JPH08171855A - Manufacture of phosphor layer with filter - Google Patents

Abstract

PURPOSE: To easily and sufficiently widen the work width also in an overcoating and once exposure patterning method. CONSTITUTION: A manufacture of a phosphor layer with a filter is provided with a process for forming a pigment layer on a base plate, a process for forming a phosphor layer on this pigment layer, and a process for simultaneously exposing and developing the pigment layer and the phosphor layer. The process for forming the pigment layer on the base plate is a process for applying a high molecular electrolytic salt solution containing pigment particles on the base plate and drying it, and the process for forming the phosphor layer is a process using a solution containing the material for forming the high molecular electrolyte and salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phosphor layer with a filter having a two-layer structure.

[0002]

2. Description of the Related Art On the inner surface of a face plate of a cathode ray tube or a color image receiver, red, blue, and green dot-shaped or stripe-shaped phosphor layers are formed. When the electron beam collides with the phosphor layer, the phosphor layer emits light to display an image. In order to improve image display characteristics such as contrast and color purity, the phosphor layer has been conventionally improved. For example, there is a phosphor layer with a filter in which a pigment layer having the same body color as the emission color of the phosphor layer is provided between the face plate and the phosphor layer (Japanese Patent Laid-Open No. 64-7457). This phosphor layer with a filter absorbs the green and blue component light by the red pigment, the green and red component light by the blue pigment, and the blue and red component light by the green pigment among the incident external light. Therefore, the contrast and color purity are improved.

However, this method of forming a phosphor layer with a filter has to be carried out by an extremely complicated process of repeating exposure and development for each layer. For example, there is a problem that the number of manufacturing steps is several times, such as forming a pigment layer by using a slurry method, exposing and developing it, and then forming a phosphor layer by using a slurry method, exposing and developing it. Therefore, a one-time exposure method has been proposed in which a phosphor layer is overcoated on a pigment layer and patterned by one exposure (Japanese Patent Laid-Open No. 52-7757).
No. 8, JP-A-5-266795).

[0004]

However, in the method of patterning by one exposure after overcoating, the phenomenon that the first layer elutes easily when the second layer is applied. To prevent this, if the first layer is completely cured,
After the formation of the layer, it is difficult to dissolve and remove the first layer during development.
As a result, it becomes difficult to form the same pattern as the phosphor. As described above, the method of patterning by single-exposure overcoating requires compatibility of two contradictory characteristics, that is, elution characteristics and development characteristics. Therefore, a manufacturing work width is narrow and a phosphor layer with a filter having a uniform quality can be obtained. There was a problem that I could not get it.

The present invention has been made in order to solve such a problem, and even in the method of patterning by one-time overcoating, the production of a phosphor layer with a filter which is simple and can sufficiently widen the working width. The purpose is to provide a method.

[0006]

A method for producing a phosphor layer with a filter according to the present invention comprises a step of forming a pigment layer on a substrate, a step of forming a phosphor layer on the pigment layer, a pigment layer and a fluorescent layer. In the method for producing a phosphor layer with a filter having a step of simultaneously exposing and developing the body layer, the step of forming the pigment layer on the substrate is a step of coating a salt solution of a polymer electrolyte containing pigment particles on the substrate and drying. The step of forming the phosphor layer is characterized by using a solution containing a substance that forms a salt with the polymer electrolyte. Further, the salt solution of the polymer electrolyte and the solution containing the substance that forms a salt with the polymer electrolyte are characterized by using a solvent mainly composed of water.

The salt solution of the polyelectrolyte according to the present invention is
When coated and dried on the substrate, some of the groups forming the polyelectrolyte salt are dissociated, and the polyelectrolyte contained in the pigment layer becomes insoluble in the solvent used in the step of forming the phosphor layer.
On the other hand, when the phosphor layer is formed by including a polymer electrolyte in which a part of the salt is dissociated and a substance that forms a salt again in the solvent used in the step of forming the phosphor layer, it is included in the pigment layer. The polymer electrolyte is solubilized and the pigment layer and the phosphor layer can be dissolved and removed at the same time during development.

