JPH0789720A - Coating liquid for colored film forming, colored film, colored antistatic film and colored low reflective antistatic film - Google Patents

Abstract

PURPOSE:To improve a low reflectivity and an antistatic characteristics and to produce inexpensively and in good productivity the coating liq. for color film forming by incorporating titanium oxide nitride and Sn org. acid salt and/or Co org. acid salt. CONSTITUTION:The compound product (A) is obtained by compounding the titanium oxide nitride such as TiOx (1.0<=x<2.0) containing 0.1-30wt.% N, the Sn org. acid salt such as stannous naphthenate and/or Co org. acid salt, the hydrolyzed product of the compd. of the formula (m+n=4, m is 1-4, n is 0-3, R and R' are 1-4C alkyl) and beta-diketone. Then, the coating liq. for colored film forming (B) is produced by incorporating >=1 kind selected from the group consisting of propylene glycol ether (deriv.) and propylene glycol then acetate (deriv.), >=1 kind selected among methanol and ethanol, etc., and diacetone alcohol to the component (A). Moreover, the coating liq. for colored film forming is prepared by adding the conductive oxide such as Sn, In and Sb to the component (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution for forming a colored film, a colored film, a colored antistatic film and a colored low reflection antistatic film applied to a panel for a cathode ray tube.

[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.
Much consideration has been given to consumer equipment, especially cathode ray tubes (CRTs) for TVs and computer terminals.

With respect to antistatic, for example, Japanese Patent Laid-Open No. 63-
No. 76247 proposes a method in which the surface of a cathode ray tube panel is heated to about 350 ° C. and a conductive oxide layer such as tin oxide and indium oxide is provided by a CVD method.

Regarding the coloring of the film, Japanese Patent Laid-Open No. 1-2756
No. 64 proposes a method using a water-soluble phthalocyanine compound. Regarding the colored film having antistatic performance, JP-A-1-251545 describes an antistatic film using methyl violet.

Regarding low reflectivity, for example, Japanese Patent Laid-Open No. 61-1
In order to provide an antiglare effect on the surface of the cathode ray tube as described in No. 18931, methods such as adhering a SiO ₂ layer having fine irregularities on the surface or providing irregularities by etching the surface with hydrofluoric acid have been adopted. However, these methods are called non-glare processing that scatters external light and is not a method of providing a low reflection layer by nature, so there is a limit to the reduction of reflectance, and resolution is reduced in cathode ray tubes and the like. It was also the cause.

A low-reflection antistatic film is disclosed in JP-A-3-
No. 93136 describes a method of providing an optical multilayer film by an ion plating method.

[0007]

Among the above methods, C
The method of applying the antistatic film by the VD method has a problem that the cost of the apparatus is high and that the phosphor in the cathode ray tube is dropped or the dimensional accuracy is lowered because the surface of the cathode ray tube is heated to a high temperature. . Also in this case usually 40
It requires a high temperature of about 0 ° C., and has a drawback that a film having a sufficiently low resistance cannot be obtained when baked at a low temperature.

In the method using a water-soluble phthalocyanine compound for the colored film, it is difficult to obtain uniform absorption over the entire visible light wavelength region because the organic dye is used, so that the heat resistance and weather resistance are poor and the absorption is at a specific wavelength. There is a drawback that. The antistatic film containing methyl violet described in JP-A-1-251545 has poor heat resistance and weather resistance for the same reason, and it is difficult to obtain uniform absorption over the entire visible light wavelength region.

Further, the method using ion plating is not industrially inexpensive, and since it is not possible to obtain uniform absorption over the visible light wavelength region, improvement in contrast cannot be expected when a film is formed on a cathode ray tube. Various methods can be used for applying the solution to the substrate, such as a spin coating method, a dip coating method, a roll coater method, and a meniscus coater method. In particular, the spin coating method is preferable because it is excellent in mass productivity and reproducibility. By this method, 10 nm to 1 μm
A film of a certain degree can be formed. However, when spin coating is performed with a solution in which particles are dispersed in a liquid, the flow traces of the liquid generated at the time of coating, the traces of the flow of particles, the aggregation of particles during film drying, the uneven drying, the uneven color due to the film thickness difference, etc. It is difficult to form a film with good appearance due to the problem of, and the wettability of the coating liquid to the substrate is good or bad, and the susceptibility to the influence of fluctuations in the outside air causes the productivity to deteriorate. The choice of solvent and composition ratio were important.

The present invention overcomes the aforementioned drawbacks of the prior art,
A coating solution for forming a colored film that can be formed by low-temperature heat treatment,
It is an object of the present invention to newly provide a colored film, a colored antistatic film and a colored low reflection antistatic film.

