JP3514192B2 - Method for forming low reflective conductive film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a cathode ray tube panel.
For forming a low-reflection conductive film formed on the surface of a substrate such as
About. [0002] 2. Description of the Related Art Conventionally, a cathode ray tube panel operates at a high voltage.
Static electricity on its surface when starting up or shutting down.
Triggered. This static electricity causes the CRT panel surface
Dust can cause contrast to drop,
When touching the CRT panel directly,
Often cause discomfort due to the In order to prevent the above phenomenon, a cathode ray tube
Various attempts have been made to apply an antistatic film to the panel surface
For example, heating the surface of a CRT panel to about 350 ° C
Heat and apply tin oxide or indium oxide on the surface by CVD.
A method of providing a conductive oxide layer such as of indium
-76247) has been proposed. However, in this method, the cost of the film forming apparatus is increased.
In addition to this, the surface of the CRT panel is heated to a high temperature.
Of the phosphor in the cathode ray tube,
There were problems such as a decrease in legal accuracy. In addition, the conductive layer
Tin oxide is the most common material used, but acid
The disadvantage of tin oxide is that it is difficult to obtain a high-performance film at low temperatures
was there. In recent years, shielding of electromagnetic waves has also been required.
You. The conductive coating must be interposed on the surface of the CRT panel.
As a result, electromagnetic waves hit the conductive coating, causing eddy currents in the coating.
It induces flow and reflects electromagnetic waves by this effect. But,
For this purpose, the conductive coating is a good conductor that can withstand high electric field strength.
Need to be electrically conductive, but not so good
Obtaining the membrane was even more difficult. On the other hand, as a method of manufacturing a conductive film, Brown
Conduction by applying a mixture of metal salt and reducing agent on the tube panel surface
There is a method of forming a film (JP-A-6-310058).
However, in this method, the metal conductive film was plated on the glass surface
Condition, the strength of the film is extremely weak, and the conductive film is washed.
Cleaning process to remove by-product salts
Was. Further, when fine particles such as Ag and Au are used,
When the particle size is around 10 nm, the plasma resonance absorption
Absorption of light that occurs in display devices such as CRTs
Causes problems. Ag has particularly high conductivity.
Is suitable for electromagnetic wave shielding film, but its chemical activity is high.
And migration occurs.
Not a minute. [0008] Further, gold by ultrafine metal paste
There is a method for forming a metal film (JP-A-3-281783).
This metal paste consists of alcohols with 5 or more carbon atoms, acetic acid
Ethyl, ethyl oleate, butyl acetate, or glycer
Since it contains a lid and is relatively viscous, it has a thickness of several μm.
It is excellent for forming an electro-film,
Unsuitable for forming thin films or coating large areas
is there. In addition, a coating of a conductive film and a low-reflective conductive film may be used.
Forming by the coating method has traditionally been
CRTs for consumer devices, especially TVs and computer terminals
There have been many studies on. That is, for example
In order to give the CRT panel surface an anti-glare effect
SiO with fine irregularities on the surface_TwoTo attach layers,
Etching the surface with hydrofluoric acid to provide irregularities
The method (Japanese Patent Application Laid-Open No. 61-118931) has been adopted. However, these methods scatter external light.
Is called a non-glare treatment, which essentially has a low-reflection layer.
Method, there is a limit to the reduction in reflectance.
Also, for CRT panels, etc.
It is also a cause. [0011] SUMMARY OF THE INVENTION The present invention relates to the prior art.
The above-mentioned disadvantages of the low-reflective conductive film due to
Low-reflective conductive material that can be formed by low-temperature heat treatment
It is an object to provide a method for forming a film. [0012] SUMMARY OF THE INVENTION The present invention providesPowder volume resistance
Is 0.01Ωcm or lessRu moneySol of fine metal particles
The coating liquid for forming a conductive film is applied on a substrate by coating.
After forming, a film having a lower refractive index than the conductive film on the coating film
FormationAnd a conductive film having a thickness of 50 to 150 nm.
To obtain a conductive filmShape of low reflective conductive film characterized by the following
Provide a method of forming. A feature of the present invention is that a conductive film is formed
Use a coating solution containing metal fine particles in the form of a sol
This means that this coating solution is applied on a substrate to form a conductive film.
