JP2000001339A - Colored film and display device with same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored film which does not very its transmittance in a heat treatment step in the production of a display device by carrying out baking using a coating material contg. fine noble metal particles and/or fine noble metal oxide particles. SOLUTION: The colored film is formed by baking preferably at 100-1,000 deg.C using a coating material contg. fine noble metal particles, preferably Ru and/or Pt particles having <=1 μm average particle diameter and/or fine noble metal oxide particles. A coating including the colored film can be formed on the face panel of a cathode-ray tube. The colored film is excellent in heat resistance, does not degenerate or fade in a heat treatment (350-500 deg.C) step in the production of the cathode-ray tube, is excellent also in high contrast effect and color tone adjusting effect and can maintain good transmittance even after the heat treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a colored film excellent in a high contrast effect and a color tone adjusting effect, and a display device provided with the colored film.

[0002]

2. Description of the Related Art Conventionally, in a display device such as a cathode ray tube, a liquid crystal display, and a plasma display, a colored film for lowering the transmittance may be formed on the face panel surface for the purpose of high contrast effect, color tone adjustment and the like. Further, the colored film is combined with a conductive film to form a colored conductive laminated film, thereby producing a display device having excellent antistatic effect, electromagnetic wave shielding effect, high contrast effect and the like (Japanese Patent Application Laid-Open No. Sho 62-8427). JP-A-5-178623 and the like.

In a conventional display device having an ordinary cathode ray tube, a coating in which a coloring agent is mixed is formed on a glass portion outside a phosphor layer, that is, a face glass portion, and the light transmittance is reduced over the entire visible light region. High contrast is achieved. However, the thickness of the glass is different between the central part and the peripheral part of the panel, and the coloring of the face glass alone changes the transmittance at the central part and the peripheral part of the panel. Get dark. In order to prevent this, a color film containing, for example, amorphous carbon black is formed on the face panel surface to adjust the color tone. This is a useful method for correcting the transmittance of the face glass.

[Problems] Usually, a glass bulb used for a cathode ray tube is composed of a panel for displaying an image, a funnel and a neck for forming a background of the panel. In the sealing step and the evacuation step for reducing the pressure inside the cathode ray tube, there is a heat treatment step for increasing the temperature to 350 to 500 ° C.

Therefore, if the colored film is formed before the heat treatment step, the transmittance of the colored film changes at the temperature during the heat treatment, and as a result, the favorable high contrast effect and color tone adjustment required for the cathode ray tube are impaired. Therefore, the colored film is applied at the final stage of the cathode ray tube manufacturing. However, in order to apply a colored film in the final stage, a nearly completed cathode ray tube has to be handled,
Workability was poor, and a large-scale coating device was required.

Further, when manufacturing a display device having a colored conductive laminated film including a colored film and a conductive film on an image display surface, the conductive film is formed by a CVD method, a thermal decomposition method, a sol-gel method, or the like. In some cases, heat treatment may be performed during the formation of the conductive film. In this heat treatment step, the transmittance of the colored film changes, and the favorable transmittance required for the display device changes, thereby impairing the high contrast effect and color tone adjustment. Had been.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems in the prior art, and the problems specifically set to solve the problems are as follows. An object of the present invention is to provide a colored film that does not cause a change in transmittance due to a heat treatment process, and a display device including the colored film.

[0008]

Means for Solving the Problems Claim 1 of the present invention
Is characterized by being formed by baking using a paint containing noble metal fine particles and / or noble metal oxide fine particles.

Further, the colored film according to claim 2 is characterized in that the noble metal is at least one of Ru and Pt.

[0010] According to a third aspect of the present invention, there is provided a display device, wherein the coating containing the colored film according to the first aspect is formed on the face panel surface.

The display device according to a fourth aspect is characterized in that the coating containing the colored film is a colored conductive laminated film containing at least a conductive film.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below by taking a colored film formed on a face panel of a cathode ray tube as an example. However, this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the content of the invention unless otherwise specified.

