JPH0687632A - Low-reflection conductive film having antidazzle effect and its production - Google Patents

Abstract

PURPOSE:To inexpensively obtain a high-transmittance and high-conductivity film having an antidazzle effect with good productivity by spray-coating the surface of a specified film with a soln. contg. the material capable of forming a low-refractive-index film and heating the coat to form a film having ruggednesses on its surface. CONSTITUTION:An Ru compd. capable of forming RuO2, etc., an In compd., capable of forming In2O3, etc., and the compds. of Si, Zr, Ti, Al, Sn, etc., as required, are incorporated to obtain a condcutive film forming coating soln. The soln. is sprayed over a glass substrate to form a low-reflection conductive film consisting of >=2 layers. A soln. contg. SiO2, etc., is then sprayed on the uppermost layer of the film and heated to form a low-refractive-index film having ruggednesses on its surface, and a low-reflection conductive film having an antidazzle effect is produced. The low-reflection conductive film is formed, as required, on the glass substrate to produce a vitreous article, or the conductive film is formed on the surface of the glass face panel of a cathode-ray tube to form the cathode-ray tube.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-reflective conductive film suitable for being applied to the surface of a glass substrate such as a cathode ray tube panel and a method for producing them.

[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 face panel of the cathode ray tube at the time of starting or ending. This static electricity often causes dust to adhere to the surface to cause a decrease in contrast, or causes a slight electric shock when directly touched to cause discomfort.

In the past, many attempts have been made to provide an antistatic film on the surface of a cathode ray tube face panel in order to prevent the above-mentioned problems. For example, as described in JP-A-63-76247, the surface of a CRT face panel is heated to 350 ° C.
A method has been adopted in which a conductive oxide layer such as tin oxide and indium oxide is provided by heating to a certain degree and using a CVD method.
However, in this method, there is a problem in that in addition to the cost of the apparatus, heating of the cathode ray tube at a high temperature causes the fluorescent substance in the cathode ray tube to fall off and the dimensional accuracy to decrease. 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.

In recent years, radio wave interference to electronic equipment due to electromagnetic wave noise has become a social problem, and standards have been created and regulated to prevent it. Electromagnetic noise is considered to be a problem in various countries in the human body, such as fear of skin cancer due to electrostatic charge on the cathode ray tube face panel, influence on the fetus due to low frequency electromagnetic field (ELF), and harm due to X-rays and ultraviolet rays. In this case, when an electromagnetic wave hits the conductive coating film due to the presence of the conductive coating film, an eddy current is induced in the coating film, and this action reflects the electromagnetic wave. However, for this purpose, it is necessary to have good conductivity having electric characteristics comparable to those of metals capable of withstanding high electric field strength, but it has been more difficult to obtain a film having such good conductivity.

Further, the coating method of the low reflection film is not limited to the conventional optical equipment, and the coating method for consumer equipment,
In particular, many studies have been made on cathode ray tubes (CRTs) for TVs and computer terminals.

A conventional method is disclosed in, for example, Japanese Patent Laid-Open No. 61-1189.
As described in No. 31, SiO having fine irregularities on the surface in order to have an antiglare effect on the surface of the cathode ray tube face panel.
Methods such as attaching two layers or etching the surface with hydrofluoric acid to form irregularities have been used. However, these methods are called non-glare treatment that scatters external light, and there is a limit to the reduction of reflectance because it is not a method of essentially providing a low reflection layer, and in addition, it has an antiglare effect in a cathode ray tube. Requires a film thickness, which is also a cause of lowering the resolution.