The present invention is based on such knowledge, and in the method of manufacturing a phosphor layer with a filter,
The film of the first layer should not be dissolved by the solvent during the application of the second layer (elution property), and then the pattern other than the exposed part should be formed during development to form the same pattern as the phosphor (development property).
The two contradictory characteristics described above are achieved.

The contents of each will be described below.
First, the pigment dispersion liquid that forms the first layer film will be described. The polymer electrolyte according to the present invention is a polymer compound in which a polymer structural unit has a dissociative group, and is also a dispersant for dispersing a pigment. Specifically, acrylic acid-based, acrylic acid-styrene-based, etc. acrylic acid copolymers, polymer polycarboxylic acids, styrene-polycarboxylic acid copolymers, aromatic sulfonic acid formalin condensates, polyoxyethylene alkyl ethers. Examples thereof include sodium salts such as sulfates and polyoxyethylene alkylphenyl ether sulfates, ammonium salts, amine salts and the like. More specifically, as the acrylic acid type, Despec N-40 (sodium salt) (made by Allied Colloid Co., Ltd.), Despec A-40 (ammonium salt)
(Made by Allied Colloid), as acrylic acid copolymer, Despec G-40 (sodium salt) (made by Allied Colloid), Despec GA-40 (ammonium salt) (made by Allied Colloid), high Poise 520 (sodium salt) (manufactured by Kao Corporation), DISCOTE N-14 (ammonium salt) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as molecular polycarboxylic acids, and Oxylac SH-101 as styrene-polycarboxylic acid copolymer. (Manufactured by Nippon Shokubai Chemical Co., Ltd.), as an ammonium salt of polyoxyethylene alkyl ether sulfate, Hitenol 08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and as an ammonium salt of polyoxyethylene alkylphenyl ether sulfate, Hitenol N-08 (No. Manufactured by Ichigohyo Pharmaceutical Co., Ltd., and the like. These can be used alone or as a mixture.

Among these, when the pigment layer is formed by the coating and drying method, an easily volatile ammonium salt is preferable, and an ammonium salt of an acrylic acid-based or acrylic acid-based copolymer has an elution property and a development property. It is particularly preferable for achieving both.

The pigment according to the present invention may be either an inorganic pigment or an organic pigment. In particular, a pigment that can be uniformly dispersed in the filter layer of the phosphor layer with a filter and that allows the filter layer to have sufficient transparency without causing light scattering is preferable.

The following pigments can be given as specific examples. The red pigment is ferric oxide, which is a trade name of Sicotrans Red.
L-2817 (particle size, 0.01 μm to 0.02 μm, BA
SF manufactured), anthraquinone-based product name Chromophtal Red A2B
(Particle size, 0.01 μm, manufactured by Ciba-Geigy), and as a blue pigment, cobalt aluminate (Al ₂ O ₃ —CoO) based trade name Cobalt Blue X (particle size, 0.01 μm
0.02 μm, manufactured by Toyo Pigment Co., Ltd.) 8000 (particle size, 0.3 μm, manufactured by Daiichi Kasei),
Trade name of phthalocyanine blue system Lionol Blue FG-7330 (particle size,
0.01 μm, manufactured by Toyo Ink Co., Ltd., as a green pigment, Ti
O ₂ —NiO—CoO—ZnO system trade name Typyroxide TM-Green # 3320 (particle size, 0.01 μ
m-0.02 μm, manufactured by Dainichiseika Co., Ltd., CoO-Al ₂ O ₃
-Cr ₂ O ₃ -TiO ₂ type trade name Typyroxide TM-Green # 3340 (particle size, 0.01 μm ~
0.02 μm, manufactured by Dainichiseika Co., Ltd., CoO—Al ₂ O ₃ —C
Trade name TYPIROXIDE TM-Green # 3420 (particle size, 0.01 μm to 0.02 μm, manufactured by Dainichiseika), which is an r ₂ O ₃ system, and ND-801, a trade name, which is a Cr ₂ O ₃ system.
(Particle size: 0.35 μm, manufactured by Nippon Denko), chlorinated phthalocyanine green type trade name First Gen Green S (particle size: 0.01 μm, manufactured by Dainippon Ink and Chemicals), brominated phthalocyanine green type trade name First Gen Green 2YK (particle diameter, 0.01 μm, manufactured by Dainippon Ink and Chemicals, Inc.) can be exemplified.