[Structure] The colored film comprises noble metal fine particles and / or
Alternatively, it is formed by applying a coating material for forming a colored film containing noble metal oxide fine particles (including a precursor thereof) to the surface of the substrate, drying if necessary, and baking. The baking temperature is usually 100 to 1000
C., preferably at a temperature of 300-500.degree.

The reason is that if the baking temperature is lower than 100 ° C., the colored film is not sufficiently cured, while the baking temperature is lower than 100 ° C.
If the temperature exceeds 0 ° C., the quality of the colored film deteriorates due to the high temperature, and the substrate may be damaged.

When the temperature for the baking treatment is set to 300 ° C. or more, a part or all of the noble metal fine particles, particularly, the platinum group metal fine particles represented by Ru are easily converted into the platinum group metal oxide fine particles, and the salt water resistance, It is preferable since it becomes excellent in chemical stability represented by UV resistance.

The atmosphere during the baking process is not particularly limited, and is usually performed in the air. The baking time is not particularly limited, and about 10 to 60 minutes is sufficient. By this baking process, the resulting colored film is formed of a noble metal, a noble metal and an oxide of the noble metal, or only an oxide of the noble metal.

The baked colored film is excellent in heat resistance, and is subjected to the heat treatment (350 to 350) for producing a cathode ray tube.
(500 ° C.), it is possible to easily achieve high contrast and color tone adjustment without degeneration and discoloration in the process, so that it can be used for a display device having a colored film on the face panel surface.

The transmittance required for the colored film is 50
Desirably, it is ~ 98%. If the transmittance is less than 50%, the brightness of the cathode ray tube is reduced. If the transmittance is more than 98%, the effect of the colored film is not obtained.

The coating for forming a colored film containing noble metal fine particles and / or noble metal oxide fine particles contains noble metal fine particles and / or noble metal oxide fine particles, a binder, a solvent, and if necessary, a colored pigment and the like.

The metal species of the noble metal fine particles or noble metal oxide fine particles to be used is not particularly limited, but Ru, P is preferred for reasons of coloring property, thermal stability, chemical stability and the like.
t is preferably used.

The colored film is required to be a transparent film without light scattering in order to prevent image quality deterioration. To satisfy this requirement, the noble metal fine particles or the noble metal oxide fine particles used have an average particle diameter of 1 μm. Hereinafter, the thickness is preferably 0.1 μm, more preferably 0.05 μm or less.

The reason is that if the average particle size exceeds 1 μm, Rayleigh scattering occurs, causing whitening of the colored film, lowering the resolution of the cathode ray tube, and lowering the contrast.
Further, when the average particle diameter is 0.05 μm or less, a part or all of the noble metal fine particles, particularly, platinum group metal fine particles represented by Ru are easily converted into platinum group metal oxide fine particles, and salt water resistance and ultraviolet light resistance are improved. It is preferable because it is excellent in typical chemical stability.

The binder used for the coating for forming a colored film is not particularly limited as long as it is excellent in heat resistance.
For example, a compound represented by the general formula (1) or a hydrolyzed condensed polymer thereof is suitably used.

[0024]

(R ₁ ) _n M (OR ₂ ) _4-n (1) (R ₁ represents an alkyl group, an alkenyl group, or an aryl group, and M represents a metal such as Si, Ti, Zr, or Al. , R ₂
Represents an alkyl group, and n represents an integer of 0 or 1. R
₁ and R ₂ may be the same or different in the case of an alkyl group. )

Specific examples of the compound represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxytitanium, tributoxyaluminum and the like. These can be used alone or in combination of two or more.

The catalyst used for the hydrolytic condensation polymerization of the compound represented by the general formula (1) includes inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, boric acid, formic acid, acetic acid, maleic acid, fumaric acid, and the like. Organic acids such as propionic acid, oxalic acid, malonic acid, tartaric acid, and succinic acid; and alkalis such as ammonia and trimethylammonium. Of these, hydrochloric acid,
Nitric acid is preferably used.

