparation of coating liquid for conductive film" (2-6) A3 solution was diluted with ethanol and water to adjust to 70 % by weight of ethanol and 0.27 % by weight of solid content. (A4 liquid). "Coating and curing" (2-7) 30g of A4 liquid was spin-coated on the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C by a spin coating method to obtain a film thickness of 100 rp at 45 nm.
m2 for 60 seconds, then apply 20g of B2 solution to A4
The glass for a cathode ray tube with a conductive film of the present invention was obtained by applying a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when the liquid was applied, and then heating at 160 ° C. for 30 minutes.

(Example 3) "Preparation of Ag-Ni alloy fine particle dispersion liquid" (3-1) 1 to 7.5 g of 10 wt% nickel nitrate aqueous solution
After adding 20 g of a 0 wt% silver nitrate aqueous solution, the mixture was stirred for 30 minutes. (3-2) 35 wt% trisodium citrate aqueous solution 35
After adding the liquid obtained in the above (3-1) to g, 20 g of a 5 wt% sodium borohydride aqueous solution was added. (3-3) The liquid obtained in (3-2) above was subjected to solid-liquid separation by centrifugation, 20 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation for 15 minutes this solution was added 30 wt% trisodium citrate aqueous solution 2 5 g.

(3-4) The above step (3-3) was repeated twice, and after solid-liquid separation by centrifugation, 30 g of pure water was added and ultrasonic irradiation was carried out for another 30 minutes. (3-5) The cation exchange resin was added to the liquid obtained in (3-4) above, and the mixture was stirred for 5 minutes. Then, the cation exchange resin was filtered off, and the anion exchange resin was added to give 5 After stirring for 1 minute, the anion exchange resin was filtered off to obtain an Ag-Ni alloy fine particle dispersion liquid. The average primary particle diameter of Ag-Ni alloy fine particles in this dispersion was 12 nm, and the aggregate particle diameter in the liquid was 8
5 nm, the solid content concentration was 2.2% by weight (A5
liquid).

"Preparation of coating liquid for conductive film" (3-6) (A5 liquid) was diluted with ethanol and water,
Ethanol was adjusted to 70 % by weight and solid content was 0.27 % by weight (Liquid A6). "Coating and curing" (3-7) 30g of A6 liquid was spin-coated on the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C by a spin coating method to obtain a film thickness of 45 rp at 100 rp.
m2 for 60 seconds, and then apply 20g of B2 solution to A6
The glass for a cathode ray tube with a conductive film of the present invention was obtained by applying a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when the liquid was applied, and then heating at 160 ° C. for 30 minutes.

(Example 4) "Preparation of Ru - Pd alloy fine particle dispersion liquid" (4-1) 7.5 wt% palladium chloride aqueous solution 7.5 g
In N- methyl-2-pyrrolidone down 2. 1 After the addition of 5g
Stir for 5 minutes. 15 g of a 3.6 wt% ruthenium chloride aqueous solution was added to this liquid, and the mixture was stirred for 15 minutes. (4-2) 35 wt% trisodium citrate aqueous solution 35
After adding the liquid obtained in the above (4-1) to g, 40 g of a 5 wt% sodium borohydride aqueous solution was added. (4-3) The liquid obtained in (4-2) above was subjected to solid-liquid separation by centrifugation, 20 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation for 15 minutes this solution was added 30 wt% trisodium citrate aqueous solution 1 0 g.

(4-4) After the above step (4-3) was repeated twice, solid-liquid separation was carried out by centrifugation, 30 g of pure water was added, and ultrasonic irradiation was carried out for another 30 minutes. (4-5) The cation exchange resin was added to the liquid obtained in the above (4-4), the mixture was stirred for 5 minutes, the cation exchange resin was filtered off, and the anion exchange resin was further added to obtain 5 After stirring for 1 minute, the anion exchange resin was filtered off to obtain a Ru - Pd alloy fine particle dispersion liquid. The average primary particle size of the Ru - Pd alloy fine particles in this dispersion was 13 nm, and the aggregate particle size in the liquid was 7
5 nm, the solid content concentration was 1.8% by weight (A7
liquid).