The average particle size of the above-mentioned pigment must be considered in relation to the phosphor dispersion liquid of the second layer. For example, according to the experimental results of the present inventor, when a phosphor having an average particle size of about 5 to 10 μm is used, the phosphor will enter the gaps between the pigment particles unless the average particle size of the pigment is 1 μm or less. Therefore, a two-layer structure cannot be formed. The average particle size of the pigment is preferably 1 μm or less in order to maintain the transparency of the first layer. It is more preferably 0.1 μm or less.

The concentration of the pigment dispersed in the dispersant comprising the polyelectrolyte is in the range of 0.1% to 50% by weight, preferably 1% to 50% by weight. Pigment concentration 0.1% by weight
If it is less than 1, the coloring of the first layer will not be recognized. 1
When it exceeds the weight%, more distinct coloring is observed. On the other hand, if it exceeds 50% by weight, the viscosity of the dispersion liquid increases sharply and a uniform film cannot be applied.

In the present invention, the polyelectrolyte concentration is important in relation to the pigment concentration. The ratio of the polyelectrolyte concentration (wt%) to the pigment concentration (wt%) (= polyelectrolyte concentration / pigment concentration) is 0.005 to 1, preferably 0.01 to
It is in the range of 0.5. If this ratio exceeds 1, the first layer is solubilized before the drying of the phosphor dispersion liquid of the second layer is completed, so that the first layer and the second layer are mixed. A two-layer structure can be formed. On the other hand, if the ratio is less than 0.005, the binding force between pigment particles becomes strong and the releasability deteriorates.

By mixing and stirring the above-mentioned polymer electrolyte and pigment with pure water, a dispersion liquid for forming the first layer is obtained. If it is 5% by weight or less in pure water,
A water-soluble organic solvent such as alcohol can be included.

Furthermore, a nonionic dispersant may be used in combination with the polymer electrolyte in order to improve the peeling property. Examples of nonionic dispersants include polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene derivatives such as polyoxyethylene sorbitan monolaurate, and polyoxyalkylene derivatives such as polyoxyalkylene alkyl ethers. be able to. Specifically, Neugen EA-140, Neugen EA-170 (both manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Emulgen 106, Emulgen A-50.
0 and Leodol TW-L120 (both manufactured by Kao Corporation) can be exemplified. A preferred blending ratio for improving the peeling property is 1/30 to 1 / nonion / anion NH ₄ salt.
300.

Next, the phosphor dispersion liquid for forming the second layer film will be described. This phosphor dispersion liquid is a phosphor suspension containing a resist in order to form a phosphor having a predetermined pattern on the pigment layer.

As the phosphor according to the present invention, it is possible to use red, blue and green phosphors which have been conventionally used in cathode ray tubes and color image receivers. For example, as a red phosphor, Y
₂ O ₂ S: Eu, Y ₂ O ₃ : Eu, (Zn, Cd) S:
ZnS: Ag, Cl, ZnS: Ag, Al, Zn as blue phosphors such as Ag, Zn ₃ (PO ₄ ) ₂ : Mn
S: Ag, etc., as green phosphor, ZnS: Cu, Al,
ZnS: Au, Al, ZnS: Cu, Au, Al, Zn
₂ SiO ₄ : Mn, As and the like can be exemplified.

