JPH0913030A - Phosphor for electronic tube and electroluminescent phosphor - Google Patents

Abstract

PURPOSE: To prevent the degradation in adhesion to the surface of a face panel or to obtain sufficient moistune-proof property. CONSTITUTION: In a phosphor for electronic tubes which is formed by activating a yttrium oxysulfide or zinc sulfide matrix with an activator or in an electroluminescent phosphor which is formed by activating a zinc sulfide matrix with an activator and a coactivator, the surface of the phosphor used is treated with an alkylcarboxylic acid deriv.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor, particularly a phosphor for an electron tube or an electroluminescent phosphor.

[0002]

2. Description of the Related Art As a phosphor that emits light by the action of electric energy, a phosphor for an electron tube used in a cathode ray tube for color televisions and color displays,
There are electroluminescent phosphors used as EL elements.

The phosphor for an electron tube has zinc sulfide as a base material, and at least one of copper, aluminum, cadmium, gold and silver.
It is a phosphor for a red photoelectron tube that activates at least one of europium and samarium, which is a phosphor for a blue or green light-emitting electron tube or yttrium oxysulfide that is a matrix that activates more than one kind, and the electroluminescent phosphor is zinc sulfide. Is a phosphor containing copper and manganese as an activator, and chlorine, bromine, iodine, aluminum and the like as a co-activator, and an activator such as copper in a matrix such as zinc sulfide. The main components are common in that they are activated. Further, it is desired to maintain and improve the emission brightness of both phosphors.

The fluorescent substance for electron tubes is composed of a resist solution such as ammonium dichromate (hereinafter abbreviated as ADC),
And, a slurry having a certain viscosity is dispersed in a water-soluble polymer solution such as polyvinyl alcohol (hereinafter abbreviated as PVA) together with various surfactants for improving dispersibility, and this slurry is applied onto a face plate of a cathode ray tube. After that, it is generally dried, and after that, a suitable mask is attached and exposed and developed to be used as a fluorescent film having a desired stripe or dot shape.
Further, these phosphors for electron tubes are usually surface-treated with an inorganic compound such as aluminum oxide, silicon oxide or zinc oxide in order to maintain the binding property with the face plate at a practical level. Further, in the cathode ray tube manufacturing process, a process of laminating a lacquer film and a vapor-deposited film of aluminum follows following the production of the fluorescent film, but in order to make these thin films uniform, it is required to keep the water familiar to the surface of the fluorescent film. Further, surface treatment is generally performed with a polyacrylic acid derivative-based resin such as sodium polyacrylate.

On the other hand, the electroluminescent phosphor, particularly the organic dispersion type electroluminescent phosphor, is dispersed in a dielectric material to form a phosphor layer, and electrodes are arranged on both sides of the phosphor layer and at least one of them is disposed. The electrodes are composed of transparent electrodes, and light is emitted by applying an AC voltage between these electrodes. However, it has been clarified that the electroluminescent phosphor deteriorates rapidly when it emits light in the presence of water. Therefore, a usual dispersion type EL device adopts a structure in which a phosphor layer which is a light emitting layer is sufficiently dried at the time of manufacturing the device and then protected by a moisture-proof film. However, such a distributed EL
Further thinning of the device is desired, and therefore development of a dispersion type EL device without using a moisture-proof film is desired.

[0006]

However, the phosphor for an electron tube, which has been surface-treated by the above-mentioned method, has a large number of side chains of resin on the outermost surface of the phosphor, and also the phosphor slurry. The side chains of the PVA used for the above are intricately entangled with each other, which sometimes causes the aggregation of the phosphors, and as a result, the phosphors are partially peeled off on the phosphor film stripes, resulting in a hole opening. , Or unfavorable development such as a decrease in the adhesion of the phosphor to the face panel. Such a hole vacancy or a phenomenon of reduced adhesiveness is a great obstacle in obtaining high-definition stripes in high-definition TVs that will become the mainstream in the future.
The stable manufacture of high-luminance and high-definition cathode ray tubes, and their widespread use have made it an urgent problem to solve.