[0007]

The present inventor has proposed, as a conductive film capable of eliminating the above-mentioned drawbacks of the prior art, a low-reflection conductive film composed of a multilayer film having a conductive film containing ruthenium oxide as a main component as a lower layer. The membrane has already been proposed. However, there is a problem that a fingerprint or the like is easily noticed in the low reflection film using the multilayer interference. Therefore, in the present invention, SiO is formed on the uppermost layer of the multilayer film including the conductive film containing ruthenium oxide as a main component.
By providing a film having irregularities containing 2 as a main component, a high-performance low-reflection conductive film having both low reflectivity and antiglare effect due to the interference of light is provided, and a manufacturing method thereof is newly provided. The purpose is to

[0008]

The present invention has been made to solve the above-mentioned problems, and is a low reflection conductive film having at least two layers including a conductive film containing an oxide of Ru and In as main components. Is formed, and the surface of the uppermost layer is spray-coated with a liquid containing a material that can be a low refractive index film, and then heated to form a film having a low refractive index and unevenness on the surface to prevent glare. The present invention provides a method for producing a low reflection conductive film having an antiglare effect, which comprises forming a low reflection conductive film having an effect.

Further, according to the present invention, a glass substrate such as a face panel of a cathode ray tube is coated with a coating solution containing a Ru compound which can be a Ru oxide, an In compound which can be an In oxide, water and / or an organic solvent. By forming a multilayer film including a conductive film obtained by heating at 500 ° C. and further forming a film having irregularities containing SiO 2 as a main component on the uppermost layer, low reflection due to light interference and antiglare It is intended to provide a method for producing a low-reflection conductive film of a glass substrate such as a cathode ray tube face panel, which is characterized by simultaneously providing the effect.

Further, the present invention provides a glass substrate such as a face panel of a cathode ray tube with a coating liquid containing a Ru compound which can be a Ru oxide, an In compound which can be an In oxide, water and / or an organic solvent, a Si compound and a Ti compound. A solution containing at least one of a compound, a Zr compound, an Al compound, and a Sn compound is applied and heated at 100 to 500 ° C. to form a multilayer film including a conductive film, and SiO 2 is further formed on the uppermost layer. A method for producing a low-reflection conductive film of a glass substrate, such as a cathode ray tube face panel, characterized in that low-reflectivity and anti-glare effect due to interference of light are simultaneously provided by forming a film having irregularities as a main component. Is provided.

The Ru compound used in the coating solution of the present invention is not particularly limited as long as it turns into ruthenium oxide by heating. For example, salts such as ruthenium chloride and ruthenium nitrate, β-diketones or ketoesters and complexes with them can be used. Ru to be formed, a salt of the Ru, ruthenium red,
Hexaammine ruthenium (III) salt, pentaammine (dinitrogen) ruthenium (II) salt, chloropentaammine ruthenium (III) salt, cis-dichlorotetraammine ruthenium (III) chloride monohydrate, tris (ethylenediamine) ruthenium ( II) Any one of salts, ruthenium acetate, ruthenium bromide, ruthenium fluoride, and hydrolysates thereof can be used.

Examples of the solvent for the coating liquid include water and organic solvents. As the hydrophilic organic solvent, alcohols such as methanol, ethanol, propanol and butanol, and ethers such as ethyl cellosolve can be arbitrarily used.

The In compound used in the present invention is not particularly limited as long as it can be converted into indium oxide by heating, and examples thereof include inorganic salts such as indium chloride and indium nitrate, and organic salts such as indium octylate and indium naphthenate. Examples thereof include acid salts, alkoxides such as tributoxyindium and triethoxyindium, complexes in which β-diketones such as acetylacetone and ketoesters such as methylacetylacetonate are coordinated, and organic In compounds.

The coating liquid used in the present invention contains S as a binder in order to improve the adhesion strength and hardness of the film.
i (OR) y R '(4-y) (y = 3 or 4, R, R':
It is also possible to add a solution containing a Si compound or a partial hydrolyzate thereof which becomes SiO2 by heating (alkyl group) or the like. At that time, as a hydrolysis catalyst, HCl, HN
O3, CH3 COOH or the like can be used. Further, various surfactants can be added to improve the wettability with the substrate.

Furthermore, in order to adjust the refractive index of the conductive film,
When heated, TiO2, ZrO2, Al2 O3,
Ti compound, Sn compound, Al compound, which becomes SnO2,
One or a plurality of Sn compounds and the like can be mixed in the coating liquid. As each compound of Ti, Zr, Al, and Sn, any of alkoxides of these metals, metal salts, and hydrolysates thereof can be used.