As the resist agent, a combination of polyvinyl alcohol, ammonium dichromate (ADC), sodium dichromate (SDC), a crosslinking agent such as diazonium and polyvinyl alcohol, polyvinylpyrrolidone, casein or a stibasol type resist is used. can do.

In the present invention, a substance which solubilizes the polymer electrolyte which has become insoluble in water or the like by forming a salt again with the polymer electrolyte in which a part of the salt is dissociated is added to the phosphor dispersion liquid. Blend into. This substance may also serve as a resist that cross-links polyvinyl alcohol and the like by irradiation with light. Examples of such substances include LiC
1, LiNO ₃ , NaCl, Na ₂ CO ₃ , Na ₂ S ₂
There are various salts of alkali metals such as O ₃ , NaOH, sodium dichromate (SDC) and ammonium dichromate (ADC), metal hydroxides and ammonium salts. These can be used alone or in a mixture.

In the present invention, when an ammonium salt of acrylic acid-based or acrylic acid-based copolymer is used as a dispersant, a preferable substance capable of forming a two-layer film without deteriorating peelability is an alkali. Is a metal salt,
A compound containing Li or Na ions having a small ionic radius is preferable, and sodium dichromate (SDC) is particularly preferable.

By mixing and stirring the above-mentioned resist agent and phosphor with pure water, a phosphor dispersion liquid for forming the second layer can be obtained. The mixing ratio of the phosphor dispersion liquid is 1 to 40% by weight of the phosphor, 0.1 to 10% by weight of the polymer substance constituting the resist agent, and the alkali metal salt.
The range of 0.1 to 40% by weight is preferable for achieving both the dissolution property and the development property.

Next, the developing solution in the process of exposing and developing will be described. As the developer, when the pigment dispersion and the phosphor dispersion are aqueous solvents, warm water or an alkaline aqueous solution can be preferably used, preferably 35 ° C. or higher warm water or PH 8 or higher alkaline aqueous solution is used. That is.

The manufacturing method of the present invention is carried out by the following procedure, for example, when a phosphor layer with a filter is formed on a color cathode ray tube panel. First, the pigment dispersion is applied to the inner surface of the face plate and dried. As a coating method, the inner surface of the face plate is fixed in a predetermined direction such as upward, sideways, or downward, and the coating is performed. The pigment dispersion can be selected depending on the solid content, viscosity, uneven coating, etc., so that uniform coating can be performed. Further, as a coating method, a spin coating method, a roller method, a dipping method or the like can be used.
The spin coating method is particularly preferable in order to obtain a uniform and predetermined film thickness. As a drying method, various methods can be adopted without particular limitation as long as water can be volatilized and a part of the salt in the polymer electrolyte salt can be dissociated. For example, the first layer can be formed by drying with a heater, drying with hot air, or drying at room temperature for a long time. It is also possible to form a patterned light absorbing layer on the inner surface of the face plate before forming the first layer. Next, the phosphor dispersion liquid is applied in the same manner as the first layer, and the second layer is formed by superimposing it on the first layer. Finally to the desired pattern through the shadow mask,
For example, exposure is performed using a high pressure mercury lamp or the like. After that, development is performed by atomizing the developing solution and spraying it. The above operation is performed for each color.

[0026]

When the pigment layer is formed on the substrate, the salt of the polyelectrolyte is used as a dispersant and the coating is dried, whereby part of the salt in the polyelectrolyte salt is dissociated to form the pigment layer. It becomes insoluble in the solvent for forming the phosphor layer. For example, polyacrylic acid ammonium salt forms polyacrylic acid and becomes insoluble in water. Therefore, a good two-layer film can be formed without mixing the pigment layer and the phosphor layer.

On the other hand, if the liquid for forming the phosphor layer contains Li or Na ions that form a salt again with the polymer electrolyte, these ions diffuse into the first layer film when the phosphor layer is formed. It is considered that the compound replaces the salt of the polymer electrolyte and becomes soluble in the solvent. For example, the above-mentioned polyacrylic acid becomes polyacrylic acid sodium salt and becomes soluble in water.