Various methods have been investigated as a moisture-proof treatment for electroluminescent phosphors, but they are not sufficient. For example, a method has been proposed in which triethylaluminum is blown into a container containing a phosphor kept at a high temperature and attached as aluminum oxide to the surface of an EL phosphor (JP-A-2-38482, US Pat. No. 4,585,678). ing. Although this method has a large moisture-proof effect, the EL phosphor is exposed to high temperatures, so that the emission luminance tends to decrease and the color tone tends to change greatly. Also, triethylaluminum is explosive and has a safety problem.

Further, a method in which titanium chloride and water vapor are blown into a container containing a phosphor maintained at 100 to 150 ° C. to cause vapor-phase hydrolysis and adhere as titanium oxide to the surface of the EL phosphor (Japanese Patent Laid-Open No. 4-16053). 230996, US Patent 51
56885) has been proposed. Although this method has a large moisture-proof effect, it tends to be difficult to obtain a uniform coating film and the emission luminance tends to be greatly reduced. In addition, titanium chloride is easily hydrolyzed by moisture in the air and is unstable, which causes a problem in handling.

As described above, the conventional moisture-proof treatment for the electroluminescent phosphor itself has a problem that it adversely affects the phosphor characteristics such as maintaining and improving the emission brightness.

The present invention has been made to solve such a problem. In order to maintain and improve the emission brightness of the phosphor, the phosphor for an electron tube has a reduced adhesive force on the face panel surface. In the case of an electroluminescent phosphor that can be prevented, it is an object of the present invention to provide a phosphor that can obtain practically sufficient moisture resistance.

[0011]

A phosphor for an electron tube according to claim 1 is a phosphor for an electron tube which is obtained by activating an activator on a yttrium oxysulfide or zinc sulfide matrix.
The surface of this phosphor is characterized by being treated with an alkylcarboxylic acid derivative.

The electroluminescent phosphor of claim 2 is an electroluminescent phosphor obtained by activating a zinc sulfide matrix with an activator and a co-activator. The surface of the phosphor is treated with an alkylcarboxylic acid derivative. It is characterized by

The phosphor for an electron tube according to claim 3 is the phosphor for an electron tube according to claim 1, wherein the surface treatment amount of the alkylcarboxylic acid derivative is 0.01% by weight (hereinafter wt%) of the phosphor for an electron tube.
Abbreviated name) to 0.20 wt%.

The electroluminescent phosphor according to claim 4 is the electroluminescent phosphor according to claim 2, wherein the surface treatment amount of the alkylcarboxylic acid derivative is 4 × 10 ⁻³ per 100 g of the electroluminescent phosphor.
It is characterized by being in the range of up to 2 × 10 ^-2 mol.

An electron tube phosphor or an electroluminescent phosphor according to claim 5 is the electron tube phosphor according to claim 1 or the electroluminescent phosphor according to claim 2, wherein the alkylcarboxylic acid derivative is an alkyl group having 12 to 20 carbon atoms. It is a carboxylic acid derivative. Here, the carbon number means the total number of carbon atoms of the alkyl group and the carboxyl group.

In the invention of claim 1 or 2,
The alkylcarboxylic acid derivative is represented by the general formula: C _n H _{2n + 1} CO
It is represented by OR and includes straight chain and branched chain. In particular, a linear n-alkylcarboxylic acid derivative is more easily entangled than a branched derivative, which is desirable. R is Na, K,
NH _{2 and the} like can be given.

Further, n is preferably in the range of 11-19. In the phosphor for an electron tube, if n is less than 11, the effect of preventing the agglomeration between the phosphors during the production cannot be sufficiently obtained. When n is 20 or more, the hydrophilicity of the fluorescent film is significantly impaired, which makes it difficult to form a uniform aluminum thin film.

On the other hand, in the electroluminescent phosphor, n is 11
If it is less than the above range, the solubility of the phosphor in water becomes high at the time of production, and sufficient surface treatment characteristics cannot be obtained. When n is 20 or more, the solubility in water is too low and it becomes difficult to form an emulsion used for the treatment.