In the case where it is formed, it is described in JP-A-6-310058 and the like.
Plating film using a coating solution consisting of a metal salt and a reducing solution.
In contrast, microscopic holes are introduced into the conductive film. Then, a silicon compound is formed on the conductive film.
Coating containing hydrolyzate of Si alkoxide to be formed
When a liquid is applied, a silicon compound penetrates into these holes,
The film strength is significantly improved. Further, according to the present invention, Japanese Patent Laid-Open No. 6-31
0058 and the like, unlike the conventional method,
No by-products are formed during the formation of the conductive film and it is formed on the conductive film
There is no deterioration in film strength with the film to be formed. further,
Metal paste described in JP-A-3-281783
Solvent with a relatively high boiling point (boiling point 150 to 300 ° C)
Is not necessarily required, so that the film is kept at a low temperature (150 to 160
℃), the organic components remaining in the film
A very thin and strong film can be formed. Therefore
According to Ming, glass substrates, such as CRT panel surfaces,
Low reflectivity including at least one conductive film that solves the above-mentioned problems
A conductive film can be formed. [0016] BEST MODE FOR CARRYING OUT THE INVENTION
The invention will be described in more detail. Coating solution for conductive film formation (hereinafter
The Ru metal used in the present coating solution is fine particles.
Used. As metal fine particles, for example, evaporation of Ru metal
Fine particles generated by condensation can be used, but good
Chemical reduction of Ru metal salt
Fine particles produced by the above method are preferably used. In the present invention, the Ru metal fine particles by chemical reduction are used.
Examples of the metal salt used for producing particles include, for example, nitro
Ruthenium rosononitrate, ruthenium chloride, ruthenium chloride
Ammonium, ruthenium potassium chloride, ruthenium chloride
Sodium, ruthenium acetate and the like. As the reducing agent for the metal salt, for example, water
Sodium borohydride, potassium borohydride, hydrogenation
Hydride such as sodium and lithium hydride, formic acid, silicon
Oxalic acid, hypophosphorous acid, sodium hypophosphite, forma
Rudehyde can be used. Reduction precipitation method of metal fine particles
Is not particularly limited.
Dissolved in an organic solvent and adjust the pH with ammonia if necessary.
After adjustment, a method of adding a reducing agent can be adopted. this
Sometimes citric acid, sodium citrate, polyvinylpyro
Gold such as lidone, polyvinyl alcohol, polyacrylic acid
It is also preferable to add a genus particle dispersion protective agent. In this method, depending on the type of the metal salt,
It is preferable to adjust the reaction temperature. Fine metal particles generated
The pups are washed and dried as appropriate. Powder of metal fine particles
The product resistance is preferably 0.01 Ωcm or less. This coating liquid is obtained by dissolving the above metal fine particles in water or an organic
It is prepared by uniformly dispersing it in a sol form in a solvent, etc.
Made. Metal particle powder has a very large particle size
Is difficult to disperse, and sedimentation occurs during storage of the coating solution.
Storage stability tends to be inferior.
The average agglomerated particle size of the genus fine particles is 200 nm or less,
It is preferably from 0 to 160 nm. Average aggregate particle size
Fine particles having a particle size of less than 10 nm are not practical in the preparation thereof, and
The fine particles having an average agglomerated particle size of more than 160 nm
Aggregation of fine particles easily occurs with each other, and the storage stability of the coating solution
Is remarkable. The storage stability of the coating solution as the average primary particle size
From the viewpoint of 100 nm or less, particularly preferably 5 to 80 nm.
New Fine particles having an average primary particle size of less than 5 nm have low crystallinity.
Contact between metal fine particles in the film
Resistance tends to increase and the conductivity of the coating film tends to be poor. Also,
Fine particles with an average primary particle size of more than 80 nm are easy to use in coating solutions
Aggregation of fine particles occurs on the surface, resulting in poor storage stability of the coating solution
The tendency is remarkable. In order to improve the dispersibility of the metal fine particles,
Heating, UV irradiation, immersion in oxidizing agents, etc.
The surface of the particles may be partially oxidized. Fine metal particles in coating liquid
The content of the particles is not particularly limited, but usually 0.05 to
About 10% by weight, and the formed conductive film has a predetermined thickness.