[0011]

According to the present invention, a coating solution for forming a colored film containing titanium oxynitride and a Sn organic acid salt and / or a Co organic acid salt, and titanium oxynitride and Si (O 2
R) _m R ′ _n (m + n = 4, m = 1 to 4, n = 0 to 3,
R, R ′ = C ₁ -C ₄ alkyl group) or a hydrolyzate thereof, Sn organic acid salt and β-diketone, and further propylene glycol ether, its derivative, propylene glycol ether acetate and its derivative At least one selected from the group consisting of, at least one selected from the group consisting of methanol, ethanol, and propanol, and the coating solution for forming a colored film, which further comprises diacetone alcohol, There is provided the above coating solution for forming a colored film, which contains a conductive oxide composed of at least one of Sn, In, Sb, Zn, Al and Ga.

Further, the present invention is characterized by being obtained by applying the above-mentioned coating solution and then heating and / or irradiating it with ultraviolet rays, which has a reduced transmittance in the wavelength range of 380 nm to 700 nm. I will provide a.
Furthermore, the present invention is characterized in that the substrate surface is coated with a solution containing titanium oxynitride and further containing at least one of Sn organic acid salt and Co organic acid salt, and then heated and / or irradiated with ultraviolet rays. On the colored film and substrate surface
Includes titanium oxynitride, Sn organic acid salt, and S
At least one of n, In, Sb, Zn, Al, and Ga
A colored antistatic film comprising applying a solution containing a seed oxide and then heating and / or irradiating ultraviolet rays, and forming a film having a low refractive index on the colored antistatic film. Provided is a colored low-reflection antistatic film, which is characterized by comprising a multilayered film on a substrate, at least one layer of which is the above-mentioned colored antistatic film.

The present invention is best suited for coating the surface of glass articles for display applications. In recent years, when a cathode ray tube as such a glass article is used for a terminal display of a computer or the like, a demand for high resolution and a demand for high contrast are increasing. However, if the transmittance of the glass itself is reduced in order to improve the contrast, the faceplate will become thicker as the display becomes larger, so that the transmittance will decrease significantly, especially for large displays. Become. In the present invention, contrast can be improved by forming a film on the surface of the glass without lowering the transmittance of the glass itself and causing light absorption by this film.

Therefore, it can be very easily applied to glass panels for displays having various wall thicknesses.
The emission spectrum of the cathode ray tube is composed of multiple spectra, but in order to improve the contrast without disturbing the balance of the emission spectrum, it has more uniform light absorption over the visible light region than the colored film with specific light absorption. Colored films are preferred. As a result of earnest research from such a viewpoint, it was possible to achieve uniform light absorption in the visible light region and solve the above problems by forming a colored film containing titanium oxynitride.

On the other hand, titanium oxynitride is relatively excellent in heat resistance, but when it is burned at a high temperature for a long time in an oxidizing atmosphere such as air, oxidative discoloration impairs uniform absorption in the visible light region, and the cathode ray tube is damaged. Even when the film is formed on the substrate, a predetermined contrast improving effect may not be expected. In the present invention, it was found that Sn organic acid salt and Co organic acid salt are effective in improving the oxidation resistance of titanium oxynitride.

Further, organic acid tin such as stannous naphthenate and tin 2-ethylhexanoate is easily hydrolyzed and precipitates when mixed with a solvent containing water. Therefore, a solvent for obtaining a film having a good appearance is used. Since the dispersion medium of the conductive oxide and the titanium oxynitride particles is limited, it may react with the water in the air, and there was a problem in the stability of the coating liquid. In the present invention, it was found that by stabilizing the organic acid tin with β-diketone, hydrolysis is suppressed, the film characteristics are improved, and the stability of the liquid is also improved.

Further, in the present invention, a film having a good appearance with few traces of liquid flow, traces of particle flow, agglomeration of particles during drying of the film, unevenness of drying, film thickness difference, etc., during coating is obtained. In order to form a film, at least one selected from the group consisting of water, a C ₁ -C ₄ lower alcohol, propylene glycol ether, a derivative thereof, propylene glycol ether acetate and a derivative thereof is added to the coating solution in an amount of 0.
1-70 wt% and diacetone alcohol 0.1-3
Since 0 wt% is added, a coating liquid having good wettability with respect to the substrate and being hardly affected by the outside air can be obtained.

Further, in the present invention, Sn, I
By containing at least one oxide of n, Sb, Zn, Al, and Ga, it is possible to add antistatic performance that suppresses static electricity generated when the display is turned on and off, and it is also possible to suppress the adhesion of dust and the like. And 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 suppressing the reflection of a fluorescent lamp without impairing the resolution.

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 conductivity, it functions as a conductivity auxiliary component when forming an antistatic film. Titanium oxynitride has a N content of 0.1
TiO _x (1.0 ≦ x <2.0) containing ˜30 wt%
Is preferred. In the case of a colored film, the content of titanium oxynitride in the solution is 1 with respect to the total solid content in the solution.
90 wt% or less is preferable, 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 a colored antistatic film or a colored low reflection antistatic film, 1 to 80 wt% is preferable. If the amount of titanium oxynitride is too small, the coloring performance is sufficient, and if it is too large, the antistatic ability and the film transmittance are deteriorated, which is not preferable.