Therefore, by developing after that,
The soluble first layer is patterned with the second layer. That is, in the case of a negative resist, the unexposed area is developed together with the second layer, and the exposed area is covered with the second layer and remains as it is on the substrate. By this method, a two-layer film pattern that is inexpensive and does not elute and has good developability can be stably obtained.

[0029]

【Example】

Example 1 Of the phosphor layers with a filter, the blue phosphor layer was formed on the inner surface of the face plate of the color cathode ray tube. The pigment dispersion is cobalt aluminate (trade name: Cobalt Blue X
(Particle size, 0.01 μm to 0.02 μm, manufactured by Toyo Pigment Co., Ltd.)
30% by weight, and an ammonium salt of a polyacrylic acid copolymer (Despec GA-40 (manufactured by Allied Colloid Co.)) at 0.3% by weight were dispersed in pure water. The polymer electrolyte concentration / pigment concentration ratio in this example is 0.01.

The phosphor dispersion liquid is a blue phosphor (ZnS: A
g, Cl) 40 g, sodium dichromate (SDC)
A suspension of the phosphor was prepared by weighing and mixing 0.16 g, polyvinyl alcohol (average molecular weight 2400, saponification degree 88%) 1.4 g and pure water 54 g.

The color cathode ray tube panel was maintained at a temperature of 30 ° C. and the pigment dispersion liquid was applied to the inner surface of the face plate.
The panel was then spun at 100-150 rpm to shake off excess pigment dispersion. It was dried at a heater temperature of 120 ° C. for 3 to 4 minutes to form a blue pigment layer.

The phosphor dispersion liquid is applied to the inner surface of the face plate on which the blue pigment layer is formed by the same method as described above,
It was rotated at 230 rpm to shake off excess phosphor dispersion.
A blue phosphor layer was formed on the blue pigment layer by drying at a heater temperature of 120 ° C. for 2 to 3 minutes.

Through a shadow mask, a high-pressure mercury lamp was used to expose to a predetermined pattern. The atomized developer was sprayed at a developer pressure of 2 to 10 kg / cm ² for development to obtain a blue phosphor layer with a blue filter having a predetermined pattern. The developer used was pure water at 40 ° C.

The obtained phosphor layer with a filter was evaluated by the following characteristics. Dissolution property: Dissolution means that the first layer film is dissolved by the second layer liquid, the first layer component is mixed with the second layer film, and the second layer component is mixed with the first layer film. It means to end up. The elution characteristics were evaluated based on how much the absorptivity of the absorption peak of reflection of the first pigment layer deteriorated as compared with the case where no elution occurred. When the sample is not deteriorated at all, it is ○, and when it is deteriorated compared with the absorption rate when it is not eluted, 80
% Is left, and less is marked with x.

Adhesive force characteristic: Adhesive force means a characteristic that a two-layer film remains in an exposed portion after development. When the exposed area is 100%, it is ○, over 80% and 100%
When it was less than Δ, Δ was given, and when 80% or less, it was given x.

Peelability: Peelability refers to how much the non-exposed area drops after development. Unexposed area is 100
% When it fell, was rated as over 80% and less than 100%, and x when 80% or less. Table 2 shows the evaluation results.

Examples 2 to 7 A blue phosphor layer with a blue filter was obtained by the same material and method as in Example 1 except that the blending ratio in the pigment dispersion was changed. Table 1 shows the mixing ratio in the pigment dispersion liquid. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.

Comparative Example 1 and Comparative Example 2 The same materials as in Example 1 except that the blend ratio of polymer electrolyte concentration / pigment concentration in the pigment dispersion was 0.0033 (Comparative Example 1) and 1.5 (Comparative Example 2). A blue phosphor layer with a blue filter was obtained by the method. Table 1 shows the mixing ratio in the pigment dispersion liquid. The obtained phosphor layer with a filter was used in Example 1.
It evaluated by the same method as. Table 2 shows the evaluation results.

