JPH0762323A - Coating liquid for forming colored film, colored film and preparation thereof - Google Patents

Abstract

PURPOSE:To improve long-term stability, mass productivity and reproducibility by incorporating water, a lower alcohol, an ester ether and a ketone alcohol in a solution comprising titanium oxide nitride particles and a specific compound. CONSTITUTION:This coating liquid is obtained by adding water, a lower alcohol, 0.1-60wt.% of an ester ether, 0.1-30wt.% of a ketone alcohol and, if necessary, at least one compound selected from among Sn, In, Sb, Zn, Al and Ga to a solution comprising titanium oxide nitride particles having a nitrogen content of 0.1-0.3wt.% and a compound of formula Si(OR)mRn (wherein m+n=4; m=1-4; n=0-3; and R is a 1-4C alkyl) or a hydrolyzate thereof. The coating liquid is spread on a substrate and dried by heating and/or irradiating UV rays to form a colored film with a reduced transmittance in a wavelength region of 380-700nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating liquid applied to a panel for a cathode ray tube and the like, and an antistatic film, a low reflection antistatic film, a colored film, a colored antistatic film obtained by applying the coating liquid.
Alternatively, the present invention relates to a colored low reflection antistatic film and a method for producing them.

[0002]

2. Description of the Related Art Antistatic films, colored films, colored antistatic films,
It goes without saying that the coating method of the low-reflection antistatic film and the colored low-reflection antistatic film is more conventional in optical equipment than before.
Many studies have been made on consumer electronic devices, particularly cathode ray tubes (CRTs) for TVs and computer terminals.

Regarding antistatic, JP-A-63-762.
Japanese Patent Publication No. 47 proposes a method of heating the surface of a cathode ray tube panel to about 350 ° C. and providing a conductive oxide layer such as tin oxide and indium oxide by the CVD method. However, the method of applying the antistatic film by the CVD method has a problem in that in addition to the cost of the apparatus, since the surface of the cathode ray tube is heated to a high temperature, the fluorescent substance in the cathode ray tube comes off and the dimensional accuracy decreases. . Also in this case usually 4
It requires a high temperature of about 00 ° C., and has a defect that a sufficiently low resistance film cannot be obtained when baked at a low temperature.

Regarding the coloring of the film, Japanese Patent Laid-Open No. 1-2756
Method of using water-soluble phthalocyanine compound in Japanese Patent No. 64
Is proposed. In addition, the colored film with antistatic ability
Japanese Patent Application Laid-Open No. 1-251545 discloses methyl violet.
There is a description of an antistatic film using a battery. Regarding low reflectivity
For example, as described in JP-A-61-118931.
The surface of the cathode ray tube is made fine to have an anti-glare effect.
With irregularities ₂ By applying a layer or by hydrofluoric acid
Methods such as etching the surface to make unevenness are adopted
Came.

However, these methods are called non-glare processing for scattering external light and are not methods for providing a low reflection layer by nature, so that there is a limit to the reduction of reflectance, and in a cathode ray tube or the like, resolution is limited. Was also the cause of lowering. The low reflection antistatic film is described in JP-A-3-9
Japanese Patent No. 3136 describes a method of providing an optical multilayer film by an ion plating method. However, the method using ion plating is not industrially inexpensive.

As a film forming method other than the above, a method of applying a solution to a substrate and then heating and / or irradiating with ultraviolet rays is being studied. There are various possible methods for applying the solution to the substrate, such as a spin coating method, a dip coating method, a spray method, a roll coater method, and a meniscus coater method.
In particular, the spin coating method is excellent in mass productivity and reproducibility and is preferably used. A film of about 10 nm to 1 μm can be formed by such a method.