In the phosphor for an electron tube according to claim 1, the surface treatment amount of the alkylcarboxylic acid derivative is the same as that of the phosphor for an electron tube.
When it is in the range of 0.01 wt% to 0.20 wt%, it is possible to prevent the phosphors from aggregating during the production and form a uniform aluminum thin film.

In the electroluminescent phosphor according to claim 2, the surface treatment amount of the alkylcarboxylic acid derivative is the electroluminescent phosphor 1.
When it is in the range of 4 × 10 ^-3 to 2 × 10 ^-2 mol with respect to 00 g, sufficient moisture resistance can be obtained without lowering the emission brightness of the phosphor.

Next, a method for surface-treating the phosphor for an electron tube according to claim 1 with an alkylcarboxylic acid derivative will be described. Disperse a fixed amount of the alkylcarboxylic acid derivative in pure water or ethanol solution, and heat the dispersion to 80 ℃ to obtain a solution with a constant concentration (about 1wt%). Add this solution to a phosphor dispersion liquid that has been heated to 80 ° C in advance and
Dropwise so that the concentration becomes 1 wt% to 0.20 wt%, and then slowly cool the reaction system to room temperature. The phosphor for an electron tube before the surface treatment with an alkylcarboxylic acid derivative is a surface treatment with a commonly used inorganic compound such as aluminum oxide, silicon oxide or zinc oxide, and subsequent polyacrylic acid amide or polyacrylic acid. It can be performed subsequent to the surface treatment with a polyacrylic acid derivative-based resin such as acid soda.

Further, the phosphor is a phosphor for a red light emitting electron tube, in which yttrium oxysulfide is a base material and at least one activator selected from europium and samarium is used for a blue or green light emitting electron tube. In the phosphor, zinc sulfide is used as a base material, and at least one activator selected from copper, aluminum, cadmium, gold and silver is mixed to prepare a raw material, and then this raw material is mixed. After firing, a predetermined washing process is performed to obtain a phosphor for an electron tube.

A method of surface-treating the electroluminescent phosphor of claim 2 with an alkylcarboxylic acid derivative will be described.
A raw material is prepared by using zinc sulfide as a base, and mixing at least one of copper or manganese as an activator and at least one selected from chlorine, bromine, iodine or aluminum as a co-activator. Next, after firing this raw material, a predetermined cleaning treatment is performed to obtain an EL phosphor.
Next, an alkyl carboxylic acid derivative such as sodium n-alkyl carboxylic acid is added to the dispersion liquid of the EL phosphor and sufficiently stirred, and the phosphor suspension is allowed to stand. In this way, the electroluminescent phosphor is treated with the alkylcarboxylic acid derivative.

[0024]

In the phosphor for an electron tube of the present invention, the surface treatment with the alkylcarboxylic acid derivative is performed subsequently to the surface treatment with the resin, so that the side chains of the resin existing in large numbers on the outermost surface of the phosphor are effectively rounded. Is possible. Therefore, it becomes possible to prevent the aggregation of the phosphors in the phosphor slurry, which can improve the adhesive force of the phosphors. It is particularly effective to perform this treatment after the acrylic emulsion treatment.

By subjecting the electroluminescent phosphor of the present invention to a surface treatment with an alkylcarboxylic acid derivative having excellent hydrophobicity, the reaction between the phosphor surface and adsorbed moisture can be suppressed. This makes it possible to prevent deterioration of the phosphor due to moisture.

[0026]

EXAMPLE The phosphor for an electron tube of the present invention will be described with reference to Examples 1 to 6 and Comparative Examples 1 and 2, and the electroluminescent phosphor with examples 7 to 11 and Comparative Example 3.