"Preparation of coating liquid for conductive film" (4-6) A7 solution was diluted with ethanol and water to adjust to 70 % by weight of ethanol and 0.27 % by weight of solid content. (A8 liquid). "Coating and curing" (4-7) 30 g of A8 liquid was spin-coated on the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C. by a spin coating method to obtain a film thickness of 45 rp at 100 rp.
m2 for 60 seconds, and then apply 20g of B2 solution to A8
The glass for a cathode ray tube with a conductive film of the present invention was obtained by applying a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when the liquid was applied, and then heating at 160 ° C. for 30 minutes.

(Example 5) "Preparation of Au-Pd alloy fine particle dispersion liquid" (5-1) 7.5% by weight aqueous solution of palladium chloride 7.5 g
In N- methyl-2-pyrrolidone down 2. 1 After the addition of 5g
Stir for 5 minutes. 20% of 3 wt% aqueous chloroauric acid solution
After adding g, the mixture was stirred for 15 minutes. (5-2) 35 wt% in 20 g of 30 wt% iron sulfate aqueous solution
35 g of trisodium citrate aqueous solution was added, and the liquid obtained in the above (5-1) was further added to this liquid. (5-3) The liquid obtained in (5-2) above was subjected to solid-liquid separation by centrifugation, 30 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation for 10 minutes in this solution was added 30 wt% trisodium citrate aqueous solution 3 0 g.

(5-4) After repeating the above step (5-3) three times, solid-liquid separation was carried out by centrifugation, 35 g of pure water was added, and ultrasonic irradiation was further carried out for 30 minutes. (5-5) A cation exchange resin was added to the liquid obtained in (5-4) above, and the mixture was stirred for 15 minutes. Then, the cation exchange resin was filtered off, and the anion exchange resin was added. After stirring for 1 minute, the anion exchange resin was filtered off to obtain an Au-Pd alloy fine particle dispersion liquid. The average primary particle size of the Au-Pd alloy fine particles in this dispersion was 5 nm, the aggregate particle size in the liquid was 52 nm, and the solid content concentration was 3.5% by weight (A
9 solution).

"Preparation of Coating Solution for Conductive Film" (5-6) A9 solution was diluted with ethanol and water to adjust to 80 % by weight of ethanol and 0.25 % by weight of solid content. (A10 liquid). "Coating and curing" (5-7) 35g of A10 liquid was spin-coated on the surface of a 14-inch (type) CRT panel heated to a surface temperature of 48 ° C by a spin coating method to obtain a film thickness of 50nm at 100rp.
m 2 for 60 seconds, and then apply 20g of B2 solution to A 1
After coating with a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when coating the 0 liquid, at 30 ° C. at 160 ° C.
The glass for a cathode ray tube with a conductive film of the present invention was obtained by heating for a minute.

(Example 6) "Preparation of Pt-Pd alloy fine particle dispersion liquid" (6-1) 7.5 g by weight aqueous solution of palladium chloride 7.5 g
In N- methyl-2-pyrrolidone down 2. 1 After the addition of 5g
Stir for 5 minutes. Add 3 wt% chloroplatinic acid aqueous solution to this solution 1
After adding 5 g, the mixture was stirred for 15 minutes. (6-2) 35 wt% in 20 g of 30 wt% iron sulfate aqueous solution
35 g of trisodium citrate aqueous solution was added, and the liquid obtained in the above (6-1) was added to this liquid. (6-3) The liquid obtained in (6-2) above was subjected to solid-liquid separation by centrifugation, and 30 g of pure water was added to the precipitate and stirred. After ultrasonic irradiation for 10 minutes in this solution was added 30 wt% trisodium citrate aqueous solution 3 0 g.