Comparative Examples 3 and 4 Pigment dispersions were prepared by using 30% by weight of cobalt aluminate (trade name: Cobalt Blue X (particle size, 0.01 μm to 0.02 μm, manufactured by Toyo Pigment Co., Ltd.)) and polyacrylic acid copolymer A combined sodium salt (Despec G-40 (manufactured by Allied Colloid Co.)) was prepared by dispersing 1.5% by weight (Comparative Example 3) and 15% by weight (Comparative Example 4) in pure water. Example 1
Using the same phosphor dispersion liquid as in Example 1, a blue phosphor layer with a blue filter was obtained in the same manner as in Example 1. Table 1 shows the mixing ratio in the pigment dispersion liquid. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.

Comparative Examples 5 to 13 In the blue phosphor dispersion liquid, sodium dichromate (S
Blue phosphor layers with blue filters were respectively obtained by the same materials and methods as in Examples 1 to 7 and Comparative Examples 1 and 2 except that ammonium dichromate (ADC) was used instead of DC). . The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3 together with the pigment dispersion composition.

[0041]

[Table 1]

[Table 2]

[Table 3] As shown in Table 2, when the sodium salt of the polyacrylic acid copolymer is used in the pigment dispersion (Comparative Example 3 and Comparative Example 4), the elution characteristics are poor. When the pigment layer is formed by the coating and drying method, it is not appropriate to use the non-volatile, non-combustible salt alone.

In Comparative Example 1 in which the dispersant / pigment ratio was 0.0033, the peeling property was poor and good patterning could not be performed. It is considered that this is because the amount of polyelectrolyte is small, and even if the polyelectrolyte is solubilized by the alkali metal ions contained in the phosphor dispersion liquid, the binding force between pigment particles becomes strong and the polyelectrolyte does not dissolve in the developer. To be Further, Comparative Example 2 in which the dispersant / pigment ratio was 1.50 had poor elution characteristics. It is considered that this is because the amount of the polymer electrolyte was too large and the pigment layer was solubilized before the drying of the phosphor dispersion liquid was completed.

As shown in Tables 1 and 2, a two-layer film pattern having excellent elution characteristics was stably obtained over a wide range of the dispersant / pigment ratio from 0.005 to 1.00.

Example 8 A blue phosphor layer with a blue filter was obtained by using the same material and method as in Example 1 except that ultramarine blue was used instead of cobalt aluminate in the pigment dispersion liquid. When the obtained phosphor layer with a filter was evaluated by the same method as in Example 1, the same result as in Example 1 was obtained. Example 2
From Example 2, the amount of the dispersant was changed in the same manner as in Example 7 to prepare and evaluate a blue phosphor layer with a blue filter.
The same result as that shown in was obtained.

Example 9 A blue phosphor layer with a blue filter was obtained by using the same material and method as in Example 1 except that ZnS: Ag, Al was used as the blue phosphor. When the obtained phosphor layer with a filter was evaluated by the same method as in Example 1, the same result as in Example 1 was obtained. Further, when the amount of the dispersant was changed and the blue phosphor layer with the blue filter was prepared and evaluated in the same manner as in Examples 2 to 7, the same results as those shown in Table 2 were obtained.

Examples 10 to 51 Example 1 except that the pigment dispersions shown in Table 4 and the phosphor dispersions shown in Table 5 were prepared and the combinations shown in Table 6 were used.
A blue phosphor layer with a blue filter was obtained by the same method as described above. However, in Examples 10 to 28, the temperature of the developing solution was set to 25 ° C. and PH was set to 7.0, and in Examples 29 to 51, the temperature of the developing solution was 40 ° C. and PH was 9.
Set to 0. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 6 and 7. Table 6 shows the evaluation results when the developer temperature was set to 25 ° C and PH was set to 7.0. Table 7 shows the developer temperature.
These are the evaluation results when 40 ° C and PH were set to 9.0.