The content is adjusted so that Less than 0.05% by weight
In this case, it is difficult to obtain a conductive film having a predetermined thickness.
When the amount is more than%, it tends to be difficult to obtain a conductive film having a uniform thickness.
(Particularly remarkable in the spin coating method)
Tend to have poor storage stability. In the preparation of the present coating solution, the fine metal particles are dissolved in water.
It is preferable to uniformly disperse in an organic solvent or the like. So
The contact between the solvent and the metal particles.
For this purpose, it is necessary to perform sufficient stirring. Stirring means
Examples include colloid mill, ball mill, sand
Commercially available milling and dispersing machines such as mills and homomixers
Wear. In addition, when dispersing, the temperature is in the range of 20 to 200 ° C.
Can also be heated. When stirring above the boiling point of the solvent
In this case, pressurization is performed so that the liquid phase can be maintained. Like this
Water in which Ru metal fine particles are dispersed as colloid particles
Sols or organosols are obtained. In the present invention, the aqueous sol is used as it is.
Although it can be used as a main coating solution,
In order to increase the particle size, disperse the metal fine particles in an organic solvent or
Or even when the water in the aqueous sol is replaced with an organic solvent.
You. Formation of the organosol and placement of the medium described above
As the organic solvent used for exchange, for example, a hydrophilic organic solvent
Are preferred, for example, methanol, ethanol,
Alcohols such as alcohol and butanol, and ethyl
Cellosolve, methyl cellosolve, butyl cellosolve,
Ethers such as propylene glycol methyl ether,
2,4-pentanedione, diacetone alcohol, etc.
Esters such as ketones, ethyl lactate and methyl lactate
And the like. This coating solution contains the above-mentioned organic solvent and water.
Can be applied to form an optical thin film on a large area substrate
The viscosity of the liquid is preferably 0.1 to 5 cP. Viscosity from 5 cP
Is high, it tends to be difficult to form a uniform optical thin film.
You. Practically, 0.2 to 5 cP is particularly preferable. The coating liquid has a surface tension, spreading property and the like of the liquid.
From the point of adjusting Si (OR)_y・ R '_4-y(Y is 3
Or 4, R and R 'are alkyl groups).
Elemental compound or its partial hydrolyzate (hereinafter referred to as
Simply decomposable silicon compound or its partial hydrolyzate
"Silicon compound"). For metal fine particles
On the other hand, a silicon compound can be added at an arbitrary ratio,
Considering the properties and the strength of the conductive film, the metal fine particles / Si
O_TwoThe converted silicon compound (weight ratio) is 1/6 to 10 /
1 is preferred, and 1/4 to 5/1 is more preferred. In addition, the present coating liquid contains a conductive film having an appropriate thickness.
For this purpose, Sn, Sb, In, Zn, Ga, Al and
Oxides of one or more metals selected from the group consisting of
Can be contained in the form of a sol similar to fine metal particles.
You. Metal oxide is used at an arbitrary ratio to metal fine particles
However, metal fine particles / metal oxide (weight ratio) is 99 /
1-60 / 40, more preferably 95 / 5-70 / 30
Good. Further, in order to improve the wettability with the substrate,
Various surfactants can be added to the present coating solution. Metal granules
Containing silicon compounds and metal oxides together with
The concentration (solid content) of this coating solution is about 0.05 to 10% by weight.
Degrees are preferred. Predetermined film thickness when less than 0.05% by weight
It is difficult to obtain a conductive film of
There is a tendency that a conductive film with a uniform thickness is difficult to obtain (especially spin coating
Method, and the storage stability of the solution is poor.
There is a tendency. The coating solution thus obtained is dried on a substrate.
After drying, apply to a predetermined thickness and heat to conduct conductive film
Is formed. The thickness of the conductive film is not particularly limited,
Usually, 50 to 150 nm is preferable. Below 50nm
In some cases, conductivity may not be sufficiently exhibited.
Reduces the transmittance and is applied to display devices such as cathode ray tubes
Becomes difficult. Further, when the thickness exceeds 150 nm, the
Form a low-refractive-index film and form a low-reflective conductive film with two layers
In some cases, it may be difficult to maintain the specified low reflection performance.