In the coating liquid for forming the conductive film, the Ru compound and the In compound can be mixed at an arbitrary ratio, but the higher the RuO2 / In2O3 ratio in terms of oxide, the higher the conductivity. However, if the content of RuO2 is too large, the transmittance decreases, so RuO2 / In2O3
Is preferably about 8/2 to 1/9 by weight.

The Ru compound, the In compound and the Si compound can be mixed in any ratio, but in consideration of the development of conductivity and the film strength, the mixing ratio (weight ratio) is (Ru
O2 + In2O3) / SiO2 conversion 1/6 to 20 /
Mixing up to 1 is preferred. More preferably 1 /
4 to 10/1 is recommended. The solid content of the liquid may be 0.05 to 10 wt%, and more preferably 0.3 to 5.0 wt%. This is because if the concentration is high, the storage stability of the liquid becomes poor, and if the concentration is too low, the film thickness becomes thin and sufficient conductivity cannot be obtained.

The coating method of the coating liquid on the substrate is not particularly limited except for the uppermost film having irregularities, and spin coating, dip coating, spray coating and the like can be preferably used.

Since the solution containing the Ru compound and the In compound in the present invention can be provided as a coating solution on a substrate by itself, a uniform film can be obtained by drying at room temperature when a solvent having a low boiling point is used. When a high boiling point solvent is used or when it is desired to improve the strength of the film, the coated substrate is heated.
The upper limit of the heating temperature is determined by the softening point of glass, plastic, etc. used for the substrate. Considering this point, the preferable temperature range is 100 to 500 ° C.

In the present invention, a low reflection conductive film utilizing light interference is formed. For example, when the substrate is glass (refractive index n = 1.52) in a two-layer low-reflection film, the ratio of n1 (conductive film) / n2 (low-refractive index film) is above the conductive film. The reflectance can be reduced most by forming a low refractive index film having a thickness of about 1.23.

As the structure of the multilayer low-reflection film having the antireflection property, the wavelength to be antireflection is set to λ, and the high refractive index layer-low refractive index layer is formed to have an optical thickness of λ / 2-λ / 4 from the substrate side. Alternatively, a two-layer low reflection film formed of λ / 4-λ / 4, a medium refractive index layer-high refractive index layer-low refractive index layer from the side of the substrate has an optical thickness of λ / 4-λ.
/ 2--λ / 4 three-layer low-reflection film, from the substrate side low refractive index layer-medium refractive index layer-high refractive index layer-low refractive index layer optical thickness λ / 4-λ / 4-λ A 4-layer low-reflection film formed of / 2-λ / 4 is known as a typical example, and a conductive film containing Ru and In oxides as main components is used as a high-refractive-index film. It is also possible to form a low reflection layer film of

Further, in order to impart an antiglare effect to this low reflective conductive film, the surface of the uppermost layer of the above-mentioned low reflective conductive film utilizing the interference effect of light has a low refractive index and has irregularities on the surface. It can be provided by forming a film having the same by a spray coating method. Alternatively, a film having a low refractive index and unevenness on the surface is directly formed on the conductive film containing the oxide of Ru and In as a main component, and the thickness after heating causes an antireflection effect due to interference. Formed by spray coating method
At the same time as imparting an antiglare effect, low reflectivity can be imparted.

When imparting antiglare property to the low reflection antistatic film formed on the front surface of the cathode ray tube, the degree of antiglare property is preferably 60 or more and 70 or less in terms of gloss value. If it is less than 60, the haze becomes high and the resolution becomes poor,
This is because if it exceeds 70, the film tends to appear glaring.