Comparative Example 14 to Example 31 Example 1 except that the pigment dispersions shown in Table 4 and the phosphor dispersions shown in Table 5 were prepared and the combinations shown in Table 6 were used.
A blue phosphor layer with a blue filter was obtained by the same method as described above. However, in Comparative Examples 14 to 24, the temperature of the developing solution was set to 25 ° C. and PH was 7.0, and in Comparative Examples 25 to 31, the temperature of the developing solution was 40 ° C. and PH was 9.
Set to 0. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 6 and 7. Table 6 shows the evaluation results when the developer temperature was set to 25 ° C and PH was set to 7.0. Table 7 shows the developer temperature.
These are the evaluation results when 40 ° C and PH were set to 9.0.

[0048]

[Table 4]

[Table 5]

[Table 6]

[Table 7] Example 52 Of the phosphor layers with a filter, the blue phosphor layer was formed on one surface of the plate glass. The same material as in Example 1 was used for the pigment dispersion and the phosphor dispersion. Flat glass temperature 30
The pigment dispersion was applied while maintaining the temperature at 0 ° C. Then, the panel
The excess pigment dispersion was shaken off by rotating at 100 to 150 rpm. It was dried with hot air at a hot air temperature of 70 ° C. for 3 to 4 minutes to form a blue pigment layer. Apply the phosphor dispersion liquid on the glass surface on which the blue pigment layer is formed by the same method as described above, and 150 to 230 rpm.
It was rotated by and the excess phosphor dispersion liquid was shaken off. Hot air temperature
A blue phosphor layer was formed on the blue pigment layer by drying with hot air at 70 ° C. for 2 to 3 minutes. The pattern was exposed through a mask using a high pressure mercury lamp. The atomized developer was sprayed at a developer pressure of 2 to 10 kg / cm ² for development to obtain a blue phosphor layer with a blue filter having a predetermined pattern. When the obtained phosphor layer with a filter was evaluated by the same method as in Example 1, the same results as those shown in Table 2 were obtained.

Example 53 Of the phosphor layers with a filter, the red phosphor layer was formed on the inner surface of the face plate of the color cathode ray tube. The pigment dispersion liquid is fine particles of Fe ₂ O ₃ (particle diameter, 0.01 μm to 0.0
2 μm) in an amount of 25% by weight, and an ammonium salt of polyoxyethylene alkyl ether sulfate (Hitenol 0
8 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) at a concentration of 0.25% by weight in pure water. The polymer electrolyte concentration / pigment concentration ratio in this example is 0.01.

The phosphor dispersion liquid is a red phosphor (Y ₂ O
₂ S: Eu) 40 g, sodium dichromate (SDC)
0.16 g, polyvinyl alcohol (average molecular weight 2400,
A saponification degree of 88%) of 1.4 g and pure water of 54 g were weighed and mixed to prepare a phosphor suspension.

Using the above pigment dispersion and phosphor dispersion, a red phosphor layer with a red filter was obtained in the same manner as in Example 1. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.

Examples 54 to 58 Example 53 except that the blending ratio in the pigment dispersion is changed.
The phosphor layer with a filter obtained by the same material and method as in Example 1 was evaluated by the same method as in Example 1. Table 8 shows the blending ratio in the pigment dispersion liquid and the evaluation results.

Comparative Example 32 and Comparative Example 33 The same materials as in Example 53 except that the blend ratio of polymer electrolyte concentration / pigment concentration in the pigment dispersion was 0.003 (Comparative Example 14) and 1.5 (Comparative Example 15), A red phosphor layer with a red filter was obtained by the method. The obtained phosphor layer with a filter was evaluated in the same manner as in Example 1. Table 8 shows the blending ratio in the pigment dispersion liquid and the evaluation results.

[0054]

[Table 8] Example 59 A red phosphor layer with a red filter was obtained using the same material and method as in Example 53 except that Y ₂ O ₃ : Eu was used as the red phosphor. When the obtained phosphor layer with a filter was evaluated by the same method as in Example 53, the same result as in Example 53 was obtained. In addition, Example 54 to Example 5
When a red phosphor layer with a red filter was prepared and evaluated by changing the amount of the dispersant in the same manner as in No. 8, the same results as shown in Table 8 were obtained.