As the Sn organic acid salt and the Co organic acid salt used in the present invention, various compounds such as acetate salt, tartrate salt, and carboxylate salt can be used, but they are soluble and have an oxidation resistance to titanium oxynitride. From the viewpoint of the improvement effect, it is preferable to use stannous naphthenate, tin 2-ethylhexanoate, and stannous naphthenate and cobalt 2-ethylhexanoate, respectively. The content of the Sn organic acid salt or the Co organic acid salt in the solution is preferably in the range of 1 to 60 wt% with respect to the previous solid content in terms of SnO ₂ and Co ₃ O ₄ , respectively. If it is less than this range, the effect of improving the oxidation resistance of titanium oxynitride and the color tone are poor, and if it is more than this range, the film strength decreases, which is not preferable.

Further, in the present invention, Si (OR) _m R'is contained in the liquid.
_n (m + n = 4, m = 1 to 4, n = 0 to 3, R, R ′ =
The stability of the particles in the solution is improved by adding a C ₁ -C ₄ alkyl group) or a hydrolyzate thereof, and alcohols, ketones, ethers, esters, alcohol esters, ketone esters, 1 of ether alcohols, ketone ethers and ester ethers
Even when diluted with an organic solvent consisting of one kind or a mixture of two or more kinds, no cohesive precipitation occurs. The content is 0.5 to 65 wt% in terms of oxide based on the total solid content.
% Is preferable, and if it is less than this range, precipitation may occur when an organic solvent is mixed with the solution containing particles, and if it is more than this range, the coloring performance and antistatic performance deteriorate.

Various β-diketones can be used in the present invention and are not particularly limited, but acetylacetone is particularly preferably used. The content in the solution is preferably 0.1 to 10 times the mol of the Sn organic acid salt.
If it is less than this, it does not contribute to the stability of the liquid, and if it is more than this, the film strength is lowered, which is not preferable.

At least one selected from the group consisting of propylene glycol ether, its derivative, propylene glycol ether acetate and its derivative in the present invention is not particularly limited, and includes propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene. Glycol monopropyl ether, propylene glycol monobutyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Any of propylene glycol acetate propyl ether acetate and the like can be used.

The conductive oxide used in the present invention includes Sb-doped SnO ₂ , ITO, and Al-doped Zn.
ZnO doped with O or Ga can be used. These oxides have electroconductivity, can impart electroconductivity to the formed film, and can impart antistatic performance. These oxides can be used by dispersing them as fine particles in a coating solution, or can be used as a solution to be oxidized on a substrate.

The dispersion medium and dispersion method of these particles or salts are not particularly limited, and various solvents and dispersion methods can be used. Preferably, particles can be added to an organic solvent such as water or alcohol, an acid or an alkali can be added to adjust the pH, and the particles can be dispersed by a commercially available crusher such as a colloid ball mill, a sand mill or a homogenizer. In this case, the average particle diameter of the dispersed particles is preferably 300 nm or less. When a solution is used, an organic compound such as a chelate complex or an inorganic compound such as nitrate is used and mixed with a liquid in which the above particles are dispersed.

Various methods of applying the solution to the substrate are conceivable, such as spin coating, dipping, spraying, roll coater, meniscus coater, etc. In particular, spin coating is excellent in mass productivity and reproducibility. It can be preferably adopted. By this method, a film having a thickness of about 100 to 1 μm can be formed.

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 medium having 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, a minimum value is obtained, and at this time, R = ((n ₂ −n ₀ n _S ).
/ (N ₂ + n ₀ n _s )) ² (1) is obtained.

In order to satisfy the antireflection condition, R = 0 in the equation (1),

N = (n ₀ n _S ) ^1/2 (2) is required.

When the equation (2) is expanded to a two-layer structure, n _S
n ₁ ² = n ₂ ² n ₀ (3) is obtained (n ₁ : medium layer, n ₂ : substrate 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 as well as the refractive index difference between the multilayer films are important factors. 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-low refractive index layer is formed with an optical thickness of λ / 2-λ / 4 from the substrate side. Reflective film, from the side of the substrate: a medium-refractive-index layer-high-refractive-index layer-low-refractive-index layer formed with an optical thickness of λ / 4-λ / 2-λ / 4. Layer-Medium Refractive Index Layer-
High Refractive Index Layer-Low Refractive Index Layer with Optical Thickness λ / 4-λ / 4-λ
A 4-layer low-reflection film formed of / 2-? / 4 is known as a typical example.

Using the colored film of the present invention as a high refractive index film,
When a low refractive index film is provided on the upper layer, it is formed by using a solution containing at least one selected from a solution containing MgF ₂ sol and a solution containing a Si compound such as Si alkoxide which becomes SiO ₂ by heating. To do. 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.

As a solution containing a Si compound for forming a low refractive index film, Si (OR) _{m R'n} (m + n = 4, m = 1
To 4, n = 0 to 3, R, R ′ = C _{1 to} C ₄ alkyl group) or a partial hydrolyzate is preferably used, and examples thereof include silicon ethoxide, silicon methoxide, and silicon isooxide. Although a monomer or polymer of propoxide or silicon butoxide can be preferably used, Si obtained by precipitating a solution obtained by saturating a silicon dioxide powder in an aqueous solution containing hydrosilicofluoric acid and boric acid.
Compounds can also be used. As a method for applying the compound represented by Si (OR) _m R ′ _n or the partial hydrolyzate onto the colored antistatic film, various methods can be preferably employed as in the method described above.