The amount of water used for the hydrolysis-condensation polymerization is appropriately determined, but is preferably used in the range of 0.001 to 0.5 mol per 1 mol of the compound represented by the above general formula (1). .

Examples of the solvent used in the paint for forming a colored film include alcohols, glycol derivatives, esters, ketones, and ethers, and they can be used alone or in combination of two or more.

Examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, isobutanol, octanol and the like.

Examples of the glycol derivative include ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol n-propyl ether,
Examples include propylene glycol n-propyl ether, ethylene glycol n-butyl ether, and propylene glycol n-butyl ether.

Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone acetylacetone and the like. Examples of ethers include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, and the like.

In the colored film, in addition to the noble metal fine particles and the noble metal oxide fine particles, other colored pigments having an absorption band at a specific wavelength may be used as long as the effect of adding the noble metal fine particles and / or noble metal oxide fine particles is not impaired. It can also be contained. By using other colored pigments in this way, the high contrast effect can be improved and the color tone can be easily adjusted.

As other colored pigments, those having high heat resistance and which do not deteriorate by heat treatment can be used. For example, Sn, Cu, Cr, Fe, Mn, Co, S
i, P, Ca, Pb, Ti, Ba, Ni, Sb, Zn,
Examples include metals containing at least one element of Al, Li, Ag, and Pb, oxides of these metals, organic substances containing these metals, and graphite carbon. It is desirable that the particle size of the colored pigment is 0.1 μm or less.

The noble metal fine particles and noble metal oxide fine particles can be produced by a known method. For example, a dispersion of noble metal fine particles can be obtained by adding a solution of a relatively unstable hydrogen compound such as sodium borohydride or hydrogen sulfide or a reducing agent such as sulfite to an aqueous solution of a metal salt of a noble metal. .

In dispersing the noble metal fine particles, noble metal oxide fine particles, and colored pigments, at least one of an anion, a cation, and a nonionic surfactant may be used. 0.1 for substance fine particles or these and colored pigments
Use about 300% by weight.

The compound represented by the above general formula (1) or a hydrolyzed polycondensate thereof, noble metal fine particles and / or noble metal oxide fine particles, a solvent and, if necessary, a colored pigment are mixed and dispersed, and colored. A paint for film formation is obtained. As a dispersing means, a homogenizer, a ball mill, a sand mill,
Known means such as an ultrasonic homogenizer can be used.

The content of the noble metal fine particles and / or noble metal oxide fine particles or these and the colored pigment in the paint for forming a colored film is preferably 3 to 60% by weight, so that the film strength, reliability and high contrast performance can be obtained. Can be exhibited in a well-balanced manner.

If the noble metal fine particles and / or noble metal oxide fine particles or these and the colored pigment are excessively added to the paint for forming a colored film, the total light transmittance of the film is remarkably reduced,
As a result, the brightness of the cathode ray tube is reduced, the film strength is also reduced, and the reliability is remarkably deteriorated. Conversely, if the noble metal fine particles and / or noble metal oxide fine particles or these and the colored pigment are too small, the film is sufficiently colored. Otherwise, a disadvantage occurs that the contrast of the cathode ray tube cannot be improved.

As a method of applying the paint for forming a colored film used here, a spin coating method, a spray method, a dipping method, or the like can be applied. Note that a spin coating method is preferably used to form a uniform film thickness.

Since a colored film formed by baking using such a colored film forming paint has excellent heat resistance,
Even if a colored film is formed on a panel before a process of assembling a display device, for example, a cathode ray tube, a desired colored film can be obtained without fading in a heat treatment process at the time of manufacturing the display device.

This colored film is used as a colored conductive laminated film in combination with a conductive film containing antimony-doped tin oxide, tin-doped indium oxide, gold, silver, palladium, etc., or a low refractive index film containing silicon oxide. You can also. As a method for forming a conductive film, a PVD method, a CVD method,
A method of depositing fine particles using a thermal decomposition method or a wet method can be applied. In particular, it is preferable to use a CVD method to form a uniform film thickness.