However, when a solution in which particles are dispersed in a liquid is applied by spin coating, a trace of liquid flow generated during coating, a trace of particle flow, agglomeration of particles during film drying, uneven drying, and film thickness difference. It is difficult to form a film having a good appearance because of problems such as color unevenness due to the above. In addition, the wettability of the coating liquid with respect to the substrate is good or bad, and the susceptibility to the influence of the fluctuation of the outside air causes the productivity to be deteriorated.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, is excellent in long-term stability, and
Providing a coating liquid that is industrially inexpensive and can be applied with good appearance by a coating method that is excellent in mass productivity and reproducibility, and a colored film that can be heat-treated at low temperature using the coating liquid, or a colored antistatic film, colored low reflection The purpose is to provide a new antistatic film.

[0009]

The present invention has been made to solve the above-mentioned problems, and titanium oxynitride particles,
Si (OR) _m R _n (m + n = 4, m = 1 to 4, n = 0
To 3, R = C _{1 to} C ₄ alkyl group) or a hydrolyzate thereof, in a solution containing water, C ₁
~ C ₄ lower alcohol, ester ethers 0.1
~ 60 wt% and ketone alcohol 0.1-3
The coating liquid for forming a colored film, which contains 0 wt%, and Sn, In, Sb, Zn, Al in the coating liquid.
And a coating liquid for forming a colored film, which comprises at least one compound selected from the group consisting of Ga and Ga.

The present invention is directed to a liquid flow trace, a particle flow trace,
It is intended to provide a coating liquid which can be coated with good appearance with less aggregation of particles during drying of the film, unevenness of drying, difference in film thickness, and the like, and which has good wettability to the substrate and is not easily affected by the outside air.

The present invention also provides a colored film characterized in that the transmittance is reduced in the wavelength region of 380 nm to 700 nm by applying the coating liquid.

In the coating liquid, Sn, In, Sb,
By applying a solution containing at least one compound selected from the group consisting of Zn, Al and Ga, the transmittance decreases in the wavelength region of 380 nm to 700 nm, and a colored antistatic film having antistatic ability is obtained. Is obtained.

Further, according to the present invention, in a multilayer film formed on a substrate, at least one layer of the multilayer film is the colored film, and further, the multilayer film. The present invention provides a multilayer film, wherein the colored film and a film having a refractive index lower than that of the colored film are sequentially formed on the substrate side.

Further, the present invention provides a method for producing a colored film, which comprises applying the coating solution and then heating and / or irradiating ultraviolet rays in the method for producing a colored film formed on the surface of a substrate. Is.

The colored film, the colored antistatic film and the colored low reflection antistatic film of the present invention are preferably used for glass articles provided for display applications. In recent years, a cathode ray tube as a glass article has been required to have high contrast as well as high resolution when it is used for display of a computer terminal. However, if the transmittance of the glass itself is reduced in order to improve the contrast, the faceplate becomes thicker as the display becomes larger, so that particularly in a large display, a significant decrease in transmittance becomes a problem. Become.

In the present invention, the contrast is improved by forming a film on the surface of the glass without lowering the transmittance of the glass itself and causing the film to absorb light. Therefore,
It can be applied to a display glass panel having various wall thicknesses very easily.

Although the emission spectrum of the cathode ray tube is composed of a plurality of spectra, in order to improve the contrast without disturbing the balance of the emission spectrum, it is possible to obtain more uniform light over the visible light region than a coloring film having a specific light absorption. A colored film with absorption is preferred. As a result of earnest research from such a viewpoint, the above problems can be solved by forming a coating liquid that contains titanium oxynitride and can inexpensively produce a film with a good appearance that enables uniform light absorption in the visible light region. I was able to solve it.

The ester ethers and ketone alcohols in the present invention are not particularly limited. Examples of such ester ethers include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoacetate acetate. Examples thereof include ethyl ether, propylene glycol monobutyl ether acetate, glycol diacetate, trimethoxy glycol acetate and the like. Of these, propylene glycol monomethyl ether acetate is particularly preferable.

Examples of the ketone alcohol include acetonylylmethanol, diacetone alcohol, dihydroxyl acetone and pyruvyl alcohol. Of these, diacetone alcohol is particularly preferable.