As a method for producing a low refractive index film which constitutes a low reflective conductive film or a film having a low refractive index and having irregularities on its surface, a solution containing MgF2 sol, a Si alkoxide which becomes SiO2 by heating, etc. It is formed by using a solution of at least one selected from the solutions containing Si compounds. From the viewpoint of the refractive index, MgF2 is the lowest of the materials, and it is preferable to use a solution containing MgF2 sol to reduce the reflectance, but SiO2 is the main component in terms of film hardness and scratch resistance. Membranes are preferred.

Various substances can be used as the solution containing the Si compound for forming the low refractive index film forming the low reflective conductive film and / or for forming the film having the low refractive index and the uneven surface. However, Si (OR) mR'n (m = 1 to 4,
A liquid containing a Si alkoxide or a partial hydrolyzate represented by n = 0 to 3 and R, R '= C1 to C4 alkyl group). For example, a monomer or polymer of silicon ethoxide, silicon methoxide, silicon isopropoxide or silicon butoxide can be preferably used.

The Si alkoxide can be used by dissolving it in alcohol, ester, ether or the like, or can be used by adding hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid or aqueous ammonia solution to the solution and hydrolyzing it. Further, the Si alkoxide is preferably 30 wt% or less with respect to the solvent. Further, to improve the strength of the film, an alkoxide of Zr, Ti, Al or the like or a partial hydrolyzate of these is added to this solution to give Z
One or a mixture of two or more of rO2, TiO2 and Al2 O3 may be simultaneously deposited with MgF2 and SiO2. Alternatively, a surfactant may be added to improve the wettability with the surface to which such liquid is applied. Examples of the surfactant to be added include linear sodium alkylbenzene sulfonate, alkyl ether sulfate, and the like.

As a substrate for forming the low-reflection conductive film of the present invention, a cathode ray tube face panel, a glass plate for a copying machine, a computer panel, a glass for a clean room, various glasses such as a front plate of a display device such as a CRT or LCD, and a plastic. A substrate can be used.

[0028]

The present invention will be further described below with reference to examples of the present invention, 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 value of the film surface was measured by a Loresta resistance measuring device (manufactured by Mitsubishi Yuka).

2) Scratch resistance Under a load of 1 kg, the surface of the film is exposed to 2 by 50-50 manufactured by LION.
After reciprocating 00 times, scratches on the surface were visually judged.
The evaluation criteria are as follows. ◯: No scratches were found Δ: Some scratches were found ×: Film peeling occurred partly

3) Pencil Hardness Under a load of 1 kg, the surface of the film was scanned with a pencil, and then the pencil hardness at which scratches on the surface began to occur was judged to be the pencil hardness of the film. 4) Luminous reflectance Multilayer film 4 by GAMMA spectral reflectance spectrum measuring device
The luminous reflectance at 00 to 700 nm was measured. 5) Gloss value It was measured with a gloss meter manufactured by HORIBA.

Example 1 RuCl3.nH2O was dissolved in ethanol to prepare a Ru concentration of 3% by weight in terms of RuO2. This liquid is called liquid A. Dissolve indium chloride in acetylacetone so that acetylacetone becomes 1.5 times (molar ratio) of indium chloride, and
Heating was carried out at 10 ° C. for 1 hour. This solution was dissolved in ethanol to prepare an In concentration of 3% by weight in terms of In2O3. This solution is referred to as solution B. Ethyl silicate is dissolved in ethanol and hydrolyzed with an aqueous HCl solution.
It was set to 3% by weight in terms of 2. This solution is referred to as solution C.

RuO2, In2 O3 and Si in terms of oxide
The solution obtained by mixing the liquids A, B, and C so that O2 has various weight ratios is further diluted with a solvent such as alcohol to prepare 1
6 cm spin glass coating at 100 RPM
It was applied for 0 seconds and then heated at 300 ° C. for 10 minutes. Further, the liquid C was applied onto this film by a spin coating method at a rotation speed of 100 RPM for 60 seconds, and then heated at 60 ° C. for 10 minutes. Further, the liquid C was applied onto this film by a spray coating method and heated at 450 ° C. for 10 minutes. Table 1 shows the relationship between the composition of the first layer and the characteristics of the finally formed film.