You. The method of applying the coating solution to a substrate is particularly limited.
Although not specified, for example, spin coating, dip coating
And a method such as spray coating can be suitably used. Ma
In addition, irregularities are formed on the surface using the spray coating method to prevent
A glare effect may be imparted, and a silica coating may be applied on the substrate.
Such a hard coat may be provided. Furthermore, the present invention
Spin coating or spray coating
Formed by any of the above methods, and the silicon compound
Spray-coat with a solution containing substances to make the surface uneven
A non-glare coat of a silica coating may be provided. When a low boiling point solvent is used in the present coating solution,
Drying at room temperature gives a uniform coating, but with a boiling point of 100
When using a medium to high boiling solvent in the range of ~ 250 ° C
When drying at room temperature, the solvent remains in the coating film.
Work. The upper limit of the heating temperature depends on the glass and plastic used for the substrate.
It is determined by the softening point of a substrate such as a stick. this
Considering the points, the preferable heating temperature range is 100 to 500.
° C. In the present invention, the conductor formed by the above method is used.
A low-reflection film is formed on the film using the interference of light
it can. For example, when the substrate is glass (refractive index n = 1.
52) On the conductive film, (refractive index of conductive film) / (low refractive index)
Low refractive index such that the ratio of the refractive index of the refractive index film is about 1.23.
The reflectance is reduced most by forming a refractive index film.
be able to. To reduce the reflectivity in the visible light region,
In particular, it is preferable to reduce the reflectance of 555 nm light.
However, in practice, it should be determined appropriately taking into account the reflection appearance, etc.
Is preferred. The low-reflective conductive film having two layers has the
The low refractive index film of the outer layer is made of MgF_TwoSolution containing sol or silicon
Using one or more solutions selected from solutions containing compounds
The formed film is preferred. MgF in terms of refractive index_TwoIs the most
MgF for low reflectance_TwoThe solution containing the sol
MgF used_TwoA film mainly composed of
In terms of hardness and scratch resistance, SiO_TwoIs mainly composed of
preferable. Solution containing a silicon compound for forming a low refractive index film
Various liquids can be used.
Tetraethoxide, silicon tetramethoxide, silicon
Contetraisopropoxide, silicon tetrabutoxy
Preferred are monomers such as chlorides, or polymers thereof. The silicon compound is usually alcohol,
Dissolved in ter, ether, etc.
Add hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, maleic acid,
Add acid or aqueous ammonia solution to hydrolyze and use
You can also be. The content of the silicon compound in the solution is
The storage stability is not limited to too much
The solid content is less than 30% by weight of the solvent
It is preferred to use. Further, MgF is used for forming a low refractive index film._Twouse
If so, use MgF_TwoUsing the fine particles of
To form a colloid that is stable in a solvent such as water or an organic solvent.
Aqueous sol or organ
Used as nosol. MgF in dispersion_TwoPreferred
The concentration is the same as in the case of the silicon compound. As an organic solvent
In addition, the above-mentioned organic solvents can be used. In addition, the above solution or dispersion has a strong membrane.
Zr, Ti, S
alkoxides such as n and Al, and partial hydrolysis thereof
And then add ZrO_Two, TiO_Two, SnO_Two, Al_TwoO_Three
One or more composites such as MgF_TwoAnd SiO_Two
At the same time, they may be precipitated. To the above solution or dispersion
The amount of binders such as these alkoxides is
Compound and / or MgF_Two0.1 to 10 times
% Is preferred. Further, if necessary, the wettability with the substrate is improved.
Surfactant to the above solution or dispersion
May be added. Examples of added surfactants include
For example, sodium linear alkyl benzene sulfonate,
Alkyl ether sulfate and the like. The above solution or dispersion for forming a low refractive index film
Using the same method as in the case of forming the conductive film.