The composition of titanium oxynitride in the present invention is not particularly limited, but TiO _x (1.0 ≦ x ≦ 2.0) containing 0.1 to 0.3 wt% of nitrogen is preferable. In addition, for stabilization of nitrogen element in oxide, 3A to 7A, 8 and 1B shown in the short periodic table.
It is also preferable to add the group element to titanium oxynitride in an amount of 5.0 wt% or less.

In the present invention, the titanium oxynitride is added to Si.
(OR) _m R _n (m + n = 4, m = 1 to 4, n = 0 to
3, the stability of particles in the solution is improved by adding a hydrolyzate of R = C _{1 to} C ₄ alkyl group), and aliphatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones and ethers are added. , Esters, alcohol esters,
Even when diluted with an organic solvent composed of one or a mixture of two or more of ketone esters, ether alcohols, ketone ethers, and ester ethers, coagulation precipitation does not occur.

Further, in the present invention, S is added to the coating liquid for colored film.
By containing at least one compound selected from the group consisting of n, In, Sb, Zn, Al and Ga, antistatic performance for suppressing static electricity generated when the display is turned on and off after coating and deposition is imparted, and dust etc. It was also possible to suppress the adherence of. Furthermore, by forming a film having a lower refractive index than the above-mentioned colored antistatic film on the colored antistatic film, it is possible to impart low reflection performance for controlling the reflection of a fluorescent lamp without impairing the resolution.

Generally, the optical performance of a thin film is determined by the refractive index and film thickness of the film. Where the constant refractive index n
Depositing a thin film having a refractive index n on a substrate having _S ,
The energy reflectance R when the light of wavelength λ is incident from the solute with the refractive index n ₀ is the phase difference Δ when the light passes through the film.
Then, Δ = 4πnd / λ (d: film thickness), and Δ =
(2m + 1) π, that is, when the phase difference Δ is an odd multiple of a half wavelength, it takes a minimum value. At this time,

R = ((n ₂ −n ₀ n _S ) / (n ₂ + n _0).
n _S )) ² (1). In order to satisfy the non-reflection condition, R = 0 in the equation (1),

N = (n ₀ n _S ) ^1/2 ... (2) is required. When formula (2) is expanded to a two-layer structure,

N _S n ₁ ² = n ₂ ² n ₀ ... (3) However, n ₁ is the refractive index of the medium side layer, and n ₂ is the refractive index of the substrate side layer.

Here, n ₀ = 1 (air), n _S = 1.52
When (glass) is applied to the equation (3), n ₂ / n ₁ =
It becomes 1.23, and in this case, the maximum low reflectivity of the two-layer constitution film is obtained. Of course, even if n ₂ / n ₁ = 1.23 is not satisfied, low reflectivity can be obtained when the refractive index of the two-layer film can take a value close to this. Therefore, it is desirable that the high refractive index layer provided on the substrate side and the low refractive index layer provided on the medium side have a refractive index ratio of both as close to 1.23 as possible. In the present invention, in order to obtain a desired low reflection film, the film thickness is an important factor together with the refractive index difference between the multilayer films.

The multilayer low-reflection film having the antireflection property has a structure in which the wavelength for which antireflection is desired is λ, and the high refractive index layer and the low refractive index layer are optical thicknesses λ / 2 and λ / 4 from the substrate side. Low reflection film, medium refractive index layer from the substrate side,
The high refractive index layer and the low refractive index layer have optical thicknesses of λ / 4 and λ / 2.
And a three-layer low-reflection film sequentially formed with λ / 4, a low-refractive index layer, a medium-refractive index layer, a high-refractive index layer, and a low-refractive index layer from the substrate side, with optical thicknesses of λ / 4, λ / 4, λ / A typical example is a four-layer low-reflection film formed in the order of 2 and λ / 4.