[0033]

[Table 1]

Example 2 The coating solutions for forming various conductive films in Example 1 were applied on a glass plate having a thickness of 1 cm by spin coating at 100 RPM for 60 seconds, and then heated at 300 ° C. for 10 minutes. On top of that, Ti (C5 H7 O2) 2 (OC3 H
7) 2 and ethyl silicate converted to TiO2: SiO
2 = 7: 3 was prepared, and a solution obtained by simultaneous hydrolysis with an aqueous HCl solution was applied by spin coating at 100 RPM for 60 seconds, and then heated at 60 ° C. for 10 minutes. Further, liquid C is applied onto this film by spray coating, and the temperature is 1 ° C at 450 ° C.
Heated for 0 minutes. Table 2 shows the relationship between the composition of the first layer and the properties of the finally formed film.

[0035]

[Table 2]

[Embodiment 3] SnCl4.nH2O was added to Sn.
A solution dissolved in ethanol so as to be 3% by weight in terms of O2 is referred to as liquid D. Ti (C5 H7 O2) 2 (OC3 H
7) Solution E is prepared by hydrolyzing 3) 2 in TiO2 to 3% by weight and hydrolyzing it with hydrochloric acid in ethanol. Al
A solution prepared by dissolving (OC3 H7) 2 (C6 H10 O3) in ethanol so as to be 3% by weight in terms of Al2 O3 is referred to as solution F. Zr (C5 H7 O2) 2 (OC4 H9) 2 to Z
A solution hydrolyzed with hydrochloric acid in ethanol so as to be 3% by weight in terms of rO2 was designated as solution G. Example 1 except that the first layer conductive film was formed by mixing one of liquids D, E, F, and G with liquid A and liquid B or liquid A, liquid B, and liquid C. I went the same way. Table 3 shows the composition of the first layer and the properties of the finally formed film.

[0037]

[Table 3]

Comparative Example 1 Liquids A and B in Example 1
Liquid and C liquid converted to oxides RuO2, In2 O3 and SiO
The solution mixed so that the ratio of 2 becomes 30:45:25 is further diluted with a solvent such as alcohol and coated on a glass plate having a thickness of 1 cm by spin coating at 100 RPM for 60 seconds.
Then, it heated at 300 degreeC for 10 minutes. Furthermore, C on this film
The solution was applied by spin coating for 60 seconds at a rotation speed of 100 RPM, and then heated at 450 ° C. for 10 minutes. The surface resistance of this coating film was 1 × 10 4 (Ω / □), the scratch resistance was Δ, the pencil hardness was 3H, and the luminous reflectance was 0.4%, but the gloss value was 78%. Fingerprints on the paint film were visible.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, an excellent low-reflection conductive material having a high transmittance, a high electrical conductivity and an antiglare effect can be efficiently produced by a simple method such as spray coating or spin coating by applying a liquid. It is possible to provide a membrane. Since the present invention is excellent in productivity and does not require a vacuum, the apparatus may be relatively inexpensive. In particular, it can be applied to a large-area substrate such as a panel face surface of a CRT and can be mass-produced, so that its industrial value is very high.

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[Procedure amendment]

[Submission date] September 11, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

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[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

A conventional method is disclosed in, for example, Japanese Patent Laid-Open No. 61-1189.
As described in No. 31, SiO having fine irregularities on the surface in order to have an antiglare effect on the surface of the cathode ray tube face panel.
Methods such as attaching _two layers or etching the surface with hydrofluoric acid to form irregularities have been used. However, these methods are called non-glare treatment that scatters external light, and there is a limit to the reduction of reflectance because it is not a method of essentially providing a low reflection layer, and in addition, it has an antiglare effect in a cathode ray tube. Requires a film thickness, which is also a cause of lowering the resolution.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