A refractive index film is formed. Formation of low reflective conductive film of the present invention
The method is applied to a low-reflection conductive film due to the multilayer interference effect.
it can. Composition of multilayer low-reflection film with antireflection performance
For example, let λ be the wavelength of light that you want to prevent reflection
From the substrate side, the high refractive index layer-the low refractive index layer
/ 2-λ / 4 or λ / 4-λ / 4
Low reflective film, medium refractive index layer-high refractive index layer-low bending
3 in which the refractive index layer was formed with an optical thickness of λ / 4−λ / 2−λ / 4
Low-reflective film, low refractive index layer from substrate side-medium refractive index layer-
The high refractive index layer-the low refractive index layer is formed into an optical thickness λ / 2-λ / 2-λ.
A typical example is a four-layer low-reflection film formed at λ / 2-λ / 4
Also known as The conductive film containing the Ru metal fine particles can be used.
Contrast because absorption occurs throughout the visual field
Contributes to the improvement of In the present invention, a low reflective conductive film is formed.
1) CRT panel, 2) Copy machine
Glass plate, 3) Computer panel, 4) Clean room
Glass, 5) a front panel of a display device such as a CRT or an LCD,
Such as various glass substrates or plastic substrates
No. [0043] The present invention will be described below with reference to Examples and Comparative Examples.
As will be described more specifically, the present invention is limited to these examples.
Not done. In addition, the usage ratio in the examples and comparative examples
And% are by weight. Examples and Comparative Examples
The evaluation method for the film obtained in
The results are shown in Table 1. Note that the description “7.2E2” in the table is used.
The loading is 7.2 × 10^TwoAnd so on. 1) Conductivity evaluation: Loresta resistance measuring instrument
(Mitsubishi Chemical Corporation) was used to measure the surface resistance of the film surface. 2) Scratch resistance: Scratch resistance measuring instrument (50-5 manufactured by LION)
0), after reciprocating the membrane surface 50 times under a 1 kg load,
Surface damage was determined visually. Evaluation criteria: ○: scratches
Not at all, △: Some scratches, ×: Partial film peeling
It occurred. 3) Pencil hardness: Various under 1 kg load
Scan the membrane surface with a pencil of hardness and then visually inspect the surface
The hardness of the pencil that begins to scratch the surface is determined as the pencil hardness of the film.
Was. 4) Luminous reflectance: GAMMA spectral reflectance spectrum measurement
Luminous reflectance of the multilayer film at 400 to 700 nm
It was measured. 5) Luminous transmittance: Spectrophotometer U-3500
Visibility at 380-780nm by (Hitachi)
The percentage was measured. 6) Evaluation of weather resistance: Photodry cleaner P
25 by L7-200 (manufactured by Sen Engineering Co., Ltd.)
Of the film after irradiation with ultraviolet light having a main wavelength of 4 mm for 200 hours.
The surface resistance was measured. 7) Chemical resistance evaluation: dipped in 5% NaCl solution for 100 hours
After that, the surface resistance value of the film was measured. The powder volume resistance of the obtained metal fine particles
Is the average agglomerated particle size of the obtained sol, measured by a four-terminal method.
Is a laser diffraction particle size analyzer LPA-3 manufactured by Otsuka Electronics Co., Ltd.
100. The average primary particle size of the obtained sol is
Observed by JEOL transmission electron microscope 100CX
The average particle diameter of 20 representative particles was determined. Obtained
The film thickness is measured by scanning electron microscopy of the fracture surface
The viscosity of the conductive liquid was measured at 20 ° C with an E-type viscometer.
Was. Silicon tetraethoxide to ethanol
Dissolve and hydrolyze with hydrochloric acid aqueous solution._TwoExchange
The solution was adjusted with ethanol so as to be 5% in total (Solution B). Water: ethanol: methanol: propylene glycol
No methyl ether = 50: 42: 5: 3 (weight ratio) mixture
A mixed solution was prepared (Solution D). Example 1 Ruthenium trichloride aqueous solution (solid content)
Sodium citrate to ruthenium in 10%)
Twice the molar amount of sodium borohydride solution
Reduces metal ruthenium by adding 4 times the amount of mol
Was deposited. After this, the excess ions are removed by ultrafiltration,
Ruthenium sol containing 5.8% metal ruthenium
Prepared (Solution F). The average aggregate particle size of the obtained sol was 60 nm.
there were. The average primary particle size is 9 nm, and the primary particle size is 9 nm.
The difference between the maximum value and the minimum value of
It was uniform. The sol was dried at 100 ° C.