Since the colored antistatic film of the present invention contains titanium oxynitride, it has a high refractive index and can easily exhibit 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 for forming the colored film, the colored antistatic film and the colored low reflection antistatic film 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. Further, its applications extend to various applications such as CRT face panels, copying machines, computers, clean rooms, and display devices such as CRTs and LCDs.

[0037]

In the present invention, the mechanism of the effect of improving the oxidation resistance of titanium oxynitride by the Sn organic acid salt and the Co organic acid salt is not clear, but due to the presence of Sn and Co in the divalent state, the temperature is high in an oxidizing atmosphere. When fired, it is considered that the oxidation resistance of titanium oxynitride is improved due to the reducing effect of Sn, Co and organic acids.

Although the effect of β-diketone is not clear, it is considered that the stability of the liquid is increased by coordinating with the Sn organic acid salt and the Co organic acid salt. Low reflection characteristics are 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.

[0039]

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 evaluation results of the obtained film are as follows.

Transmittance evaluation: 380 nm, 550 nm by a spectrophotometer U-3500 manufactured by Hitachi Ltd.
The transmittance at 780 nm was measured.

Haze evaluation: The haze of the film itself was measured by a direct-reading haze computer manufactured by Suga Test Instruments.

Conductivity evaluation: Colored antistatic film and low-reflection antistatic film The surface resistance value of the film surface was measured in an atmosphere with a relative humidity of 30% or less by a Hiresta resistance meter manufactured by Mitsubishi Petrochemical.

Scratch resistance: under a load of 1 kg (LION
50-50), and after reciprocating the membrane surface 50 times with an eraser, scratches on the surface were visually judged. The evaluation criteria are as follows. ◯: No scratches, Δ: Some scratches, ×: Many scratches or peeling.

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

Luminous reflectance: Colored low-reflection antistatic film 38 of the film was measured by a GAMMA spectroscopic reflection spectrophotometer.
The luminous reflectance of 0 to 700 nm was measured.

Evaluation of dispersion stability of particles in liquid: The average particle size of the particles in the liquid was measured by a laser particle size analysis system LAP-3100 manufactured by Otsuka Electronics immediately after liquid synthesis and after being stored at 5 ° C. for 4 weeks. did.

Example 1 15 g of titanium oxynitride powder was added to 85 g of an aqueous solution whose pH was adjusted to 3.0 in advance, pulverized in a sand mill for 4 hours, heated at 90 ° C. for 1 hour, and then adjusted to a concentration of 10 wt%. A sol having an average particle size of 90 nm was obtained (Liquid A). Si (OEt) ₄ was added to an ethanol solution of Si (OEt) ₄ (solid content 20 wt% in terms of oxide).
8mo to the acidic aqueous hydrochloric acid solution adjusted to pH 3.0
1 ratio was added, and the mixture was refluxed under stirring at 80 ° C. for 2 hours (B
liquid). Tin 2-ethylhexanoate was diluted with ethanol so that the solid content was 3 wt% in terms of oxide (Liquid C).

Liquid A, liquid B, and liquid C are 1.2 in terms of each oxide.
After diluting with ethanol so as to be wt%, solution A: B
Liquid: C liquid = 65:20:15 mixed in a weight ratio, coated on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 160 ° C for 30 minutes to about 1
A film with a thickness of 00 nm was obtained.

Example 2 Liquids A and C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then the ratio of liquid A: liquid C was 65:35. The same procedure as in Example 1 was repeated except that
A film with a thickness of m was obtained.

Example 3 15 g of SnO ₂ powder (primary particle size 100 Å) 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 an hour, the concentration was adjusted to 10 wt% and the average particle size was 5
A sol of 0 nm was obtained (solution D).

Solution D, solution A, solution B and solution C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and solution A: solution B: solution C: solution D = 45: 2
The mixture was mixed at a weight ratio of 0:15:20, coated on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 160 ° C. for 30 minutes to obtain a film having a thickness of about 90 nm.

Example 4 Cobalt 2-ethylhexanoate was diluted with ethanol so that the solid content was 3 wt% in terms of oxide (Liquid E).

The liquids A, B and C in Example 1 and the liquids D and E in Example 3 were calculated as 1.
After being diluted with ethanol to be 2 wt%, solution A:
Solution B: Solution C: Solution D: Solution E = 35: 20: 15: 20: 1
Mix so that the weight ratio becomes 0, and coat the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds.
It was heated at 0 ° C. for 30 minutes to obtain a film having a thickness of about 90 nm.

[Embodiment 5] 15 g of SnO ₂ powder (primary particle size 100 Å) doped with 8 mol% of Sb was added to 85 g of water.
Add to the inside and pulverize with a sand mill for 4 hours and heat at 90 ° C for 1 hour, then adjust to a concentration of 10 wt%, average particle size 50
nm sol was obtained (Liquid D).