The present inventor has proposed, as a conductive film capable of eliminating the above-mentioned drawbacks of the prior art, a low-reflection conductive film composed of a multilayer film having a conductive film containing ruthenium oxide as a main component as a lower layer. The membrane has already been proposed. However, there is a problem that a fingerprint or the like is easily noticed in the low reflection film using the multilayer interference. Therefore, in the present invention, SiO is formed on the uppermost layer of the multilayer film including the conductive film containing ruthenium oxide as a main component.
By forming a film having irregularities containing ₂ as a main component, a high-performance low-reflection conductive film having both low reflectivity and antiglare effect due to the interference effect of light, and a method for producing the same are newly provided. The purpose is to

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

Further, according to the present invention, a glass substrate such as a face panel of a cathode ray tube is coated with a coating solution containing a Ru compound which can be a Ru oxide, an In compound which can be an In oxide, water and / or an organic solvent. By forming a multilayer film including a conductive film obtained by heating at 500 ° C. and further forming a film having irregularities containing SiO ₂ as a main component on the uppermost layer thereof, low reflection due to light interference and prevention of It is intended to provide a method for producing a low-reflection conductive film of a glass substrate such as a cathode ray tube face panel, which is characterized by imparting a glare effect at the same time.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Further, the present invention provides a glass substrate such as a face panel of a cathode ray tube with a coating liquid containing a Ru compound which can be a Ru oxide, an In compound which can be an In oxide, water and / or an organic solvent, a Si compound and a Ti compound. compound, Zr compound, Al compound, the solution was applied by adding at least one of Sn compound, the multilayer film is formed including the obtained conductive film is heated at 100 to 500 ° C., further SiO ₂ on the top layer The production of a low-reflection conductive film of a glass substrate such as a cathode ray tube face panel, which is characterized by simultaneously providing low reflectivity and anti-glare effect due to the interference of light by forming a film having irregularities containing as a main component. It provides a method.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The coating liquid used in the present invention contains S as a binder in order to improve the adhesion strength and hardness of the film.
i (OR) _y · R ′ _(4-y) (y = 3 or 4, R, R ′:
It is also possible to add a solution containing a Si compound or a partial hydrolyzate thereof that becomes SiO ₂ by heating (alkyl group) or the like. At that time, as a hydrolysis catalyst, HCl, HN
O ₃ , CH ₃ COOH or the like can be used. Further, various surfactants can be added to improve the wettability with the substrate.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Furthermore, in order to adjust the refractive index of the conductive film,
By heating, TiO ₂ , ZrO ₂ , Al ₂ O ₃ ,
Ti compound, Zr compound, Al compound which becomes SnO ₂ ,
One or a plurality of Sn compounds and the like can be mixed in the coating liquid. As each compound of Ti, Zr, Al, and Sn, any of alkoxides of these metals, metal salts, and hydrolysates thereof can be used.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0016

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[Correction content]

In the coating liquid for forming the conductive film, the Ru compound and the In compound can be mixed in any ratio, but the higher the RuO ₂ / In ₂ O ₃ ratio in terms of oxide, the higher the conductivity. . However, if the content of RuO ₂ is too large, the transmittance decreases, so RuO ₂ / In ₂ O ₃
Is preferably about 8/2 to 1/9 by weight.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The Ru compound, the In compound and the Si compound can be mixed in any ratio, but in consideration of the development of conductivity and the film strength, the mixing ratio (weight ratio) is (Ru
O ₂ + In ₂ O ₃ ) / SiO ₂ conversion from 1/6 to 20 /
Mixing up to 1 is preferred. More preferably 1 /
4 to 10/1 is recommended. The solid content of the liquid may be 0.05 to 10 wt%, and more preferably 0.3 to 5.0 wt%. This is because if the concentration is high, the storage stability of the liquid becomes poor, and if the concentration is too low, the film thickness becomes thin and sufficient conductivity cannot be obtained.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

In the present invention, a low reflection conductive film utilizing light interference is formed. For example, when the substrate is glass (refractive index n = 1.52) in a low-reflection film consisting of two layers, a film with a ratio of n ₁ (conductive film) / n ₂ (low refractive index film) is formed on the conductive film. The reflectance can be most reduced by forming a low refractive index film having a value of about 1.23.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