As the titanium oxynitride particles used in the present invention, titanium oxide subjected to reduction treatment is used. N ₂ gas, N for reduction treatment
H ₃ gas or the like can be used. Since titanium oxynitride itself has electric conductivity, it functions as a conductive auxiliary component when forming an antistatic film.

The content of titanium oxynitride in the coating is preferably 1 to 90% by weight in the case of a colored film, and if it is less than this, the coloring performance is not sufficient, and if it is more than this, the strength of the film decreases, which is not preferable.

In the case of the colored antistatic film or the colored low reflection antistatic film, the content ratio of titanium oxynitride in the coating film is 1 to
It is preferably 80 wt%. When the amount of titanium oxynitride is too small, the coloring performance is insufficient, and when it is too large, the antistatic ability and the transmittance of the film are deteriorated, which is not preferable.

In addition, Si (OR) _m R _n (m +
Regarding the content of the hydrolyzate of n = 4, m = 1 to 4, n = 0 to 3, and R = C _{1 to} C ₄ alkyl group, it is 0 based on the total solid content in terms of oxide. 0.5-65 wt% is preferable.
If the amount is less than this, agglomeration may occur when an organic solvent is mixed with the solution containing titanium oxynitride. On the other hand, if it is more than the above range, coloring performance and antistatic ability are deteriorated, which is not preferable.

The oxide used in the present invention may be Sb-doped SnO ₂ , ITO, Al-doped ZnO, Ga-doped ZnO, or the like.
These oxides can be used by being dispersed as particles in a coating liquid, or can be used as a solution to be oxidized on a substrate.

When particles are added to the liquid, the average particle diameter of the particles in the dispersion medium is preferably 30 nm or less. When a solution is used, an organic compound such as a chelate complex and an inorganic compound such as a nitrate are used and the above titanium oxynitride and Si (OR) _m R _n (m + n = 4, m = 1 to 4,
Used as a mixture with a solution consisting of a hydrolyzate of n = 0 to 3 and R = C _{1 to} C ₄ alkyl group).

Further, as the substance constituting the low refractive index film in the colored low reflection antistatic film, a silicon compound is preferably used from the viewpoint of the refractive index and the film strength. As a silicon compound, Si (OR) _m R _n (m + n = 4, m = 1 to 4, n = 0
To 3, R = C _{1 to} C ₄ alkyl group) or a partial hydrolyzate is preferably used, but a solution prepared by saturating an aqueous solution containing hydrosilicofluoric acid and boric acid with silicon dioxide powder. It is also possible to use a silicon compound formed by further precipitation.

The coating method of the compound represented by Si (OR) _m R _n or the partial hydrolyzate on the colored antistatic film is a spin coating method, a dip coating method, a spraying method, a roll coater method or a meniscus coater method. However, the spin coating method is preferably used because it is excellent in mass productivity and reproducibility. 10n by this method
A film having a thickness of about m to 1 μm can be formed. Since the colored film of the present invention contains titanium oxynitride, it has a high refractive index and easily exhibits the above-mentioned low reflection performance when it is composed of two layers including the above low refractive index film.

In the present invention, the substrate on which the colored film, the colored antistatic film and the colored low-reflection antistatic film are formed is not particularly limited, and soda lime silicate glass, aluminosilicate glass, borosilicate can be used according to the purpose. Glass such as salt glass, lithium aluminosilicate glass, and quartz glass, single crystals such as corundum, translucent ceramics such as magnesia and sialon, and plastics such as polycarbonate can also be used.

[0038]

In the colored film of the present invention, since titanium oxide containing nitrogen as a coloring component is used, the coloring film is excellent in thermal stability and weather resistance. Also, when applied to a cathode ray tube because it does not cause absorption in a specific visible light region,
It is possible to improve the contrast without disturbing the balance of the spectrum emitted by the phosphor in the cathode ray tube. Low reflectance is also improved due to uniform absorption in the entire visible light region.