Examples of the colored conductive laminated film include antimony-doped tin oxide as one layer surface on the panel surface of a cathode ray tube;
A colored conductive film in which a conductive film of tin-doped indium oxide or the like is formed and a colored film containing, for example, noble metal fine particles and / or noble metal oxide fine particles is stacked on two layers.

The structure of the colored conductive laminated film is as described in 2 above.
It is not limited to a layer film. For example, as an example of a three-layer film, a film made of silicon oxide and titanium oxide is formed as a first layer on the panel surface of a cathode ray tube, and a conductive film such as antimony-doped tin oxide or tin-doped indium oxide is formed as a second layer. A film in which a colored film containing noble metal fine particles and / or noble metal oxide fine particles is laminated as a third layer, a colored film containing noble metal fine particles and / or noble metal oxide fine particles as a first layer, and a second layer A film in which a conductive film such as antimony-doped tin oxide or tin-doped indium oxide is formed and a film made of silicon oxide is stacked as a third layer, or contains noble metal fine particles and / or noble metal oxide fine particles as the first layer A colored film is formed, a conductive film such as antimony-doped tin oxide and tin-doped indium oxide is formed as a second layer, and noble metal fine particles and / or noble metal oxide fine particles are formed as a third layer. Film such as a laminate of uncolored film can be exemplified.

As an example of a four-layer film, a film made of silicon oxide is formed as a first layer on the panel surface of a cathode ray tube, a film made of silicon oxide and titanium oxide is formed as a second layer, and A conductive film such as antimony-doped tin oxide or tin-doped indium oxide is formed as a layer, a colored film containing noble metal fine particles and / or noble metal oxide fine particles is stacked as a fourth layer, and silicon oxide is used as a first layer. A second layer of a colored film containing noble metal fine particles and / or noble metal oxide fine particles, and a third layer of antimony-doped tin oxide;
A conductive film of tin-doped indium oxide or the like is formed, and a film in which a film made of silicon oxide is stacked as a fourth layer, or a film made of silicon oxide is formed as a first layer, and noble metal fine particles and / or Alternatively, a colored film containing noble metal oxide fine particles is formed, and as the third layer, antimony-doped tin oxide,
For example, a film in which a conductive film such as tin-doped indium oxide is formed and a colored film containing noble metal fine particles and / or noble metal oxide fine particles is laminated on the fourth layer can be exemplified. The configuration of the colored conductive laminated film is as described above. Needless to say, it is not limited.

Generally, the antireflection function of the laminated film is as follows.
Since the refractive index and the thickness of the film are determined by the number of laminated films, the refractive index and the thickness of the film are appropriately selected in consideration of the number of laminated films in the film including the colored film and the colored conductive laminated film. Thereby, an effective anti-reflection effect can be obtained.

When a colored conductive laminated film including a conductive film is formed, an alkali barrier film containing silicon oxide is formed as the first layer on the panel surface of the cathode ray tube.
It is also possible to prevent deterioration of conductivity caused by an alkali component eluted from glass.

Further, if necessary, an organic pigment and / or dye and a binder may be provided on the colored conductive laminated film in order to adjust the color tone of the formed colored conductive laminated film and to obtain a more preferable body color of a cathode ray tube. It is also possible to form the colored film consisting of at a low temperature after assembling the cathode ray tube.

Examples of the organic pigment include disazo pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments from the viewpoints of light resistance, dispersibility, spectral transmission characteristics and the like.
Phthalocyanine pigments and the like are used. As a dye,
Direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, sulfur dyes, sulfur vat dyes, vat dyes, soluble vat dyes, azoic dyes, disperse dyes, reactive dyes, oxidation dyes and the like are used.

Further, a silica film can be formed by a spray method in order to impart a non-glare property on the colored conductive laminated film. The colored film and the laminated film,
Specifically, the present invention can be applied to a display device such as a cathode ray tube and a liquid crystal display panel.