Solution D and solution A, solution B and solution C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and solution A: solution B: solution C: solution D = 45: 2
The mixture was mixed in a weight ratio of 0:15:20, and 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 obtain a film having a thickness of about 100 nm. On this film, an ethanol solution of Si (OEt) ₄ (solid content 20 wt% in terms of oxide) was added to Si (OEt).
t) ₄ ) 8 mol ratio of hydrochloric acid acidic aqueous solution adjusted to pH 3.0 was added, stirred at 80 ° C. for 2 hours, and then diluted with ethanol to an oxide conversion of 0.9 wt% (E)
Liquid) was applied at a rotation speed of 100 rpm for 60 seconds and then heated at 380 ° C. for 30 minutes to obtain a colored low-reflection antistatic film having a two-layer structure.

[Example 6] Cobalt 2-ethylhexanoate was diluted with ethanol so that the solid content was 3 wt% in terms of oxide (F liquid).

Solution F and solutions A and B in Example 1,
The liquid C and the liquid D in Example 3 were converted into the respective oxides by 1.
After being diluted with ethanol to be 2 wt%, solution A:
Solution B: Solution C: Solution D: Solution F = 35: 20: 15: 20: 1
Mix so that the weight ratio becomes 0, and coat the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds.
It was heated at 0 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm. On this film, a solution of Si (OEt) ₄ in ethanol (solid content 20 wt% in terms of oxide) was added to p with respect to Si (OEt) ₄ .
After adding 8 mol ratio of hydrochloric acid acidic aqueous solution adjusted to H3.0 and stirring at 80 ° C. for 2 hours, a solution (solution E) diluted with ethanol to an oxide conversion of 0.9 wt% was added to 100 r.
Apply at a rotation speed of pm for 60 seconds, then at 380 ° C for 3 seconds.
It was heated for 0 minutes to obtain a colored low-reflection antistatic film having a two-layer structure.

[Example 7] ITO powder (Sn / In (m
ol ratio) = 10/90, primary particle size 300Å) 15 g was added to water 85 g, and the mixture was pulverized in a sand mill for 4 hours and then 90 ° C.
After heating for 1 hour, the concentration was adjusted to 10 wt% to obtain a sol having an average particle diameter of 90 nm (solution G).

Solution G and solution A, solution B and solution C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and solution G: solution A: solution B: solution C = 20: 4
The mixture was mixed in a weight ratio of 5:20:15, coated 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 30 minutes to obtain a film having a thickness of about 100 nm. On this film, an ethanol solution of Si (OEt) ₄ (solid content 20 wt% in terms of oxide) was added to Si (OEt).
t) ₄ to 8 mol ratio of hydrochloric acid acidic aqueous solution adjusted to pH 3.0 was added, stirred at 80 ° C. for 2 hours, and then diluted with ethanol to an oxide conversion of 0.9 wt% (E
Liquid) was applied at a rotation speed of 100 rpm for 60 seconds, and then heated at 380 ° C. for 30 minutes to obtain a colored low-reflection antistatic film having a two-layer structure.

Example 8 14 g of titanium oxynitride and S
SnO ₂ powder doped with b of 8 mol% (primary particle size 1
00Å) 6.0 g of water 8 adjusted to pH 13 in advance
Add to 0 g and pulverize with a sand mill for 16 hours and 90 ° C
After heating for 1 hour at a temperature of 10% by weight, a sol having an average particle size of 90 nm was obtained (solution H).

Solution H and solutions A, B and C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then solution A: solution B: solution C: solution H = 45: 2
The mixture was mixed in a weight ratio of 0:15:20, coated 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 30 minutes to obtain a film having a thickness of about 100 nm. On this film, an ethanol solution of Si (OEt) ₄ (solid content 20 wt% in terms of oxide) was added to Si (OEt).
t) ₄ to 8 mol ratio of hydrochloric acid acidic aqueous solution adjusted to pH 3.0 was added, stirred at 80 ° C. for 2 hours, and then diluted with ethanol to an oxide conversion of 0.9 wt% (E
Liquid) was applied at a rotation speed of 100 rpm for 60 seconds, and then heated at 380 ° C. for 30 minutes to obtain a colored low-reflection antistatic film having a two-layer structure.

Example 9 Liquids A and C in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then the ratio of liquid A: liquid C = 80: 20 was obtained. And mix it up to 100 rpm on the surface of the cathode ray tube panel.
Was applied for 60 seconds at a rotation speed of, and then heated at 160 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Embodiment 10] Liquid A and B in Embodiment 1.
Solution A, Solution C and Solution D in Example 3 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then A
Liquid: Liquid B: Liquid C: Liquid D = 40: 18: 2: 40 Mix in a weight ratio of 100 rp on the surface of the cathode ray tube panel.
coating at a rotation speed of 60 m for 60 seconds, and then at 160 ° C. for 30 seconds.
After heating for a minute, a film having a thickness of about 100 nm was obtained.