As a method for producing a low refractive index film which constitutes a low reflective conductive film or a film having a low refractive index and unevenness on the surface, a solution containing MgF ₂ sol or Si which becomes SiO ₂ by heating It is formed using a solution of at least one selected from the solutions containing Si compounds such as alkoxides. From the viewpoint of the refractive index, MgF ₂ is the lowest of the materials, and it is preferable to use a solution containing MgF ₂ sol to reduce the reflectance, but SiO ₂ is mainly used in terms of film hardness and scratch resistance. Membranes of component are preferred.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Various substances can be used as the solution containing the Si compound for forming the low refractive index film forming the low reflective conductive film and / or for forming the film having the low refractive index and the uneven surface. However, Si (OR) _m R ′ _n (m = 1 to 4,
Examples of the liquid include a liquid containing a Si alkoxide or a partial hydrolyzate represented by n = 0 to 3 and R, R ′ = C _{1 to} C ₄ alkyl group). For example, a monomer or polymer of silicon ethoxide, silicon methoxide, silicon isopropoxide or silicon butoxide can be preferably used.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

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The Si alkoxide can be used by dissolving it in alcohol, ester, ether or the like, or can be used by adding hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid or aqueous ammonia solution to the solution and hydrolyzing it. Further, the Si alkoxide is preferably 30 wt% or less with respect to the solvent. Further, to improve the strength of the film, an alkoxide of Zr, Ti, Al or the like or a partial hydrolyzate of these is added to this solution to give Z
One or two or more composites of rO ₂ , TiO ₂ , and Al ₂ O ₃ may be simultaneously deposited with MgF ₂ and SiO ₂ . Alternatively, a surfactant may be added to improve the wettability with the surface to which such liquid is applied. Examples of the surfactant to be added include linear sodium alkylbenzene sulfonate, alkyl ether sulfate, and the like.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

Example 1 RuCl ₃ .nH ₂ O was dissolved in ethanol to prepare a Ru concentration of 3% by weight in terms of RuO ₂ . This liquid is called liquid A. Dissolve indium chloride in acetylacetone so that acetylacetone becomes 1.5 times (molar ratio) of indium chloride, and
Heating was carried out at 10 ° C. for 1 hour. This solution was dissolved in ethanol to prepare an In concentration of 3% by weight in terms of In ₂ O ₃ . This solution is referred to as solution B. Ethyl silicate is dissolved in ethanol and hydrolyzed with an aqueous HCl solution.
_It was set to 3% by weight in terms of ₂ . This solution is referred to as solution C.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In terms of oxide, RuO ₂ , In ₂ O ₃ and Si
The solution obtained by mixing the liquids A, B, and C so that O ₂ has various weight ratios is further diluted with a solvent such as alcohol to prepare 1
6 cm spin glass coating at 100 RPM
It was applied for 0 seconds and then heated at 300 ° C. for 10 minutes. Further, the liquid C was applied onto this film by a spin coating method at a rotation speed of 100 RPM for 60 seconds, and then heated at 60 ° C. for 10 minutes. Further, the liquid C was applied onto this film by a spray coating method and heated at 450 ° C. for 10 minutes. Table 1 shows the relationship between the composition of the first layer and the characteristics of the finally formed film.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

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[0033]

[Table 1]

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

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Example 2 The coating solutions for forming various conductive films in Example 1 were applied on a glass plate having a thickness of 1 cm by spin coating at 100 RPM for 60 seconds, and then heated at 300 ° C. for 10 minutes. On top of that Ti (C ₅ H ₇ O ₂ ) ₂ (OC ₃ H
₇ ) ₂ and ethyl silicate in terms of oxide, TiO ₂ : SiO
₂ = 7: 3 was prepared, and a solution obtained by simultaneous hydrolysis with an aqueous HCl solution was applied by spin coating at 100 RPM for 60 seconds, and then heated at 60 ° C. for 10 minutes. Further, liquid C is applied onto this film by spray coating, and the temperature is 1 ° C at 450 ° C.
Heated for 0 minutes. Table 2 shows the relationship between the composition of the first layer and the properties of the finally formed film.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035]