[0050]

EXAMPLES In Examples, the following 11 kinds were prepared. [1] Preparation of aqueous sol (1a) Ruthenium aqueous sol (a) A ruthenium chloride aqueous solution 0.15 mmol / L and sodium borohydride aqueous solution 0.024 mmol / L were mixed, and the obtained colloidal dispersion was concentrated to 0.198. Aqueous sol containing ruthenium microparticles in mole / liter (a)
I got The particle size of the ruthenium fine particles was 0.02 μm or less.

(1b) Platinum aqueous sol (b) 0.15 mmol / L of chloroplatinic acid aqueous solution and 0.024 mmol / L of aqueous sodium borohydride solution were mixed, and the obtained colloidal dispersion was concentrated. An aqueous sol (b) containing 0.198 mol / liter of platinum fine particles was obtained. The particle size of the platinum fine particles was 0.03 μm or less.

(1c) Ruthenium oxide aqueous sol (c) A precipitate obtained by adding ammonium hydrogencarbonate (0.024 mmol / L) to a ruthenium chloride aqueous solution (0.15 mmol / L) is filtered off, washed, dried and calcined to obtain ruthenium oxide fine particles. I got The ruthenium oxide fine particles were dispersed in water and pulverized using a sand mill to obtain an aqueous sol (c) containing 0.198 mol / l of ruthenium oxide. The particle size of the ruthenium oxide was 0.03 μm or less.

[2] Preparation of coating liquid for forming transparent film (2a) Coating liquid for forming transparent film containing silica (A) 23.08 g of tetraethoxysilane and ethyl alcohol 1
86.03 g, 1.06 g of 1N hydrochloric acid, and 4.81 g of pure water were mixed and aged at a temperature of 60 ° C. for 1 hour to obtain a coating liquid (A) for forming a silica-containing transparent film.

(2b) Coating solution for forming a transparent film containing titania and silica (C) 23.08 g of tetraisopropoxytitanium, 166.78 g of ethyl alcohol, 15.6 g of acetylacetone and 1N
Mix 1.06 g of hydrochloric acid and 4.31 g of pure water, and add
For 1 hour to obtain a uniform solution (B). Then, 40 g of the liquid (A) and 60 g of the liquid (B) were mixed to obtain a coating liquid (C) for forming a transparent film containing titania and silica.

[3] Preparation of Coating Solution for Forming Colored Film (3a) Ruthenium-based Coating Solution (D) 30 g of aqueous sol (a) is mixed with the above-mentioned coating solution (A) for forming a silica-containing transparent film. The resulting mixture was dispersed with an ultrasonic homogenizer for 10 minutes to obtain a coating solution (D) for forming a colored film.

(3b) Platinum-based coating liquid (E) Further, 30 g of the aqueous sol (b) was mixed with the above-mentioned silica-containing transparent film-forming coating liquid (A), and the resulting mixed liquid was subjected to an ultrasonic homogenizer for 10 minutes. By dispersing, a coating liquid (E) for forming a colored film was obtained.

(3c) Ruthenium oxide-based coating liquid (F) Further, 30 g of the aqueous sol (c) was mixed with the above-mentioned coating liquid (A) for forming a silica-containing transparent film, and the resulting mixture was subjected to ultrasonic homogenization. The mixture was dispersed for 1 minute to obtain a coating liquid (F) for forming a colored film.

(3d) Ruthenium-ruthenium oxide-based coating solution (G) Further, 15 g of an aqueous sol (a) and 15 g of an aqueous sol (c) are mixed with the coating solution (A) for forming a transparent film containing silica. The obtained mixture was dispersed with an ultrasonic homogenizer for 10 minutes to obtain a coating liquid (G) for forming a colored film.