[Example 11] Cobalt naphthenate was diluted with ethanol so as to be 3 wt% in terms of oxide (liquid H).

Solution A and solution B in Example 1, and solution D and solution H in Example 3 were solution A: solution B: solution D: solution H = 4.
The mixture was mixed in a weight ratio of 5: 20: 20: 15, coated 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 30 minutes to obtain a film having a thickness of about 100 nm. On this film, 1 part of the liquid E in Example 7 was applied.
Apply for 60 seconds at a rotation speed of 00 rpm, then 380
It was heated at 30 ° C. for 30 minutes to obtain a colored low reflection antistatic film having a two-layer structure.

Comparative Example 1 Liquids A and B in Example 1 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then the ratio of liquid A: liquid B was 80:20. The mixture was mixed, coated on the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then heated at 160 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Comparative Example 2] Liquids A and B in Example 1 and liquid D in Example 3 were 1.2 w in terms of each oxide.
After being diluted with ethanol to be t%, solution A: B
Liquid: D liquid = 40:20:40 mixed in a weight ratio, coated 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 30 minutes to about 10
A film with a thickness of 0 nm was obtained.

[Comparative Example 3] Liquids A and B in Example 1
Solution A, Solution C and Solution D in Example 3 were diluted with ethanol so as to be 1.2 wt% in terms of each oxide, and then A
Liquid: Liquid B: Liquid C: Liquid D = 40: 19.5: 0.5: 40
Mix in a weight ratio to give 1 to the surface of the cathode ray tube panel.
Apply for 60 seconds at a rotation speed of 00 rpm, then 160
It was heated at 0 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm. On this film, a solution of Si (OEt) ₄ in ethanol (solid content 20 wt% in terms of oxide) was added to p with respect to Si (OEt) ₄ .
After adding 8 mol ratio of hydrochloric acid acidic aqueous solution adjusted to H3.0 and stirring at 80 ° C. for 2 hours, a solution (solution E) diluted to 0.9 wt% in terms of ethanol oxide was added at 100 rp.
m rotation speed for 60 seconds, then at 380 ° C for 30 seconds
After heating for a minute, a colored low reflection antistatic film having a two-layer structure was obtained.

The above results are shown in Table 1.

[0070]

[Table 1]

Example 12 15 g of titanium oxynitride was added to 85 g of an aqueous solution whose pH was adjusted to 3.0 in advance, pulverized in a sand mill for 4 hours, heated at 90 ° C. for 1 hour, and then adjusted to a concentration of 5 wt%. A sol having an average particle size of 90 nm was obtained (solution I). Si a (OEt) ₄ in ethanol nitric acid aqueous solution adjusted to pH3.0 with respect to Si (OEt) ₄ (having a solid part 5 wt% in terms of oxide) was added 8mol ratio, and the mixture was refluxed for 2 hours at 80 ° C. ( Solution J). Ethanol 1
Acetylacetone 7.5 g was added to 00 g, tin 2-ethylhexanoate 16 g was added, and the mixture was stirred for 1 hour (K.
liquid).

Solution I, solution J and solution K are prepared as solution I: solution J: solution K =
The mixture was mixed at a weight ratio of 6: 3: 1. This mixture 1
Ethanol 8.4 g, propylene glycol monomethyl ether acetate 27.3 g, isopropyl alcohol 7.8 g, diacetone alcohol 3.9 g in 2.6 g
Were mixed to obtain a coating liquid for colored film.

Example 13 15 g of SnO ₂ fine particles (primary particle size 10 nm) doped with 8 mol% of Sb was KO.
The mixture was added to 85 g of water that had been adjusted to pH 8.0 with H in advance, pulverized with a sand mill for 16 hours, heated at 90 ° C. for 1 hour, and then adjusted to have a concentration of 5 wt% to obtain a sol (Liquid L).

Liquid I, liquid J, liquid K and liquid L are liquid I: liquid J: K
Liquid: L liquid = 15: 30: 10: 45 were mixed in a weight ratio. Ethanol 8.4 was added to 12.6 g of this mixed solution.
g, propylene glycol monomethyl ether acetate 27.3 g, isopropyl alcohol 7.8 g, and diacetone alcohol 3.9 g were mixed to obtain a colored antistatic coating solution.

[Embodiment 14] IT instead of SnO ₂ fine particles doped with 8 mol% of Sb in Embodiment 13 was used.
Example 13 was repeated except that O fine particles (Sn / In = 10/90 mol ratio, primary particle size 30 nm) were used.

[Embodiment 15] Al instead of the SnO ₂ particles doped with 8 mol% of Sb in Embodiment 13 is replaced by Al.
ZnO fine particles (primary particle size 2
The same procedure as in Example 13 was performed except that 0 nm) was used.

[Example 16] In place of the SnO ₂ fine particles doped with 8 mol% of Sb in Example 13, Ga was used.
ZnO fine particles (primary particle size 40
nm) was used, and the same procedure as in Example 13 was performed.