Example 1 Yttrium oxide (Y ₂ O ₃ ) was mixed with europium oxide (E
coprecipitation 1.5kg the u ₂ O ₃₎ was added 4.7wt% with Eu terms
1050 g of sodium carbonate (Na ₂ CO ₃ ), 750 g of sulfur (S), and 120 g of potassium phosphate (K ₃ PO ₄ ) were mixed with each other, and this was put into an alumina crucible, and a sulfur atmosphere 115
The product was baked at 0 ° C. for 4 hours, and this baked product was washed with dilute nitric acid several times to obtain a Y ₂ O ₂ S: Eu ⁺ phosphor. This phosphor 1
Disperse kg in 4 liters of pure water, add 12.5 g of red iron oxide dispersion 7.3 wt% and stir for 10 minutes. further
After adding 0.5 ml of a 45 wt% acrylic emulsion solution, adjust the pH to 1.9 with dilute sulfuric acid, stir for 60 minutes, and let stand to remove the supernatant. After that, it was washed three times with warm water at 70 ° C., adjusted to pH 7.0 with diluted ammonia water, and allowed to stand still, and the supernatant was removed. After this, as surface treatment, suspend in 500 ml of pure water, add 25 ml of 25% water glass and 0.4 ml / liter zinc sulfate (ZnSO ₄ ) 2 ml, stir for 30 minutes, and after standing, leave the supernatant liquid to remove pure water. Wash 3 times at.

Further, 1 kg of this phosphor was dispersed in 2 liters of pure water, 330 ml of a 1 wt% polyacrylamide solution was added, and the mixture was heated to 80 ° C. with stirring for 60 minutes, and 1 wt% at 80 ° C.
10 g of a% sodium octadecanoate solution (carbon number = 18) was added. This was filtered, dried at 100 ° C. for 20 hours, and then screened to obtain a red phosphor for an electron tube. Disperse 50 g of this phosphor in 65 ml of pure water, and then add 60 g of PVA and A
DC 3ml, sodium dodecyl sulfate 0.5g, tamol 1
0 ml was added and the mixture was stirred for 24 hours to obtain a phosphor slurry. This phosphor slurry was applied on a cathode ray tube face panel, and a 0.28 pitch dot-shaped mask and filters with different transmittances were attached, and then exposed and developed with 12 mJ / cm ² of ultraviolet rays to produce the fluorescent substance of Example 1. A CRT having a body was obtained.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 1 shows the results. Table 1
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 1, and the effect of improving the adhesive force is recognized.

Example 2 1 wt% sodium octadecanoate solution (carbon number = 18) 10 g
Instead of 1 wt% sodium tetradecanoate solution (carbon number =
14) A cathode ray tube having a red phosphor for an electron tube was obtained by the same material and method as in Example 1 except that 100 g was used.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 1 shows the results. Table 1
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 1, and the effect of improving the adhesive force is recognized.

Example 3 10 g of 1 wt% sodium octadecanoate solution (carbon number = 18)
Instead of 1 wt% sodium dodecanoate solution (carbon number = 12
A cathode ray tube having a red phosphor for an electron tube was obtained by the same material and method as in Example 1 except that 200 g was used.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 1 shows the results. Table 1
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 1, and the effect of improving the adhesive force is recognized.

Comparative Example 1 Europium oxide (E) was added to yttrium oxide (Y ₂ O ₃ ).
coprecipitation 1.5kg the u ₂ O ₃₎ was added 4.7wt% with Eu terms
1050 g of sodium carbonate (Na ₂ CO ₃ ), 750 g of sulfur (S), and 120 g of potassium phosphate (K ₃ PO ₄ ) were mixed with each other, and this was put into an alumina crucible, and a sulfur atmosphere 115
The product was baked at 0 ° C. for 4 hours, and this baked product was washed with dilute nitric acid several times to obtain a Y ₂ O ₂ S: Eu ⁺ phosphor. This phosphor 1
Disperse kg in 4 liters of pure water, add 12.5 g of red iron oxide dispersion 7.3 wt% and stir for 10 minutes. further
After adding 0.5 ml of a 45 wt% acrylic emulsion solution, adjust the pH to 1.9 with dilute sulfuric acid, stir for 60 minutes, and let stand to remove the supernatant. After that, it was washed three times with warm water at 70 ° C., adjusted to pH 7.0 with diluted ammonia water, and allowed to stand still, and the supernatant was removed. After this, as surface treatment, suspend in 500 ml of pure water, add 25 ml of 25% water glass and 0.4 ml / liter zinc sulfate (ZnSO ₄ ) 2 ml, stir for 30 minutes, and after standing, leave the supernatant liquid to remove pure water. Wash 3 times at.