(6-4) After repeating the above step (6-3) four times, solid-liquid separation was carried out by centrifugation, 35 g of pure water was added, and ultrasonic irradiation was further carried out for 60 minutes. (6-5) To the liquid obtained in (6-4) above, a cation exchange resin was added and stirred for 5 minutes, then the cation exchange resin was filtered off, and an anion exchange resin was added to give 5 After stirring for a minute, the anion exchange resin was filtered off to obtain a Pt-Pd alloy fine particle dispersion liquid. The average primary particle diameter of the Pt-Pd alloy fine particles in this dispersion was 6 nm, and the aggregate particle diameter in the liquid was 63.
nm, and the solid content concentration was 2.1% by weight (A11
liquid).

"Preparation of Coating Liquid for Conductive Film" (6-6) A11 liquid was diluted with ethanol and water and adjusted to 80 % by weight of ethanol and 0.25 % by weight of solid content. (A12 liquid). "Coating and curing" (6-7) 35g of A12 liquid was spin-coated on the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C by a spin coating method to obtain a film thickness of 55 rp at 100 rp.
m 2 for 60 seconds, and then apply 20g of B2 solution to A 1
Under the same spin-coating conditions as when applying the two liquids, a coating amount of 60 nm is obtained at the time of curing, and then 30 at 160 ° C.
The glass for a cathode ray tube with a conductive film of the present invention was obtained by heating for a minute.

(Example 7) "Preparation of TiO _x (1.0 ≤ x <2.0) fine particle dispersion containing nitrogen" (7-1) TiO _x (1.0 containing 1.0% by weight of nitrogen) ≤
x <2.0) 15 g of fine particles were added to 85 g of an aqueous solution adjusted to pH 3.5 in advance, pulverized with a sand mill for 4 hours, and heated at 90 ° C. for 1 hour. (7-2) A cation exchange resin was added to the liquid obtained in (7-1) above, and the mixture was stirred for 30 minutes. Then, the cation exchange resin was filtered off, and an anion exchange resin was added to the solution. After stirring for 1 minute, the anion exchange resin was filtered off and the concentration was adjusted to 10% by weight with distilled water to obtain a dispersion liquid having an average aggregate particle diameter of 43 nm. Water was added to this dispersion to give a solid content of 3.5% by weight.
Was adjusted so that (C1 liquid).

[0065] "conductive film coating solution preparation of" (7-3) the A1 solution and the C1 solution of Example 1 Symbol placement A1
Liquid: C1 liquid = 20: 1, ultrasonically dispersed for 30 minutes, then diluted with ethanol and water to give 80 % by weight of ethanol and 0.30 % by weight of solids.
(A13 solution).

[Coating and curing] (7-4) 35 g of A13 solution was spin-coated on the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C. by a spin coating method so that the film thickness upon curing would be 40 nm. 100 rp
m2 for 60 seconds, and then apply 20g of B2 solution to A1
Under the same spin-coating conditions as when applying the three liquids, a coating amount of 60 nm is obtained at the time of curing, and then 30 at 160 ° C.
The glass for a cathode ray tube with a conductive film of the present invention was obtained by heating for a minute.

(Example 8) "Preparation of liquid containing silicon compound" (8-1) 35 g of ethyl silicate was dissolved in 215 g of ethanol, and a mixed solution of 1.5 g of concentrated nitric acid and 33 g of pure water was added dropwise with stirring. Then, the mixture is stirred at room temperature for 2 hours to obtain a SiO ₂ concentration of 3.
A 5 wt% liquid was obtained (B3 liquid).

"Preparation of coating liquid for conductive film" (8-2) A1 liquid described in Example 1 and C1 described in Example 7
Liquid and the above B3 liquid are A1 liquid: C1 liquid: B3 liquid = 50: 3:
After mixing so as to be 47, ultrasonic dispersion treatment was carried out for 30 minutes and then diluted with ethanol and water to adjust to 70 % by weight of ethanol and 1.1 % by weight of solid content ( A14 solution).