The powder volume resistance of the obtained metal powder is 0.0003Ωcm.
there were. Water: butyl cellosolve: N-methylpyrroli
A mixed solution of don = 87: 10: 3 (weight ratio) was prepared.
(G solution). Solution F is liquid G and solid content is 0.6% (in this case,
Diluted (H)
liquid). The viscosity of the liquid H was 1.02 cP. Isopropyl alcohol: propylene glycol
Coal monoethyl ether acetate: diacetone al
A mixed solution of Cole = 6: 3: 1 (weight ratio) was prepared (U
1 solution). Solution H was spin-coated on the surface of a 14-inch CRT.
After coating by the liquid method, B solution is applied on the film (conductive film) with U1 solution.
The one diluted to 0.85% is applied by spin coating,
It was baked at 160 ° C. for 30 minutes to obtain a low reflective conductive film. In addition,
The thickness of the conductive film was 70 nm. Example 2 Ruthenium trichloride aqueous solution (solid content)
(10%), formic acid was added at 3 times the molar amount of ruthenium, and
After that, citric acid was added 10 times mol to ruthenium,
Add sodium borohydride solution to ruthenium
The metal ruthenium was reduced and precipitated by adding 4 times mol. This
After that, the metal ruthenium is separated by centrifugation and distilled water is added.
After redispersion, remove excess ions with ion exchange resin
Ruthenium sol containing 4.3% metallic ruthenium
A liquid was prepared (F2 liquid). The average agglomerated particle size of the obtained sol was 32 nm.
there were. The average primary particle size is 5 nm, and the primary particle size is 5 nm.
The difference between the maximum value and the minimum value of
It was uniform. The sol was dried at 100 ° C.
The powder volume resistance of the obtained metal powder is 0.0003Ωcm.
there were. Solution F2 is solution G and has a solid content of 0.45% (this example)
In the case of only ruthenium metal fine particles)
(H2 solution). The viscosity of the H2 liquid was 1.01 cP.
Was. Spin coat H2 liquid on 14 inch CRT surface
After applying by the method, B solution is applied on the film (conductive film) with U1 solution.
The one diluted to 0.85% is applied by spin coating,
It was baked at 160 ° C. for 30 minutes to obtain a low reflective conductive film. In addition,
The thickness of the conductive film was 60 nm. Example 3 Stannic chloride (SnCl)_Four) Water soluble
The solution and the aqueous solution of indium nitrate were combined with Sn / In = 15/85.
(Atomic ratio) and mix this solution with ammonia
Adjusted to pH 12 with water and dropped into the solution maintained at 60 ° C
And precipitated. This precipitate is filtered off by washing, and 100
After drying at 10 ℃ for 10 hours, baking in nitrogen at 600 ℃ for 5 hours
To obtain tin-doped indium oxide (ITO) fine particles
Was. The particles have an average agglomerated particle size in the liquid of 80 nm (average
Pulverized by an impact pulverization method until the next particle size becomes 30 nm).
Was concentrated to obtain a liquid having a solid content of 4.3% (K2
liquid). The F2 solution and the K2 solution were prepared by mixing the F2 solution / K2 solution with 9
It was mixed so as to be 3/7 (weight ratio). In addition, Rutheni
The average agglomerated particle size of the fine metal particles was 32 nm. Ma
The average primary particle size is 5 nm, and the maximum primary particle size is
The difference from the minimum value was within 5 nm and the particle size was extremely uniform.
Was. Thereafter, this mixed solution is solidified with solution G (ruthenium metal
The total amount of fine particles and ITO fine particles) is 0.55%
(H4 solution). The viscosity of H4 liquid is 1.15 cP
Met. Ruthenium metal fine particles / ITO fine particles
(Weight ratio) was 93/7. Spray H4 solution onto the surface of a 14-inch cathode ray tube.
After coating by the uncoating method, the solution B
The solution diluted to 3% is applied by spin coating,
C. for 30 minutes to obtain a low reflective conductive film. The conductive film
Was 80 nm. [Example 4] pH of ruthenium chloride aqueous solution with ammonia water
Adjusted to 10 and dropped into the solution maintained at 60 ° C.