[Comparative Example 4] In 100 g of ethanol, 2
15 g of tin ethylhexanoate was added and stirred for 1 hour (M liquid). The procedure of Example 13 was repeated except that the solution M was used instead of the solution K in Example 13.

Table 2 shows the evaluation results of the coating solutions prepared in Examples 12 to 16 and Comparative Example 4.

[0080]

[Table 2]

Example 17 The coating liquid obtained in Example 12 was applied onto the surface of a 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 having a thickness of about 90 nm. .

[Example 18] The coating liquid obtained in Example 13 was applied on the surface of a 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 having a thickness of about 90 nm. .

Example 19 The coating liquid obtained in Example 14 was applied on the surface of a 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 having a thickness of about 90 nm. .

[Example 20] The coating liquid obtained in Example 15 was applied to the surface of a 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 having a thickness of about 90 nm. .

[Example 21] The coating solution obtained in Example 16 was applied on the surface of a 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 having a thickness of about 90 nm. .

Example 22 15 g of titanium oxynitride and 5.0 g of SnO ₂ particles (primary particle size: 10 nm) doped with 8 mol% of Sb were added to 80 g of water whose pH was adjusted to 13 in advance, and a sand mill was used for 16 hours. Crushed 90
After heating at 0 ° C. for 1 hour, the concentration was adjusted to 10 wt% to obtain a sol having an average particle size of 90 nm (N liquid). The N liquid and the J liquid and the K liquid in Example 12 were mixed at a J: K: N = 3: 1: 6 weight ratio (P liquid). 12.6 g of the P liquid were mixed with 8.4 g of ethanol, 27.3 g of propylene glycol monomethyl ether acetate, 7.8 g of isopropyl alcohol, and 3.9 g of diacetone alcohol to prepare a coating liquid for a colored antistatic film. Coat the surface of the cathode ray tube panel at a rotation speed of 100 rpm for 60 seconds, and then 3
After heating at 80 ° C. for 30 minutes, a film having a thickness of about 90 nm was obtained.

[Example 23] Liquid P 1 in Example 22
Ethanol 8.4g Propylene glycol monomethyl ether acetate 19.5g, isopropyl alcohol 15.6g, diacetone alcohol 3.9g to 2.6g
Were mixed to obtain a coating liquid for a colored antistatic film. It 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 having a thickness of about 90 nm.

[Example 24] Liquid P 1 in Example 22
2.6 g of ethanol was mixed with 8.4 g of ethanol and 35.1 g of propylene glycol monomethyl ether acetate and 3.9 g of diacetone alcohol to prepare a coating liquid for a colored antistatic film. It 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 having a thickness of about 90 nm.

[Example 25] Liquid P 1 in Example 22
2.6 g of ethanol was mixed with 8.4 g of ethanol, 27.3 g of propylene glycol monopropyl ether, 7.8 g of isopropyl alcohol, and 3.9 g of diacetone alcohol,
It was used as a coating liquid for a colored antistatic film. It was applied on the surface of a cathode ray tube panel for 60 seconds at a rotation speed of 100 rpm, and then heated at 380 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Example 26] 20 g of J liquid was mixed with 52.5 g of propylene glycol monomethyl ether acetate, 42.0 g of isopropyl alcohol and 10.5 g of diacetone alcohol (liquid Q). The heat treatment at 380 ° C. for 30 minutes in Example 22 was changed to the heat treatment at 60 ° C. for 10 minutes to obtain a film having a thickness of about 100 nm. Liquid H was applied onto this film by the spin coating method described in Example 17, and heat-treated at 380 ° C. for 30 minutes to obtain a colored low-reflection antistatic film.

[Embodiment 27] 380 in Embodiment 23
The heat treatment at 30 ° C. for 30 minutes was changed to the heat treatment at 60 ° C. for 10 minutes to obtain a film having a thickness of about 100 nm. On this membrane,
Solution H was applied by the spin coating method described in Example 17 to give 38
Heat treatment was carried out at 0 ° C. for 30 minutes to obtain a colored low reflection antistatic film.

[Comparative Example 5] The coating solution obtained in Comparative Example 4 was applied to 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 having a thickness of about 90 nm. .

[Comparative Example 6] 8.4 g of ethanol, 27.3 g of methyl ethyl ketone, 7.8 g of isopropyl alcohol, and 3.9 g of diacetone alcohol were added to 12.6 g of P liquid.
Were mixed to obtain a coating liquid for a colored antistatic film. It was applied on the surface of a cathode ray tube panel for 60 seconds at a rotation speed of 100 rpm, and then heated at 380 ° C. for 30 minutes to obtain a film having a thickness of about 100 nm.

[Comparative Example 7] 8.4 g of ethanol, 7.8 g of propylene glycol monomethyl ether acetate, and 23.4 g of isopropyl alcohol were added to 12.6 g of P liquid.
g and 7.8 g of diacetone alcohol were mixed to obtain a coating liquid for a colored antistatic film. 10 on the surface of a CRT panel
Apply for 60 seconds at a rotation speed of 0 rpm, then 380 ° C
After heating for 30 minutes, a film having a thickness of about 100 nm was obtained.