[Coating and Curing] (8-3) 35 g of A14 liquid was applied to the surface of a 14-inch (type) cathode ray tube panel heated to a surface temperature of 48 ° C. by a spin coating method at 100 rpm for 60 seconds, and then 16
The glass for a cathode ray tube with a conductive film of the present invention was obtained by heating at 0 ° C. for 30 minutes.

Comparative Example 1 (9-1) 29% by weight in 20 g of 10% by weight silver nitrate aqueous solution
After adding ₃ g of NH ₃ aqueous solution, the mixture was stirred for 10 minutes (D1
liquid). (9-2) 9 added wt% aqueous glucose solution 100g 0.8% by weight aqueous tartaric acid solution 100g, further ethanol
20 g was added (D2 solution). (9-3) Immediately after mixing the D1 liquid and the D2 liquid, 50 g was applied to the surface of a 14-inch (type) CRT panel heated to a surface temperature of 48 ° C. by a spin coating method at 100 rpm for 60 seconds, and the mixture was formed. After the film was formed, 1 liter of distilled water was similarly applied at 100 rpm for 600 seconds to wash the film, and 20 g of the B2 solution was applied thereon under the same spin coating conditions as when the A13 solution was applied, and then at 160 ° C. for 30 minutes. By heating, a glass for a cathode ray tube with a conductive film was obtained.

Comparative Example 2 (10-1) 35 g of a 35 wt% trisodium citrate aqueous solution was added to 20 g of a 30 wt% iron sulfate aqueous solution, and further 25 g of a 10 wt% silver nitrate aqueous solution was added to this solution. (10-2) The liquid obtained in (10-1) above was subjected to solid-liquid separation by centrifugation, 30 g of pure water was added to the precipitate, and the mixture was stirred. After ultrasonic irradiation for 5 minutes to this solution was added 30 wt% trisodium citrate aqueous solution 2 5 g.

(10-3) After repeating the above step (10-2) four times, solid-liquid separation was carried out by centrifugation, and then 35 g of pure water was added.
Was added and ultrasonic irradiation was performed for another 20 minutes. (10-4) After adding a cation exchange resin to the liquid obtained in (10-3) and stirring for 30 minutes, the cation exchange resin is filtered off, and an anion exchange resin is further added to 30
After stirring for 1 minute, the anion exchange resin was filtered off to obtain Ag fine particle dispersion liquid. The average primary particle diameter of Ag particles in this dispersion was 10 nm, the aggregate particle diameter in the solution was 75 nm, and the solid content concentration was 3.5 wt% (E1 solution).

"Preparation of coating liquid for conductive film" (10-5 ) E1 liquid was diluted with ethanol and water to adjust to 80 % by weight of ethanol and 0.27 % by weight of solid content. (E2 solution). "Coating and curing" (10-6) 20 g of E2 liquid was spin-coated on a surface of a 14-inch (type) CRT panel heated to a surface temperature of 45 ° C by a spin coating method so that the film thickness at the time of curing was 100 rp.
m2 for 60 seconds, and then apply 20g of B2 solution to E2
A glass for a cathode ray tube with a conductive film was obtained by applying a coating amount such that the film thickness upon curing was 60 nm under the same spin coating conditions as when applying the liquid, and then heating at 160 ° C. for 30 minutes.

Comparative Example 3 (11-1) In / Sn =
Mix until it becomes 85/15 and add ammonia water to pH 1
It was adjusted to 0 and added to the solution kept at 50 ° C. to precipitate the hydroxide. The precipitate is washed and filtered, and the temperature is 100 ° C.
After being dried for 12 hours at 450 ° C. , it was baked for 3 hours at 450 ° C. in an atmosphere of 5% hydrogen and 95% argon to obtain ITO fine particles. The fine particles were wet peptized and ground for 2 hours with a sand mill. The average agglomerated particle size in the liquid after deflocculation and pulverization was 65 nm. After that, concentration was performed to obtain a liquid having a concentration of 6.8 wt% (F1 liquid).