Furthermore, since titanium oxide itself containing nitrogen has conductivity, titanium oxynitride also functions as a component for exhibiting antistatic ability. Further, Si (OR) _m R _n (m + n = 4, m = 1 to
4, n = 0-3, R = C ₁ -C ₄ alkyl group) is added to improve the stability of the particles in the solution, and aliphatic hydrocarbons, halogenated hydrocarbons, alcohols Even when diluted with an organic solvent composed of one or a mixture of two or more of compounds, ketones, ethers, esters, alcohol esters, ketone esters, ether alcohols, ketone ethers and ester ethers. It can be applied to a wide range of coating conditions without causing cohesive precipitation.

The coating solution contains 0.1 to 60 wt% of ester ethers and 0.1 to 3 of ketone alcohols.
By containing 0 wt%, the surface tension, viscosity, evaporation rate, etc. of the coating liquid can be controlled, and it can be easily applied to a large-sized large-sized display. Traces of liquid flow, traces of particle flow, and film drying It is possible to obtain a coating liquid which has less particle aggregation, drying unevenness, film thickness difference, etc. and can be coated with good appearance.

[0041]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The obtained liquid was evaluated as follows.

1) [Evaluation of transmittance] Spec made by Hitachi Ltd.
38 by trophotometer U-3500
The transmittance at 0 nm, 550 nm and 780 nm was measured.

2) [Haze Evaluation] The haze of the film itself was measured by a direct-reading haze computer manufactured by Suga Test Instruments.

3) [Evaluation of electroconductivity] Regarding the colored antistatic film and the colored low-reflection antistatic film, the surface resistance of the film surface was measured in an atmosphere with a relative humidity of 30% or less by a Hiresta resistance measuring instrument manufactured by Mitsubishi Yuka.

4) [Scratch resistance] Under a load of 1 kg, the film was reciprocated 50 times with an eraser, and how the surface was scratched was visually judged. The evaluation criteria are as follows. ○: No scratches, △: Some scratches, ×: Many scratches or peeling

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

6) [Visual reflectance] The colored low-reflection antistatic film was measured for its visual reflectance from 380 nm to 700 nm with a GAMMA spectroscopic reflection spectrophotometer.

[Example 1] Titanium oxynitride (nitrogen content 1
0 wt% and contains 1 wt% vanadium) 1
5 g was added to 85 g of an aqueous solution whose pH was adjusted to 3.0 in advance, and the mixture was pulverized with a sand mill for 4 hours, heated at 90 ° C. for 1 hour, and then adjusted to have a concentration of 5 wt% to obtain a sol. (A
liquid)

To an ethanol solution of Si (OEt) 4 (solid content: 5 wt% in terms of oxide), an acidic nitric acid aqueous solution adjusted to pH 2.8 with respect to Si (OEt) 4 was added in an amount of 8 mol, and the mixture was heated at 80 ° C. for 2 hours. Refluxed. (Liquid B)

Liquid A and liquid B were mixed so that the ratio of liquid A: liquid B was 6: 4, and solid content: water: methanol: ethanol isopropyl alcohol :: propylene glycol monomethyl ether acetate: diacetone alcohol =
1.2: 5.2: 1.3: 49.6: 2.7: 25: 1
It was adjusted to be 5 to obtain a coating liquid for colored film. The obtained coating liquid was applied onto the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 200 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

Example 2 15 g of SnO 2 powder (primary particle size 10 nm) doped with 8 mol% of Sb was added to 85 g of water.
Add to the inside and pulverize with a sand mill for 16 hours at 90 ° C for 1
After heating for a time, the concentration was adjusted to 5 wt% to obtain a sol.
(C liquid)