Further, 1 kg of this phosphor was dispersed in 2 liters of pure water, and 330 ml of a 1 wt% polyacrylamide solution was added. This was filtered, dried at 100 ° C. for 20 hours, and then screened to obtain a red phosphor for an electron tube. Disperse 50 g of this phosphor in 65 ml of pure water, and then add 60 g of PVA and A
DC 3 ml, sodium dodecyl sulfate 0.5 g, tamol 10
ml was added and stirred for 24 hours to obtain a phosphor slurry. This phosphor slurry was applied to a cathode ray tube face panel, and a 0.28-pitch dot-shaped mask and filters with different transmittances were attached. Then, the phosphor slurry was exposed to 12 mJ / cm ² of ultraviolet light and developed to develop the fluorescence of Comparative Example 1. A CRT having a body was obtained. The adhesive force of the phosphor was evaluated by the chipping rate of dots with respect to the transmittance. Table 1 shows the results.

[0036]

[Table 1] Example 4 Yttrium oxide (Y ₂ O ₃ ) was mixed with europium oxide (E
u ₂ O ₃ ) is 6.0 wt% in terms of Eu, samarium oxide (S
m ₂ O ₃ ) 0.5 wt% in terms of Sm, terbium oxide (T
b ₂ O ₃ ) 0.3 wt% in terms of Tb
1.5 kg of sodium carbonate (Na ₂ CO ₃ ) 1050 g, sulfur (S) 750 g, lithium phosphate (Li ₃ PO ₄ ) 300
g were mixed and put in an alumina crucible and calcined in a sulfur atmosphere at 1200 ° C. for 4 hours, and the calcined product was washed with dilute nitric acid several times to obtain a Y ₂ O ₂ S: Eu ⁺ phosphor. Disperse 1 kg of this phosphor in 4 liters of pure water, add 12.5 g of red iron oxide dispersion 7.3 wt% and stir for 10 minutes.
Further, 0.5 ml of a 45 wt% acrylic emulsion solution was added, the pH was adjusted to 1.9 with dilute sulfuric acid, the mixture was stirred for 60 minutes, and then allowed to stand to remove the supernatant. After this, use warm water at 70 ° C for 3
It was washed twice, adjusted to pH 7.0 with diluted aqueous ammonia, and allowed to stand still, and the supernatant was removed. After that, as surface treatment, it was suspended in 500 ml of pure water, 0.2 ml of 25% water glass and 2 ml of 0.4 mol / liter zinc sulfate (ZnSO ₄ ) were added, and the mixture was stirred for 30 minutes,
After completion, leave still and remove supernatant and wash with pure water 3 times.

Further, 1 kg of this phosphor was dispersed in 2 liters of pure water, 330 ml of a 1 wt% polyacrylamide solution was added, and the mixture was heated to 80 ° C. while stirring for 60 minutes, and 1 wt% at 80 ° C.
10 g of a% sodium octadecanoate solution (carbon number = 18) was added. This was filtered, dried at 100 ° C. for 20 hours, and then screened to obtain a red phosphor for an electron tube. Disperse 50 g of this phosphor in 65 ml of pure water, and then add 60 g of PVA and A
DC 3ml, sodium dodecyl sulfate 0.5g, tamol 1
0 ml was added and the mixture was stirred for 24 hours to obtain a phosphor slurry. This phosphor slurry was applied on a cathode ray tube face panel, and a 0.60-pitch dot-shaped mask and filters with different transmittances were attached, and then exposed and developed with 12 mJ / cm ² of ultraviolet rays to produce the fluorescent light of Example 4. A CRT having a body was obtained.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 2 shows the results. Table 2
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 2, and the effect of improving the adhesive force is recognized.