[Table 2]

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

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[Example 3] SnCl ₄ · nH ₂ O was added to Sn
A solution dissolved in ethanol so as to be 3% by weight in terms of O ₂ is referred to as liquid D. Ti (C ₅ H ₇ O ₂ ) ₂ (OC ₃ H
₇ ) A solution obtained by hydrolyzing ₂ ) ₂ in hydrochloric acid with ethanol so as to be 3% by weight in terms of TiO _{2 is referred} to as solution E. Al
A solution prepared by dissolving (OC ₃ H ₇ ) ₂ (C ₆ H ₁₀ O ₃ ) in ethanol so as to be 3% by weight in terms of Al ₂ O ₃ is referred to as solution F. Zr (C ₅ H ₇ O ₂ ) ₂ (OC ₄ H ₉ ) ₂
A solution hydrolyzed with hydrochloric acid in ethanol so as to be 3% by weight in terms of rO _{2 is} designated as solution G. Example 1 except that the first layer conductive film was formed by mixing one of liquids D, E, F, and G with liquid A and liquid B or liquid A, liquid B, and liquid C. I went the same way. Table 3 shows the composition of the first layer and the properties of the finally formed film.

[Procedure amendment 20]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

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Comparative Example 1 Liquids A and B in Example 1
Liquid and C liquid are converted to oxide by RuO ₂ , In ₂ O ₃ and SiO
_The solution mixed so that the ratio of ₂ becomes 30:45:25 is further diluted with a solvent such as alcohol and applied onto a glass plate having a thickness of 1 cm by spin coating at 100 RPM for 60 seconds.
Then, it heated at 300 degreeC for 10 minutes. Furthermore, C on this film
The solution was applied by spin coating for 60 seconds at a rotation speed of 100 RPM, and then heated at 450 ° C. for 10 minutes. The surface resistance of this coating film was 1 × 10 ⁴ (Ω / □), the abrasion resistance was Δ, the pencil hardness was 3H, and the luminous reflectance was 0.4%, but the gloss value was 78%. , When the fingerprint was on the coating, it was visible.

Claims (6)

[Claims] 1. A low reflective conductive film comprising at least two layers including a conductive film containing Ru and In oxides as main components is formed, and then a material capable of forming a low refractive index film is included on the surface of the uppermost layer. Liquid is spray coated and heated to have a low refractive index,
A method for producing a low-reflection conductive film having an anti-glare effect, comprising forming a low-reflection conductive film having an anti-glare effect by forming a film having irregularities on the surface. 2. A conductive film containing an oxide of Ru and In as a main component is formed, and a film having a low refractive index and unevenness on the surface is formed on the conductive film, and the film thickness after heating is A low-reflection conductive film having an uneven surface and an antiglare effect is formed by heating after forming by a spray coating method to a thickness that produces an antireflection effect due to interference. A method for producing a low-reflection conductive film having an antiglare effect. 3. A conductive film containing an oxide of Ru and In as a main component, which is a coating liquid containing a Ru compound that can be a Ru oxide and an In compound that can be an In oxide, and is heated by heating to form SiO 2 respectively. , ZrO2, TiO2, Al2
It is formed by applying a coating liquid containing at least one of Si compound, Zr compound, Ti compound, Al compound, and Sn compound to be O3 and SnO2, and then heating and / or irradiating with ultraviolet rays. Claim 1 or 2
And a method for producing a low-reflection conductive film having an antiglare effect. 4. A low reflection conductive film having an antiglare effect, which is obtained by the manufacturing method according to claim 1. 5. A glass article in which the low reflection conductive film having the antiglare effect according to claim 4 is formed on a glass substrate. 6. A cathode ray tube having the low-reflection conductive film having the antiglare effect according to claim 4 formed on the surface of a face panel of the cathode ray tube.