Liquid A, liquid B and liquid C are liquid A: liquid B: liquid C = 4
The mixture was mixed at a weight ratio of 2:18:40, and solid content:
Water: methanol: ethanol: isopropyl alcohol: propylene glycol monomethyl ether acetate: diacetone alcohol = 1.2: 5.2: 1.5:
It was adjusted to be 57.1: 3: 20: 12 to obtain a colored antistatic coating solution. The obtained coating liquid was applied onto the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 200 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Third Embodiment] Sb in the second embodiment is 8 m.
The ol% -doped SnO2 powder is replaced with ITO powder (Sn /
In = 10/90 mol ratio, primary particle size 30 nm), and 85 g of water was changed to an aqueous solution adjusted to pH 8.0 with KOH in advance, and solid content: water: ethanol: propylene glycol monomethyl ether acetate: diacetone alcohol = It carried out like Example 2 except having adjusted to be 1.2: 5.2: 53.6: 32: 8. The obtained coating liquid was applied on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 380 ° C. for 30 minutes to obtain a film of about 90 nm.

[Embodiment 4] Sb in Embodiment 2 is 8 m.
Al is 10 mol% in SnO2 powder doped with ol%
Change to doped ZnO powder (primary particle size 20 nm), solid content: water: ethanol: propylene glycol monomethyl ether acetate: diacetone alcohol =
It carried out like Example 2 except having adjusted so that it might be set to 1.2: 5.2: 45.6: 35: 13. The coating liquid obtained in Example 4 was applied to the surface of the cathode ray tube panel at 100 r.
Apply at a rotation speed of pm for 60 seconds, then at 380 ° C for 3 seconds.
After heating for 0 minutes, a film having a thickness of about 90 nm was obtained.

[Embodiment 5] Sb in Embodiment 2 is 8 m.
Example 2 was repeated except that the ol% -doped SnO ₂ powder was changed to a GaO-doped 8 mol% ZnO powder (primary particle size 40 nm). The obtained coating liquid was applied on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then ultraviolet rays having a wavelength of 365 nm as a main wavelength were irradiated for about 30 minutes to obtain a film of about 100 nm.

[Comparative Example 1] Liquids A, B and C in Example 2 were mixed in a ratio of liquid A: liquid B: liquid C = 3: 2: 5 by weight, and solid content: water: ethanol. : Propylene glycol monomethyl ether: 2,3 butylene glycol = 1.1: 5.3: 38.6: 20: 35 to obtain a coating liquid for a colored antistatic film. The obtained coating liquid was applied onto the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 200 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Comparative Example 2] Liquid A, liquid B and liquid C in Example 2 were mixed in a ratio of liquid A: liquid B: liquid C = 42:18:40, and solid content: water: ethanol. : Propylene glycol monomethyl ether: diacetone alcohol = 1.2: 5.2: 63.6: 20: 10 to prepare a coating liquid for a colored antistatic film. The obtained coating liquid was applied onto the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 200 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Example 6] 200 ° C 3 in Example 2
The heat treatment for 0 minutes was changed to 60 ° C. for 10 minutes to obtain a film having a thickness of about 100 nm. On this film, the solution B was converted to oxide in an amount of 0.
A solution obtained by diluting 70 wt% with a mixed organic solvent consisting of ethanol and butanol (ethanol: butanol = 2: 3 wt ratio) was 100 rpm on the surface of the cathode ray tube panel.
Was applied for 60 seconds at a rotation speed of, and then heat-treated at 200 ° C. for 30 minutes to obtain a colored low reflection antistatic film.

Example 7 Titanium oxynitride (nitrogen content 1
0 wt% and contains 1 wt% vanadium) 1
0.5 g and 15 g of SnO2 powder (primary particle size 10 nm) doped with 8 mol% of Sb were added to 85 g of an aqueous solution whose pH was adjusted to 3.0 in advance, pulverized with a sand mill for 4 hours, and heated at 90 ° C. for 1 hour. Then, the concentration was adjusted to 5 wt% to obtain a sol. (D liquid)