Example 5 1 wt% sodium octadecanoate solution (carbon number = 18) 10 g
Instead of 1 wt% sodium tetradecanoate solution (carbon number =
14) A cathode ray tube having a red phosphor for an electron tube was obtained by the same material and method as in Example 4 except that 100 g was used.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 1 shows the results. Table 2
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 2, and the effect of improving the adhesive force is recognized.

Example 6 1 wt% sodium octadecanoate solution (carbon number = 18) 10 g
Instead of 1 wt% sodium dodecanoate solution (carbon number = 12
A cathode ray tube having a red phosphor for an electron tube was obtained by the same material and method as in Example 1 except that 200 g was used.

The adhesive force of the phosphor was evaluated by the dot chipping rate relative to the transmittance. Table 2 shows the results. Table 2
As shown in, the chipping rate at each transmittance is lower than that of the phosphor of Comparative Example 2, and the effect of improving the adhesive force is recognized.

Comparative Example 2 Europium oxide (E) was added to yttrium oxide (Y ₂ O ₃ ).
u ₂ O ₃ ) is 6.0 wt% in terms of Eu, samarium oxide (S
m ₂ O ₃ ) 0.5 wt% in terms of Sm, terbium oxide (T
b ₂ O ₃ ) 0.3 wt% in terms of Tb
1.5 kg of sodium carbonate (Na ₂ CO ₃ ) 1050 g, sulfur (S) 750 g, lithium phosphate (Li ₃ PO ₄ ) 300
g were mixed and put in an alumina crucible and calcined in a sulfur atmosphere at 1200 ° C. for 4 hours, and the calcined product was washed with dilute nitric acid several times to obtain a Y ₂ O ₂ S: Eu ⁺ phosphor. Disperse 1 kg of this phosphor in 4 liters of pure water, add 12.5 g of red iron oxide dispersion 7.3 wt% and stir for 10 minutes.
Further, 0.5 ml of a 45 wt% acrylic emulsion solution was added, the pH was adjusted to 1.9 with dilute sulfuric acid, the mixture was stirred for 60 minutes, and then allowed to stand to remove the supernatant. After this, use warm water at 70 ° C for 3
It was washed twice, adjusted to pH 7.0 with diluted aqueous ammonia, and allowed to stand still, and the supernatant was removed. After that, as surface treatment, it was suspended in 500 ml of pure water, 0.2 ml of 25% water glass and 2 ml of 0.4 mol / liter zinc sulfate (ZnSO ₄ ) were added, and the mixture was stirred for 30 minutes,
After completion, leave still and remove supernatant and wash with pure water 3 times.

Further, 1 kg of this phosphor was dispersed in 2 liters of pure water, and 330 ml of a 1 wt% polyacrylamide solution was added. This was filtered, dried at 100 ° C. for 20 hours, and then screened to obtain a red phosphor for an electron tube. Disperse 50 g of this phosphor in 65 ml of pure water, and then add 60 g of PVA and A
DC 3 ml, sodium dodecyl sulfate 0.5 g, tamol 10
ml was added and stirred for 24 hours to obtain a phosphor slurry. This phosphor slurry was applied to a cathode ray tube face panel, a dot-shaped mask with a pitch of 0.60 and filters with different transmittances were attached, and then exposed and developed with an ultraviolet ray of 12 mJ / cm ² to produce the fluorescence of Comparative Example 2. A CRT having a body was obtained. The adhesive force of the phosphor was evaluated by the chipping rate of dots with respect to the transmittance. Table 2 shows the results.

[0045]

[Table 2] As described in Table 1 and Table 2, the phosphor for electron tube according to the present invention has less aggregation in the slurry and therefore has a higher adhesive force than the phosphor not treated with the alkylcarboxylic acid derivative. Since a good fluorescent film can be obtained, it is particularly effective when manufacturing a high-definition cathode ray tube.

Example 7 Copper sulfate (CuS) was added to a zinc sulfide (ZnS) matrix as an activator.
O ₄ ) and sodium bromide (NaBr) and potassium bromide (KBr) as a co-activator are wet-mixed, and the slurry is dried and then in a hydrogen sulfide (H ₂ S) atmosphere.
It was baked at 900 ° C. for 2 hours to obtain a ZnS: Cu, Br type EL phosphor.