Tables 3 and 4 show the evaluation results of the appearance of the colored films, the colored antistatic films, and the colored low-reflection antistatic films and the evaluation results of the film characteristics in Examples 17 to 27 and Comparative Examples 5 to 7, respectively. .

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

INDUSTRIAL APPLICABILITY The colored film, the colored antistatic film and the colored low reflection antistatic film of the present invention can be heat-treated at a low temperature and have uniform absorption in the entire visible light region, and thus have excellent low reflection characteristics. In addition, since titanium oxide itself containing nitrogen has conductivity, it can exhibit antistatic ability.

The coating liquid of the present invention is excellent in long-term stability, and traces of liquid flow, traces of flow of particles, agglomeration of particles at the time of film drying, unevenness of drying, film thickness difference, etc. when applied by spin coating. It is possible to provide an excellent colored film, a colored antistatic film, and a colored low-reflection antistatic film which have a small amount and have uniform absorption in the entire visible light region. 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 5/00 PPQ 183/04 PMS H01J 29/89 // G02B 1/10 (72) Inventor Ohashi Keiko 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Ken Kawari 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Pref., Asahi Glass Co., Ltd.

Claims (15)

[Claims] 1. A coating solution for forming a colored film, which contains titanium oxynitride and a Sn organic acid salt and / or a Co organic acid salt. 2. Titanium oxynitride and Si (OR) _{m R'n}
(M + n = 4, m = 1 to 4, n = 0 to 3, R, R ′ = C
Alkyl group) or a hydrolyzate of ₁ -C _4, Sn
At least one selected from the group consisting of propylene glycol ether, a derivative thereof, propylene glycol ether acetate and a derivative thereof, containing an organic acid salt and β-diketone, and selected from the group consisting of methanol, ethanol, and propanol. The coating liquid for forming a colored film according to claim 1, comprising at least one selected from the group consisting of diacetone alcohol and diacetone alcohol. 3. Sn, In, Sb, Zn, Al and Ga
The coating liquid for forming a colored film according to claim 1, which contains a conductive oxide of at least one of the above. 4. The colored film forming composition according to claim 1, wherein the Sn organic acid salt is at least one of stannous naphthenate and tin 2-ethylhexanoate. Coating liquid. 5. The coating solution for forming a colored film according to claim 1 or 3, wherein the Co organic acid salt is at least one selected from primary cobalt naphthenate and cobalt 2-ethylhexanoate. 6. The titanium oxynitride has a N content of 0.1 to 30 w.
The coating liquid for forming a colored film according to claim 1, wherein the coating liquid is TiO _x (1.0 ≦ x <2.0) containing t%. 7. A coating obtained by applying the coating liquid according to claim 1 and then heating and / or irradiating with ultraviolet rays to obtain 380 nm to 700 nm.
A colored film having reduced transmittance in the wavelength region of nm. 8. A substrate surface containing titanium oxynitride, further containing at least one of Sn organic acid salt and Co organic acid salt, and further Sn, In, Sb, Zn, Al and G.
380 nm to 7 which is obtained by applying a solution containing a conductive oxide of at least one of a and then heating and / or irradiating with ultraviolet light.
A colored antistatic film having a reduced transmittance in the wavelength region of 00 nm and having antistatic ability. 9. A substrate surface containing titanium oxynitride, further containing at least one of Sn organic acid salt and Co organic acid salt, and further Sn, In, Sb, Zn, Al and G.
After coating a solution containing a conductive oxide consisting of at least one of a, a coating is formed by heating and / or irradiating with ultraviolet light, and a film having a lower refractive index than the coating is formed on the coating. 380n characterized by being formed
A colored low-reflection antistatic film having a reduced transmittance in the wavelength range of m to 700 nm and having antistatic ability and low reflectance. 10. A multilayer film formed on a substrate, at least one layer of which contains titanium oxynitride, and S
A film obtained by applying a solution containing at least one kind of n organic acid salt and Co organic acid salt and further containing at least one conductive oxide of Sn, In, Sb, Zn, Al, and Ga. Is a colored low-reflection antistatic film. 11. The colored film according to any one of claims 8 to 10, wherein the Sn organic acid salt is at least one of stannous naphthenate and tin 2-ethylhexanoate. Antistatic film and colored low reflection antistatic film. 12. The colored film according to any one of claims 8 to 10, wherein the Co organic acid salt is at least one of cobalt cobalt naphthenate and cobalt 2-ethylhexanoate. Antistatic film and colored low reflection antistatic film. 13. The titanium oxynitride has a N content of 0.1 to 30.
The colored film, the colored antistatic film, or the colored low-reflection antistatic film according to any one of claims 8 to 12, which is TiO _x (1.0 ≦ x <2.0) contained in an amount of wt%. 14. A cathode ray tube having a colored film, a colored antistatic film, and a colored low-reflection antistatic film according to any one of claims 7 to 13. 15. A glass article on which the colored film, the colored antistatic film or the colored low reflection antistatic film according to any one of claims 7 to 13 is formed.