Liquid D and liquid C were mixed in a ratio of liquid D: liquid C = 6: 4 weight ratio, and solid content: water: propylene glycol monomethyl ether acetate: diacetone alcohol = 1.2: 5.2: It was adjusted to be 43.6: 35: 15 to obtain a coating liquid for a colored antistatic film. The obtained coating solution was applied on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 60 ° C. for 10 minutes to about 1
A film of 00 nm was obtained. On this film, a solution obtained by diluting solution B to 0.70 wt% in terms of oxide with a mixed organic solvent consisting of ethanol and butanol (ethanol: butanol = 2: 3 wt ratio) was applied on the surface of the cathode ray tube panel at 100 rp.
It is applied at a rotation speed of m for 60 seconds and then at 200 ° C. for 30 seconds.
It was heat-treated for minutes to obtain a colored low-reflection antistatic film.

[Comparative Example 3] Liquids A, B and C in Example 2 were mixed in a ratio of liquid A: liquid B: liquid C = 42:18:40 by weight to obtain a solid content: water: ethanol. : Propylene glycol monomethyl ether acetate: diacetone alcohol = 1.2: 5.2: 20.6: 65: 8 to prepare a coating liquid for a colored antistatic film. The obtained coating liquid is applied to the surface of the cathode ray tube panel at 100 rpm.
Was applied for 60 seconds at a rotation speed of, and then heated at 60 ° C. for 10 minutes to obtain a film having a thickness of about 100 nm. A solution obtained by diluting the solution B to 0.70 wt% in terms of oxide with a mixed organic solvent consisting of ethanol and butanol (ethanol: butanol = 2: 3 wt ratio) was applied to the surface of the film at 60 rpm at a rotation speed of 100 rpm on the surface of the cathode ray tube panel. Apply for 20 seconds, then 20
It was heat-treated at 0 ° C. for 30 minutes to obtain a colored low reflection antistatic film.

The evaluation results of the colored films prepared in Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Tables 1 and 2.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

The coating solution of the present invention is excellent in long-term stability and traces of the solution flow when it is applied to a cathode ray tube by spin coating.
Good coating with less traces of particle flow, particle agglomeration during film drying, drying unevenness, film thickness difference, etc., and the colored film has excellent thermal stability and weather resistance, as well as absorption at specific visible light wavelengths. When applied to a cathode ray tube in order to prevent
It is possible to improve the contrast without disturbing the balance of the spectrum emitted by the phosphor in the cathode ray tube. Further, since the titanium oxide containing nitrogen used in the present invention has conductivity, the colored film of the present invention can also exhibit antistatic ability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location H01J 29/89 // G02B 1/11 (72) Inventor Keisuke Abe Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa 1150 Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Keiko Ohashi 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory

Claims (8)

[Claims] 1. Titanium oxynitride particles and Si (OR) _m R _n
(M + n = 4, m = 1 to 4, n = 0 to 3, R = C _{1 to} C
₄ alkyl group) or a hydrolyzate thereof in a solution of water, a C ₁ -C ₄ lower alcohol, an ester ether of 0.1 to 60 wt%, and a ketone alcohol of 0. A coating liquid for forming a colored film, which contains 1 to 30 wt%. 2. Sn, I in the solution according to claim 1.
A coating liquid for forming a colored film, comprising at least one compound selected from the group consisting of n, Sb, Zn, Al and Ga. 3. A colored film, which is formed by applying the solution according to claim 1 or 2 and has a reduced transmittance in a wavelength region of 380 nm to 700 nm. 4. A multilayer film formed on a substrate, wherein at least one layer of the multilayer film is the colored film according to claim 3. 5. The multi-layered film, wherein the multi-layered film is formed by sequentially forming a colored film according to claim 3 and a film having a lower refractive index than that of the colored film from the substrate side. 6. A glass article on which the colored film according to claim 3 or the multilayer film according to claim 4 or 5 is formed. 7. A cathode ray tube, wherein the colored film according to claim 3 or the multilayer film according to claim 4 or 5 is formed. 8. A method for producing a colored film, which comprises applying the coating liquid according to claim 1 or 2 to the surface of a substrate and then irradiating with heating and / or ultraviolet rays.