[4] Preparation of paint for forming colored film containing colored pigment (4a) Paint for forming colored film containing colored pigment (H) 10 g of Co-Al oxide compound and 3.0 g of polymer dispersant
And 150 g of glass beads and 87 g of ethyl alcohol were mixed and dispersed in a sand mill at 2,500 rpm for 3 hours.
The glass beads were separated to obtain a uniform dispersion (d).
99 g of the coating solution (D) for forming a colored film and 1.0 g of the dispersion (d) were mixed to obtain a coating material (H) for forming a colored film containing a colored pigment.

(4b) Paint for forming a colored film containing a colored pigment (I) 30 g of amorphous carbon black and 10.5 of a polymer dispersant
g, 150 g of glass beads and 59.5 g of ethyl alcohol were mixed and dispersed by a sand mill at 2,500 rpm for 4 hours. Then, the glass beads were separated to obtain a uniform dispersion (e). The coating liquid for forming a silica-containing transparent film (A)
99 g and 1.0 g of the dispersion (e) were mixed to obtain a colored film-forming coating material (I) containing a colored pigment.

Example 1 After cleaning a transparent glass substrate, it was preheated, and a thin film of tin oxide doped with antimony on a glass surface by a CVD method (thickness: 75 nm;
Nesa film). Then, the surface temperature of the glass substrate on which the Nesa film was formed was adjusted to a temperature of 40 ° C., and the coating liquid (D) for forming a colored film containing the ruthenium fine particles was applied by spin coating to obtain a temperature of 50 ° C. Dried in warm air for 30 seconds and baked at 450 ° C. for 30 minutes to form a second colored film (110 nm thick).
m) to form a colored conductive laminated film.

Example 2 The same operation as in Example 1 was performed for film formation. However, the second layer film was formed using the coating liquid (E) for forming a colored film.

Example 3 The same operation as in Example 1 was performed for film formation. However, the second layer film was formed using the coating liquid (F) for forming a colored film.

Example 4 The same operation as in Example 1 was performed for film formation. However, the second layer film was formed using the coating liquid (G) for forming a colored film.

Example 5 The same operation as in Example 1 was performed for film formation. However, the second layer film was formed using a coloring film forming paint (H) containing a coloring material.

Example 6 One side of a transparent glass substrate was
The temperature was adjusted to 40 ° C., and the coating solution (A) for forming a silica-containing transparent film was applied to this surface by spin coating, and the coated surface was dried with hot air at 50 ° C. for 60 seconds.
Bake at 450 ° C for 30 minutes to form the first layer (film thickness 2
00 nm).

The coating solution (C) for forming a titania- and silica-containing transparent film was applied onto the first layer film by a spin coating method, dried with hot air at a temperature of 50 ° C. for 60 seconds, and then dried at a temperature of 450 ° C. A baking process is performed for 30 minutes to form a second layer film (110 nm thick), and then a Nesa film (150 nm thick) is formed on the second layer film by CVD.
It was formed as a layer film.

Next, the coating liquid (D) for forming a colored film containing the above-mentioned ruthenium fine particles was applied on the third layer film by spin coating, and the coated surface was dried with hot air at a temperature of 50 ° C. for 60 seconds. Then, a baking treatment was performed at a temperature of 450 ° C. for 30 minutes to form a colored conductive laminated film in which a colored film (thickness: 100 nm) was formed as a fourth layer film.

Example 7 The same operation as in Example 6 was performed for film formation. However, the fourth layer film was formed using the coating liquid (E) for forming a colored film.

Example 8 The same operation as in Example 6 was performed for film formation. However, the fourth layer film was formed using the coating liquid (F) for forming a colored film.

Example 9 The same operation as in Example 6 was performed for film formation. However, the fourth layer film was formed using the coating liquid (G) for forming a colored film.

Comparative Example 1 The same operation as in Example 1 was performed for film formation. However, the second layer film was formed using the colored film forming paint (I) containing a colored pigment.

Comparative Example 2 The same operation as in Example 6 was performed for film formation. However, the fourth layer film was formed by using the colored film forming paint (I) containing a colored pigment.