Next, 100 g of this ZnS: Cu, Br type EL phosphor was dispersed in 100 ml of deionized water, 0.004 mol of sodium stearate was added to this dispersion, and the mixture was stirred for 1 hour. Then, the mixture was allowed to stand still, the supernatant was discarded, and then the steps of filtration, drying and sieving were carried out to obtain the intended EL phosphor. Next, using this EL phosphor, an EL panel without a moisture-proof film was prepared using cyanoethyl cellulose as a binder.

An AC voltage of 100 V and 400 Hz was applied to the obtained EL panel, and the initial light emission luminance and the luminance half-life were measured. Table 3 shows the measurement results. As shown in Table 3, compared with the EL panel of Comparative Example 3, the initial emission brightness was almost the same,
The brightness half-life was improved 1.2 times.

Example 8 0.008 mol instead of 0.004 mol sodium stearate
An EL panel without a moisture-proof film was prepared using the same materials and method as in Example 7, except that the sodium stearate of Example 1 was used. An AC voltage of 100 V and 400 Hz was applied to the obtained EL panel, and the initial emission brightness and the brightness half-life were measured.
Table 3 shows the measurement results. As shown in Table 3, E of Comparative Example 3
The initial luminance was almost the same as that of the L panel, and the luminance half time was 1.7 times longer.

Example 9 0.012 mol instead of 0.004 mol of sodium stearate
An EL panel without a moisture-proof film was prepared using the same materials and method as in Example 7, except that the sodium stearate of Example 1 was used. An AC voltage of 100 V and 400 Hz was applied to the obtained EL panel, and the initial emission brightness and the brightness half-life were measured.
Table 3 shows the measurement results. As shown in Table 3, E of Comparative Example 3
Compared to the L panel, the initial emission brightness was almost the same and the brightness half-life was improved by 2.0 times.

Example 10 0.016 mol instead of 0.004 mol of sodium stearate
An EL panel without a moisture-proof film was prepared using the same materials and method as in Example 7, except that the sodium stearate of Example 1 was used. An AC voltage of 100 V and 400 Hz was applied to the obtained EL panel, and the initial emission brightness and the brightness half-life were measured.
Table 3 shows the measurement results. As shown in Table 3, E of Comparative Example 3
Compared with the L panel, the initial emission brightness was almost the same, and the brightness half time was improved by 2.3 times.

Example 11 0.016 mol instead of 0.004 mol of sodium stearate
An EL panel without a moisture-proof film was prepared using the same materials and method as in Example 7, except that the sodium stearate of Example 1 was used. An AC voltage of 100 V and 400 Hz was applied to the obtained EL panel, and the initial emission brightness and the brightness half-life were measured.
Table 3 shows the measurement results. As shown in Table 3, E of Comparative Example 3
Compared with the L panel, the initial emission brightness was almost the same, and the brightness half time was improved by 2.3 times.

COMPARATIVE EXAMPLE 3 Copper sulfate (CuS) was used as an activator on a zinc sulfide (ZnS) matrix.
O ₄ ) and sodium bromide (NaBr) and potassium bromide (KBr) as a co-activator are wet-mixed, and the slurry is dried and then in a hydrogen sulfide (H ₂ S) atmosphere.
It was baked at 900 ° C. for 2 hours to obtain a ZnS: Cu, Br type EL phosphor.

Next, 100 g of this ZnS: Cu, Br type EL phosphor was dispersed in 100 ml of deionized water, allowed to stand and the supernatant liquid was discarded, and then the steps of filtration, drying and sieving were carried out. To obtain an EL phosphor. Next, using this EL phosphor, an EL panel without a moisture-proof film was prepared using cyanoethyl cellulose as a binder. Obtained EL
The initial emission brightness and the brightness half-life were measured by applying an AC voltage of 100 V and 400 Hz to the panel. Table 3 shows the measurement results.