Example 60 Among the phosphor layers with a filter, the green phosphor layer was formed on the inner surface of the face plate of the color cathode ray tube.

The pigment dispersion is TiO ₂ --NiO--CoO.
-ZnO (Product name Typyroxide TM Green # 33
20, particle size, 0.01 μm to 0.02 μm, manufactured by Dainichiseika Co., Ltd.)
30% by weight, ammonium salt of polyacrylic acid copolymer (Despec GA-40, manufactured by Allied Colloid Co.)
Was prepared by dispersing 0.3% by weight in pure water.
The polymer electrolyte concentration / pigment concentration ratio in this example is 1 /
It is 100.

The phosphor dispersion liquid is a green phosphor (ZnS: C).
u, Al) 40 g, sodium dichromate (SDC)
0.16 g, polyvinyl alcohol (average molecular weight 2400,
A saponification degree of 88%) of 1.4 g and pure water of 54 g were weighed and mixed to prepare a phosphor suspension.

Using the above pigment dispersion liquid and phosphor dispersion liquid, a green phosphor layer with a green filter was obtained in the same manner as in Example 1. When the obtained phosphor layer with a filter was evaluated by the same method as in Example 1, the same result as in Example 1 was obtained.

Example 61 A blue phosphor layer with a blue filter was formed on the inner surface of a color cathode ray tube face plate by the same method as in Example 1, and then a red phosphor layer with a red filter was formed by the same method as in Example 53. A green phosphor layer with a green filter was formed and patterned in the same manner as in Example 60 to obtain a favorable two-layer pattern of blue, red and green phosphor particles with a filter.
A two-layer film pattern having excellent elution characteristics was stably obtained over a wide working range during formation of each color pattern and between each color. Furthermore, the obtained color CRT had excellent contrast and color purity.

[0060]

In the method for producing a phosphor layer with a filter of the present invention, the step of forming the pigment layer on the substrate comprises applying a salt solution of a polymer electrolyte containing pigment particles to the substrate, and at least in a polymer electrolyte salt. Is a step of dissociating and drying a part of the salt, and a step of forming the phosphor layer is a step of using a solution containing a polyelectrolyte in which a part of the salt is dissociated and a substance that forms a salt again. Therefore, in the case of performing patterning by single overexposure, two contradictory characteristics, elution characteristics and development characteristics, can be compatible. As a result, it is possible to obtain a fluorescent layer with a filter of a cathode ray tube or a color receiver having excellent contrast and color purity with a wide working width.

[0061]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takashi Chigusa 1-9-2 Harara-cho, Fukaya-shi, Saitama Inside Fukaya Electronics Factory, Toshiba Corp. (72) Inventor Kazuo Sakai 2-chome, 23-2 Obana, Kawanishi-shi, Hyogo Fuji dye company (72) Inventor Katsu Fukuda 2-23-2 Obana, Kawanishi city, Hyogo prefecture Fuji dye company

Claims (2)

[Claims] 1. A filter having a step of forming a pigment layer on a substrate, a step of forming a phosphor layer on the pigment layer, and a step of simultaneously exposing and developing the pigment layer and the phosphor layer. In the method for producing a phosphor layer, the step of forming a pigment layer on the substrate is a step of applying and drying a salt solution of a polymer electrolyte containing pigment particles on the substrate, and the step of forming the phosphor layer is A method for producing a phosphor layer with a filter, which is a step of using a solution containing a substance that forms a salt with a polymer electrolyte. 2. The method for producing a phosphor layer with a filter according to claim 1, wherein the salt solution of the polymer electrolyte and the solution containing a substance forming a salt with the polymer electrolyte are water-based solvents. A method for producing a phosphor layer with a filter, which is used.