Was deposited. The precipitate is filtered off by washing,
After drying for 2 hours, bake in air at 500 ° C for 2 hours.
Ruthenium (RuO_Two) Fine particles were obtained. These particles in the liquid
The average aggregate particle size is 95nm (average primary particle size is 20nm)
Pulverized by the impact pulverization method until it is concentrated.
4.3% was obtained (K3 solution). The F2 liquid and the K3 liquid were mixed with the F2 liquid / K3 liquid
It was mixed so as to be 0/30. In addition, ruthenium metal
The average aggregate particle size of the fine particles was 32 nm. Also the average
The primary particle size is 5 nm, and the maximum and minimum values of the primary particle size are
Was within 5 nm and the particle size was extremely uniform. That
Thereafter, the mixed solution was solidified with solution G (with ruthenium metal fine particles).
RuO_Two(Total amount of fine particles) is 0.62%.
(H5 solution). The viscosity of the liquid H5 was 1.35 cP.
Was. In addition, ruthenium metal fine particles / RuO_TwoFine particles (heavy
Quantitative ratio) was 70/30. Spray H5 solution onto the surface of a 14-inch cathode ray tube.
After coating by the uncoating method, the solution B is coated on the film (conductive film) with U1
0.95% diluted with liquid is applied by spin coating
Then, the resultant was baked at 160 ° C. for 30 minutes to obtain a low-reflection conductive film. What
The thickness of the conductive film was 100 nm. Example 5 (Comparative Example) Stannic chloride (SnC
l_Four) And antimony chloride, Sn / Sb = 85/15
(Atomic ratio) and mix this solution with ammonia
Adjust to pH 10 with water and add to solution maintained at 50 ° C
And precipitated. This precipitate is filtered off by washing, and 100
Baked in air at 650 ° C for 3 hours,
Antimony-doped tin oxide fine particles were obtained. These fine particles
The mixture was pulverized with a sand mill for 2 hours. The anti in the liquid at this time
The average particle diameter of the mon-doped tin oxide fine particles was 65 nm.
Was. Thereafter, concentration was performed to obtain a liquid having a solid content of 5%. This liquid was diluted with liquid D to a solid content of 1.2%,
Spin coating was performed on the surface of a 14-inch CRT panel.
Solution B was further diluted to 0.9% with U1 solution on this membrane.
Apply liquid by spin coating method and bake at 160 ° C for 20 minutes
Then, a two-layer film was formed. Example 6 (Comparative Example) Silver nitrate aqueous solution (in terms of silver)
Sodium citrate 5 times that of silver to 10% solids)
After the molar addition, iron nitrate was added three times the molar amount to silver and precipitated.
Deposited. After separating this precipitate by centrifugation,
Re-disperse by adding distilled water, and then remove with ion exchange resin
Salting was performed to obtain a silver sol having a solid content of 3.2% (Solution I). Liquid I
Was diluted with liquid G such that the solid content was 0.45% (J
liquid). 14 inch cathode ray tube surface spin coating method with J solution
And dilute B solution to 0.85% with U1 solution on the film.
The coated product is applied by spin coating,
By firing for a minute, a low reflection conductive film was obtained. [0064] [Table 1] [0065] According to the present invention, spray or spin
Efficient and excellent low reflectivity by simple methods such as coating
A conductive film can be provided. According to the present invention, electromagnetic waves can be easily switched.
And can be manufactured relatively inexpensively. In particular, CR
Applicable to large area substrates such as T panel face
Its industrial value is very high because it is possible and mass production is possible.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // C03C 17/36 G02B 1/10 Z (56) References JP-A-8-77832 (JP, A) JP-A-3-281784 (JP) , A) JP-A-55-144029 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B05D 5/06 B05D 5/12 C09D 5/24 G02B 1/10 H01J 9/20 C03C 17/36

Claims (1)

(57) The Claims 1. A conductive powder volume resistivity comprising a sol of R u metals particles is below 0.01Ωcm film-forming coating liquid was applied onto the substrate After forming a coating film, a film having a lower refractive index than the conductive film is formed on the coating film, and a film having a refractive index of 50 to 150 nm is formed .
A method for forming a low-reflection conductive film, comprising obtaining a low-reflection conductive film having a thickness of a conductive film .