[0055]

[Table 3] As is apparent from Table 3, the luminance half-life of the EL phosphor according to the present invention increases with an increase in the amount of sodium stearate treated, and the moisture-proof effect is increased. In Examples 7 to 11, ZnS: Cu, Br type EL was used.
Although the example using the phosphor has been described, the alkylcarboxylic acid treatment can be applied to various zinc sulfide phosphors using copper or manganese as the activator and chlorine, bromine, iodine, aluminum, etc. as the coactivator. It is valid.

[0056]

In the phosphor for an electron tube according to claim 1, since the surface of the phosphor is treated with the alkylcarboxylic acid derivative, the phosphor is less likely to be aggregated in the slurry, and therefore the phosphor film having a good adhesive force. Is obtained. As a result, a high-luminance, high-definition CRT can be easily manufactured.

In the phosphor for an electron tube according to claim 3, the surface treatment amount of the alkylcarboxylic acid derivative is 0.01 wt% to 0.20 of the phosphor.
Since it is in the range of wt%, the above-mentioned characteristics are more exerted.

In the electroluminescent phosphor according to claim 2, since the surface of the phosphor is treated with an alkylcarboxylic acid derivative,
The moisture resistance can be significantly improved without adversely affecting the characteristics of the phosphor. Therefore, a thinner EL panel can be manufactured, which greatly contributes to practical use.

In the electroluminescent phosphor according to claim 4, the surface treatment amount of the alkylcarboxylic acid derivative is the electroluminescent phosphor 1.
Since it is in the range of 4 × 10 ⁻³ to 2 × 10 ⁻² mol with respect to 00 g, the above-mentioned characteristics are more exerted.

The phosphor for an electron tube or the electroluminescent phosphor according to claim 5 comprises an alkylcarboxylic acid derivative having 12 to 2 carbon atoms.
Since the alkylcarboxylic acid derivative consisting of 0 is obtained, the effect of preventing the aggregation between the phosphors can be sufficiently obtained in the electron tube phosphor, and the sufficient surface treatment property can be obtained in the electroluminescent phosphor.

[0061]

Front page continuation (72) Inventor Kinno Funayama 72 Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Higashi Shiba Horikawa-cho Co., Ltd. (72) Inventor, Megumi Wakui 8 Shinsita-cho, Isogo-ku, Yokohama, Kanagawa (72) Inventor Takeshi Takahara Takeshi Takahara 8 Shinsita-cho, Isogo-ku, Yokohama, Kanagawa, Ltd. Toshiba Corporation Corporate office (72) Inventor Hiroaki Tachiki 8 Shinsita-cho, Isogo-ku, Yokohama, Kanagawa In-house (72) Hiroyasu Yashima, 7-1 Nisshin-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa, Toshiba Electronic Engineering Co., Ltd. (72) In-house, Mashinori Otake, 7 Nisshin-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Toshiba Electronics Engineering Co., Ltd. In the company

Claims (5)

[Claims] 1. A phosphor for an electron tube obtained by activating an yttrium oxysulfide or zinc sulfide matrix with an activator, wherein the surface of the phosphor is treated with an alkylcarboxylic acid derivative. Phosphor. 2. An electroluminescent phosphor obtained by activating a zinc sulfide matrix with an activator and a coactivator, wherein the surface of the phosphor is treated with an alkylcarboxylic acid derivative. Luminescent phosphor. 3. The phosphor for an electron tube according to claim 1, wherein the surface treatment amount of the alkylcarboxylic acid derivative is in the range of 0.01 wt% to 0.20 wt% of the phosphor for an electron tube. Tube phosphor. 4. The electroluminescent phosphor according to claim 2, wherein the surface treatment amount of the alkylcarboxylic acid derivative is 4 × 10 ⁻³ to 2 × 10 ⁻² mo per 100 g of the electroluminescent phosphor.
An electroluminescent phosphor characterized by being in the range of l. 5. The phosphor for an electron tube according to claim 1 or the electroluminescent phosphor according to claim 2, wherein the alkylcarboxylic acid derivative is an alkylcarboxylic acid derivative having 12 to 20 carbon atoms. An electron tube phosphor or an electroluminescent phosphor.