The properties of the colored film and the colored conductive laminated film obtained in each of the examples and comparative examples were measured by the following methods, and the results are shown in Table 1. Haze and total light transmittance were measured using a haze meter (Model TC-HIII DP) manufactured by Tokyo Denshoku Co., Ltd. Surface resistance was measured using Mitsubishi Chemical's Loresta AP.
It was measured by the terminal probe method. The reflectance was measured using a specular reflection jig having an incident angle of 5 ° with U-Best 50 manufactured by JASCO Corporation. Adhesion was measured according to MIL-C-675C, using a poppy rubber ER-30R manufactured by Lion Co., Ltd., with a load of 1 kgf / cm ² , reciprocating 20 times while rubbing the surface to prevent damage to the film surface. It was visually observed and evaluated. In the heat resistance test, a heat treatment was performed in an electric furnace at a temperature of 500 ° C. for 10 hours, and a change in transmittance of the conductive colored film was measured.

[0075]

[Table 1]

According to the results shown in Table 1, in the colored conductive laminated films of Comparative Examples 1 and 2, the values of the transmittance before the heat treatment and the transmittance after the heat treatment greatly changed. In the colored conductive laminated films according to Examples 1 to 9, there is almost no change in transmittance before and after the heat treatment, and good transmittance is maintained.

[Functions and Effects] From this, it can be seen that a display device manufactured by forming a coating containing at least a colored film on the face glass surface and then performing a heat treatment at a temperature of 350 to 500 ° C. By baking using a paint containing fine particles and noble metal oxide fine particles as a coloring material, even if a heat treatment step is required after the formation of a colored film, the high contrast effect and color tone adjustment are impaired. No, a colored film that can withstand practical use can be formed.

[0078]

As described above, the colored film according to the first aspect of the present invention is formed by baking using a paint containing noble metal fine particles and / or noble metal oxide fine particles, thereby providing a colored film having excellent heat resistance. A film is obtained, and even if it is heat-treated in a heat treatment step at the time of manufacturing a display device, for example, a cathode ray tube, it does not deteriorate and discolor, and its transmittance before the heat treatment does not change, and a good transmittance can be maintained. .

Further, in the colored film according to the second aspect, since the noble metal is at least one of Ru and Pt, a colored film having more excellent coloring property, thermal stability, chemical stability and the like can be obtained. Obtainable.

Further, in the display device according to the third aspect, since the coating containing the colored film according to the first aspect is formed on the face panel surface, good transmittance can be maintained, high contrast effect, color tone adjustment, and the like can be maintained. And a display device with excellent performance can be realized.

Further, in the display device according to the fourth aspect, since the coating containing the colored film is a colored conductive laminated film containing at least a conductive film, a high contrast effect, excellent color tone adjustment, and antistatic properties can be obtained. A display device having an electromagnetic wave shielding effect can be easily realized.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) H01J 11/02 H01J 29/88 5C032 29/88 G02B 1/10 Z 5C040 (72) Inventor Atsumi Wakabayashi Funabashi-shi, Chiba 585, Sumitomo Osaka Cement Co., Ltd. New Material Business Division F-term (reference) 2H048 CA05 CA14 CA19 CA26 2H091 FA02Y FB02 FB13 FC22 FD06 FD24 GA02 LA12 LA17 2K009 AA12 BB02 CC01 CC03 CC14 DD02 EE01 EE03 4G059 AA01 DBA03 AC08 EA011 HA066 KA20 NA20 PA07 PA19 5C032 AA02 AA07 DD02 DE01 DG02 DG04 5C040 MA02 MA07 MA08

Claims (4)

[Claims] 1. A colored film formed by baking using a paint containing noble metal fine particles and / or noble metal oxide fine particles. 2. The colored film according to claim 1, wherein said noble metal is at least one of Ru and Pt. 3. A display device, wherein a coating containing the colored film according to claim 1 is formed on a face panel surface. 4. The display device according to claim 3, wherein the coating containing the colored film is a colored conductive laminated film containing at least a conductive film.