"Preparation of coating liquid for conductive film" (11-2) The F1 liquid was diluted with ethanol and water and adjusted so that the ethanol content was 80 % by weight and the solid content was 2.5 % by weight . (F2 solution). “Applying and curing” (11-3) 30 g of F2 liquid was spin-coated on the surface of a 14-inch (type) CRT panel heated to a surface temperature of 45 ° C. by a spin coating method to obtain a film thickness of 100 nm at 120 nm.
After applying under the condition of pm for 60 seconds, 20 g of B2 solution is F
Under the same spin-coating conditions as when applying the two liquids, a coating amount of 60 nm is obtained at the time of curing, and then 30 at 160 ° C.
By heating for minutes, a glass for a cathode ray tube with a conductive film was obtained.

[Evaluation Results] Tables 1 to 3 show the types and physical properties of the conductive films obtained in Examples 1 to 8 and Comparative Examples 1 to 3. In the table, 2E2 means 2 × 10 ² , and the same applies to others.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

According to the present invention, various drawbacks of the prior art are solved, the weather resistance and the chemical resistance are excellent, and the practically sufficient film strength and electromagnetic wave shielding ability are further provided. A conductive film having an excellent antireflection effect can be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-77832 (JP, A) JP-A-3-68774 (JP, A) JP-A-10-182191 (JP, A) JP-A-9- 286936 (JP, A) JP-A-8-290943 (JP, A) JP-A-63-160140 (JP, A) Summary of lectures by the Powder and Powder Metallurgy Association 1989 Autumn Meeting (November 7, 1989) Issue), pp. 84, 85 (58) Fields investigated (Int.Cl. ⁷ , DB name) C23C 18/00-20/08 C09D 5/24 H01J 9/20 H01B 1/22

Claims (9)

(57) [Claims] 1. Reduction of a mixed solution of two or more metal salts
To form an alloy fine particle dispersion,
Alkali metal ions and ammonium ions contained in the liquid
And cations such as polyvalent metal ions and inorganic anions such as mineral acids.
Deionize organic anions such as ions, acetic acid, and formic acid.
By the above, a coating liquid for forming a conductive film containing an alloy fine particle dispersion containing two or more kinds of metal elements selected from the group consisting of Ag, Ru, Pt, Pd, Ni, Cu and Au is produced. A method for producing a coating liquid for forming a conductive film . Wherein said conductive film forming coating liquid, Ag, according to claim 1 comprising an alloy particle dispersion consisting of Pd and Cu
2. A method for producing a coating liquid for forming a conductive film according to. 3. The conductive film forming coating solution comprises Ag and N.
The method for producing a coating liquid for forming a conductive film according to claim 1 , comprising an alloy fine particle dispersion made of i. 4. The conductive film forming coating solution comprises Ru and P.
The method for producing a coating liquid for forming a conductive film according to claim 1 , comprising an alloy fine particle dispersion made of d. 5. The conductive film forming coating solution is Au or P.
The method for producing a coating liquid for forming a conductive film according to claim 1 , comprising an alloy fine particle dispersion made of d. 6. The average primary particle size of the alloy fine particles is 100 n.
It is m or less, The manufacturing method of the coating liquid for electrically conductive film formation of any one of Claims 1-5. 7. The conductivity of the coating liquid for forming a conductive film is 500.
7. The method for producing a coating liquid for forming a conductive film according to claim 1, which has a μS / cm or less. 8. A TiO _x fine particle (2.0> x ≧ 1.0) containing 0.3 to 30% by weight of nitrogen atom based on the total of titanium atom and oxygen atom and / or a silicon compound. Item 8. A method for producing a coating liquid for forming a conductive film according to any one of Items 1 to 7. 9. A fine alloy particle dispersion comprising Ru and Pd.
A coating liquid for forming a conductive film, comprising: