JPS597748B2 - Pigmented phosphor and its manufacturing method - Google Patents

Description

Detailed Description of the Invention The present invention relates to a phosphor whose surface is coated with pigment particles (one color filter particle) (hereinafter referred to as a pigmented phosphor), particularly a pigmented phosphor for cathode ray tubes for color television, and the production thereof. Regarding the method.

As is well known, when blue pigment particles and red pigment particles are attached to the particle surfaces of the blue and red emitting phosphors of a cathode ray tube for color television, respectively, the emission spectrum changes due to the filter effect of these pigment particles. Part of the visible range is cut out, and the luminescent color becomes clearer.
Furthermore, the reflected light is reduced due to the absorption effect of external light due to the pigment coloring of the fluorescent film, so that the contrast B3 of the image is dramatically improved (Japanese Patent Laid-Open No. 50-56146).

The pigmented phosphor of the above-mentioned color television cathode ray tube requires (1) pigment particles (B3) to be uniformly attached to the surface of the phosphor, (2) adhesion of the pigment particles to the surface of the phosphor (t)3) (3) strong coating of the phosphor. The pigment particles do not fall off B3 during the process, the resin binder B3 used to attach the pigment particles decomposes and evaporates during baking during the formation of the fluorescent film, etc. t)3
required.

Conventionally, pigment particles were dispersed in a suitable water-soluble resin solution such as polyvinylpyrrolidone and a phosphor dispersed in a gelatin solution were mixed and stirred, and the resulting precipitate was dried. They were manufacturing phosphors.

(For example, U.S. Patent No. 3,275,466,
-56146).

However, according to B3 et al., according to this conventional method, it takes 10 days to prepare a pigment particle dispersion, and several hours to prepare a phosphor dispersion.
Furthermore, the drying process takes an extremely long time of several hours, and requires a complicated work process in which careful washing with water must be performed after mixing.

In addition, the phosphor produced by this method is coated with pigment particles on its surface in a state of agglomeration with each other, and in order to obtain a constant phosphor surface coverage, a large amount of pigment particles must be applied. It is necessary to use t)3, resulting in a significant decrease in brightness, and as mentioned above, since the pigment particles t)3 are coated on the phosphor particles in an agglomerated state, light physical friction such as with a ball mill, etc. There was a problem in that the pigment particles B3 and B5 once coated were peeled off. In order to solve the above-mentioned problems, the present applicant previously proposed a pigmented phosphor in which pigment particles are attached to the surface of the phosphor using a mixture coating of gelatin and gum arabic, and a method for producing the same (patent application). No. 51-80296).

Compared to the conventional pigmented phosphor described above, this pigmented phosphor using a mixture of gelatin and gum arabic as an adhesive adheres uniformly and firmly to the surface of the pigment particles (t)3 phosphor without aggregation. Therefore, the luminance and contrast Bj are higher than conventional pigmented phosphors, and the pigment particles are less likely to peel off due to physical friction such as in a ball mill. Pigmented phosphors in which pigment particles are attached to the surface of the phosphor using a mixture coating of gelatin and gum arabic, such as B3, have the following drawbacks, especially in the phosphor coating process.Bj found.

That is, in the fluorescent film coating process, the phosphor slurry is generally rolled for a long period of time in order to improve coating workability and coating film quality, and after coating, excess phosphor slurry is collected and reused. Therefore, the pigmented phosphor is often in a slurry state for several days to several weeks. In such a case, the gelatin and gum arabic mixture coating B3 will rot, and this rot will significantly weaken the adhesion force B3 of the pigment particles, causing the pigment particles B3 to peel off during coating and impairing the properties of the pigmented phosphor. be. The present invention relates to an improvement of a pigmented phosphor and a method for producing the same, which was proposed by applicant B3 in Japanese Patent Application No. 51-80296, and which prevents spoilage of a gelatin and gum arabic mixture film in a slurry state. An object of the present invention is to provide a pigmented phosphor that does not cause peeling of pigment particles in a phosphor coating process and a method for producing the same.

The pigmented phosphor of the present invention is characterized in that pigment particles and organic preservative particles B3 are uniformly adhered to the surface of the phosphor by a coating of a mixture of gelatin and gum arabic. is a phosphor dispersion liquid by uniformly dispersing a phosphor in either an aqueous gelatin solution or an aqueous gum arabic solution, and a phosphor dispersion liquid by uniformly dispersing pigment particles and organic preservative particles in the other. It is produced by the production method of the present invention, which is characterized in that the phosphor dispersion, pigment particles, and organic preservative particle dispersion are mixed as a dispersion.

The present invention will be explained in detail below.

In the production method of the present invention, the phosphor t)3 is added to either the gelatin aqueous solution or the gum arabic aqueous solution.
On the other hand, the pigment particles and organic preservative particles B3 are uniformly dispersed to form a phosphor dispersion liquid B3, and on the other hand, the pigment particles and organic preservative particles B3 are uniformly dispersed to form a pigment particle and organic preservative particle dispersion liquid f)j.

That is, when the phosphor t)3 is dispersed in an aqueous gelatin solution to create a phosphor dispersion t)3, pigment particles and an organic preservative? The particles are dispersed in an aqueous solution of gum arabic to prepare a dispersion of pigment particles and organic preservative particles t)3. Conversely, when the phosphor b'5 is dispersed in an aqueous gum arabic solution to create a phosphor dispersion l)j, the pigment particles and organic preservative particles are dispersed in an aqueous gelatin solution to form a dispersion of pigment particles and organic preservative particles. Bj is created. From the viewpoint of dispersibility, it is more preferable that the pigment particles and the organic preservative particles are dispersed in an aqueous gum arabic solution than in t)3, and therefore, it is more preferable that the phosphor is dispersed in an aqueous gelatin solution. As a method for uniformly dispersing the phosphor or pigment particles and organic preservative particles in the aqueous gelatin solution or aqueous gum arabic solution, conventional dispersion methods using a stirrer, ball mill, sand mill, Sassmeyer mill, etc. are employed. In this case, it is desirable that the phosphor, pigment particles, and organic preservative particles be dispersed as discrete particles in each aqueous solution. The amount of pigment particles relative to the amount of phosphor varies depending on the type of phosphor, the type of pigment particles, the desired amount of pigment particles attached, etc., but is usually 15 parts by weight or less, preferably 0 parts by weight, based on 100 parts by weight of phosphor. .1 to 10 parts by weight of pigment particles t)j are used. Pigment particle amount t)3 When the amount is more than 15 parts by weight per 100 parts by weight of the phosphor, the luminance B3 of the resulting pigmented phosphor is significantly reduced. Also, the amount of organic preservative particles relative to the amount of phosphor varies depending on the type of organic preservative, etc.
3. Organic preservative particles B3 are usually used in an amount of 0.01 part by weight to 1 part by weight, preferably 0.02 part by weight to 0.5 part by weight, per 100 parts by weight of the phosphor. If the amount of organic preservative particles is less than 0.01 part by weight based on 100 parts by weight of the B3 phosphor, the preservative effect B3 in the slurry state is not sufficient, and therefore the pigmented phosphor t)3 remains in the slurry state for a long period of time. In some cases, peeling of pigment particles is observed. On the other hand, when the amount of organic preservative particles exceeds 31 parts by weight, the preservative effect is sufficient. As a result, the adhesion of pigment particles and organic preservative particles to the surface of the phosphor becomes weaker. Furthermore, the amount of gelatin and gum arabic in the gelatin aqueous solution and the gum arabic aqueous solution are both 0.0000000000000000000 with respect to 100 parts by weight of the phosphor.
01 parts by weight to 1.2 parts by weight t) 3 Appropriate. Amount of gelatin and gum arabic f) 3 If both are less than 0.01 part by weight with respect to 100 parts by weight of the phosphor, the adhesion force of pigment particles and organic preservative particles to the surface of the phosphor B3
become weak. On the other hand, gelatin amount and gum arabic amount Bj
If the amount is more than 1.2 parts by weight per 100 parts by weight of the phosphor, the adhesion of pigment particles and organic preservative particles to the surface of the phosphor will improve/l) 3. Aggregation of phosphors with each othert) 3), the workability of coating during the preparation of the fluorescent film is 3 times lower, and the quality is also not good. t)3. Gelatin and gum arabic are each dissolved in a large amount of pure water and used as a dilute aqueous solution of 5% or less. Note that gelatin is divided into alkali-treated gelatin and acid-treated gelatin depending on the manufacturing process t) 3. Either gelatin may be used in the manufacturing method of the present invention ~ The above-mentioned phosphor dispersion, pigment particles, and By mixing and stirring the organic preservative particle dispersion liquid, the pigment particles and organic preservative particles t)5 adhere to the surface of the phosphor and precipitate.

In this case, t)3, which varies depending on the type of gelatin used, the amount of gelatin, the amount of gum arabic, etc., and the pH of the mixed system.
Values are adjusted from 3.0 to 7.0. The precipitate is separated by a known method such as sawabetsu, centrifugation, decantation, etc., washed, and then dried. In this way, it is possible to obtain a pigmented phosphor B3. After mixing and stirring the phosphor dispersion, pigment particles, and organic preservative particle dispersion, the system containing the precipitate is cooled, and formalin, alum, potassium alum, ammonium alum, and chromium alum are added to this. To obtain a pigmented phosphor with further improved adhesion strength to pigment particles and organic preservative particles by adding an appropriate amount of a curing agent such as glutaraldehyde.
l) I can do 3. As a curing agent, formalin and glutaraldehyde B3 are preferred. It goes without saying that the manufacturing method of the present invention is mainly applied to phosphors for color television, but is not necessarily limited to B3, and can be applied to phosphors in general that are commonly used. .

Examples of the phosphor used in the manufacturing method of the present invention include a manganese-activated zinc orthophosphate phosphor [Zn3(PO4)2:Mn], a manganese-activated magnesium silicate phosphor (MgSiO3:Mn), and a red-emitting phosphor. Silver-activated zinc cadmium sulfide phosphor [(Zn,Cd)S:Ag] europium-activated yttrium vanadate phosphor (YVO4
-Eu), europium-activated yttrium oxysulfide phosphor (Y2O2S:Eu), europium-activated yttrium oxide phosphor (Y2O3:Eu), and manganese-activated zinc magnesium fluoride phosphor [( ZnF2.MgF2):Mn], manganese-activated potassium/magnesium fluoride phosphor [(KF.MgF
2):Mn] J manganese activated magnesium fluoride phosphor (MgF2:Mn), silver activated zinc cadmium sulfide phosphor [(Zn,Cd)S:Ag), copper activated zinc cadmium sulfide phosphor [(Zn) , Cd)S:Cu], lead and manganese activated calcium silicate phosphor (CaS!03:Pb,M
n), manganese-activated zinc silicate phosphor (Zn2SlO4:Mn), copper-activated zinc sulfide phosphor (ZnS:Cu), copper- and aluminum-added zinc sulfide phosphor (ZnS:Cu,NO, Copper-activated zinc cadmium sulfide phosphor [(Zn,Cd)S:Cu], zinc-activated zinc oxide phosphor (ZnO:Zn), silver-activated zinc cadmium sulfide phosphor [(Zn,Cd)S:Ag] , silver-activated zinc sulfide selenide phosphor [Zn(S,Se):Ag], calcium tungstate phosphor (CaWO4), silver-activated zinc sulfide phosphor (ZnS:Ag) as a blue or violet emitting phosphor, etc.
), silver and aluminum activated zinc sulfide phosphor (ZnS
:Ag, A2), silver and chlorine activated zinc sulfide phosphor (Z
nS:Ag,C2), cerium-activated calcium/magnesium silicate phosphor (2Ca0.Mg0.2Si02:C
e), terbium-activated yttrium oxysulfide phosphor (Y2
O2S:Tb), titanium-activated calcium/magnesium silicate phosphor [(Ca,Mg)SiO3-Ti], and the like.

These phosphors preferably have an average particle diameter of 33 μm to 12 μm f)3. Further, as the pigment particles used in the production method of the present invention, for example, as red pigment particles, cadmium selenide sulfide [Cd (S1-X,Sex), 0<X
], Bent)3 et al (Fe2O3), cuprous oxide (Cu2O
), cadmium mercury red (CdS+HgS), chromium vermilion (PbCrO4.PbSO4'). Silver vermilion (Hg
S), antimony red (Sb2S3), ferrocyan copper [
Cu2Fe(CN)6] Iodine red (Hgl2), zinc iron red (Zn-Fe), other ceramic pigment particles, etc., as orange or yellow pigment particles, salt-cured lead chromate (PbCrO4), yellow lead (PbCrO4) , loess (Fe2O3.siO2.Ae,2O3), cadmium yellow (CdS), titanium yellow (TlO2-NlO-Sb2O
3) Chrome green {PbCrO) as green pigment particles such as Resurge (PbO), Red Lead (Pb3O4), Zinc Iron Yellow (Zn-Fe), and other ceramic pigment particles.
4+Fe4[Fe(CN)6]3・NH2O}, cobalt green (COO.nZnO), chromium oxide (Cr2O3)
, other ceramic pigment particles, ultramarine blue (3NaA1.Si02.Na2S2), navy blue {F
e4 [Fe(CN)6]3. nH20}, cobalt blue (
COO. nA22O3), cerulean blue (COO.
There are B3 such as nSnO2), copper sulfide (CuS), and other ceramic pigment particles.

These pigment particles used in the production method of the present invention have an average particle diameter of B3O. B3 is preferable if it is 5μ or less. In addition, the organic preservative particles used in the production method of the present invention include salicylic acid, salicylic acid derivatives (phenyl salicylate, etc.),
p-hydroxybenzoic acid, p-hydroxybenzoic acid derivatives (p-hydroxybenzoic acid esters, etc.), dehydroacetic acid, zorpic acid, o-phenyl phenol, chlorophenols (pentachlorophenol, etc.), bisphenols (hexachlorophenol, etc.) Bj, which is generally well-known as a preservative, is used.

These organic preservative particles are dispersed and volatilized in the firing process after the fluorescent film coating process.T)3 Preferably, since the firing is carried out at 450°C to 500°C, the decomposition temperature is below B345°C. B3 is preferred. In addition, the organic preservative particles preferably have an average particle size B3 of the same size as the pigment particles, that is, 0.5μ or less.
3) If the particles are large, it is better to use particles whose average particle diameter is appropriately reduced by crushing them in advance. Further, it is preferable that the organic preservative particles do not change the pH value of the slurry when it is in the state of pigmented phosphor B3 slurry. This is because the pH value of the slurry affects the workability of fluorescent film coating.
From the viewpoint of the quality of the fluorescent film obtained, etc., the pH is 6. It is necessary to maintain the PH value in the range of 0 to 7.5 due to the organic preservative particles attached to the surface of the phosphor together with the pigment particles. This is because it becomes necessary to adjust the pH value. Particularly from this point of view, organic preservative particles having the general formula t)3 (where R is a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group or benzyl group) B5 is preferred, using at least one p-hydroxybenzoic acid ester represented by:

Among the phosphors and pigment particles used in the above-mentioned manufacturing method of the present invention, a particularly preferred combination from the viewpoint of practicality as a phosphor for color television is a europium-activated yttrium oxysulfide red-emitting phosphor (Y2O2S: Eu
) and cadmium selenide sulfate [Cd(S1-X,Sex)
] or Ben B3 et al. (Fe2O3) in combination with red pigment particles and silver activated zinc sulfide (ZnS'.Ag) or silver and aluminum activated zinc sulfide (ZnS:Ag,
Al) Blue-emitting phosphor and cobalt blue (COO.nA22
O3) or ultramarine (3NaAe.S102.Na2S
2) Combination with blue pigment particles.

Among them, the combination with Y2O2S:EU (5Cd(Sl-e・Sex)) and ZnS:Ag or Zn
S:Ag, A2 and COO. The combination with nAl2O3 is the most advanced in practical use B3. According to the experiments of the present inventors,
In the case of a combination of Y2O2S:EU and Cd (SeichiX, Sex) or Fe2O3, Y2O2S:EulOO
Cd (S1-X, Sex) or Fe based on weight part
2O3b3O. When the amount is 1 part by weight to 2 parts by weight, a good pigmented phosphor can be obtained. When the amount of red pigment particles is less than 0.51 parts by weight, the contrast effect B3 is reduced, and when it is more than 2 parts by weight, the luminance B3 is reduced, and in either case, a good pigmented phosphor cannot be obtained. Also ZnS:Ag or ZnS:Ag, Al and C. O. nAe2O3 or 3NaAe-SiO, . In case of combination with Na2S2,
C based on weight part of ZnS:Ag or ZnS:Ag, A2lOO. O. nAe, 2O3 or 3NaALS
102. When the amount of Na2S2t) is 30.5 parts by weight to 10 parts by weight, a good pigmented phosphor t)3 can be obtained. Blue pigment particles B3O. If it is less than 5 parts by weight, the contrast effect B3 will be reduced, and if it is more than 10 parts by weight, the luminance B3 will decrease, and in either case, a good pigmented phosphor cannot be obtained. The pigmented phosphor obtained by the above-mentioned production method of the present invention has pigment particles and organic preservative particles t)3 uniformly adhered to the surface of the phosphor by a mixture coating of gelatin and gum arabic, and the pigment particles The adhesion strength is superior to pigmented phosphors obtained by conventional methods.

In addition, the pigmented phosphor obtained by the above-mentioned production method of the present invention does not have a mixture coating of gelatin and gum arabic that rots even if it is in a slurry state for a long period of time. B3 stripping B3 being exposed B
3 no. Figure 1 shows the results of rolling the Y2O2S:EU phosphor in a slurry state for a long period of time, with red pigment particles attached to the surface of the phosphor using a mixture coating of gelatin and gum arabic. 3 is a graph showing the relationship between the adhesion strength of pigment particles and the pigment particle adhesion strength, and curve a shows the pigment of the present invention in which p-hydroxybenzoate-n-butyl and organic preservative particles are adhered to the surface of the phosphor together with red pigment particles such as Ben B3. In the case of a phosphor (the amount of organic preservative particles is 0.1 parts by weight per 100 parts by weight of the phosphor), curve b is a pigmented phosphor in which only red pigment particles are attached to the surface of the phosphor from Ben B3. This is the case with the body.

In Figure 1, the initial value of the pigment particle adhesion strength is set to 100.
This pigment particle adhesion strength was measured in the same manner as in the practical example described below. As is clear from Fig. 1, in the case of a pigmented phosphor in which only pigment particles are attached to the surface of the phosphor (curve b has a rolling old number t), the adhesion strength of pigment particles gradually decreases as the number increases. B3, in the case of the pigmented phosphor of the present invention (curve a), even if the rolling B3 is prolonged, the pigment particle adhesion strength hardly decreases and remains almost at the initial level.

This means that in the pigmented phosphor of the present invention, the mixture coating of gelatin and gum arabic does not rot even after rolling for a long period of time. In the above-described manufacturing method of the present invention, almost all of the pigment particles and organic preservative particles contained in the pigment particle and organic preservative particle dispersion adhere to the surface of the phosphor.

This means that most of the pigment particles and organic preservative particles B3 remain in the residual liquid after separating the pigmented phosphor precipitate obtained by mixing the phosphor dispersion with the pigment particles and organic preservative particle dispersion. This is confirmed by the fact that no pigment particles and organic preservative particles t)3 are found in the cleaning solution after washing the pigmented phosphor precipitate. On the other hand, gelatin and gum arabic are not all used for adhesion of pigment particles and organic preservative particles, but some of them are used to coat the phosphor surface and make the pigment particles and organic preservative particles fluoresce. Attach it to the body surface. This is because gelatin and gum arabic remain in the residual liquid after separating the pigmented phosphor precipitate obtained by mixing the phosphor dispersion with the pigment particle and organic preservative particle dispersions. This is confirmed from this. According to the present invention, the mixture coating B3 of gelatin and gum arabic does not rot even in a slurry state for a long period of time, and therefore the pigment particles do not peel off in the slurry state, and the pigment particles are uniformly distributed on the surface of the phosphor without agglomeration. Moreover, it is possible to obtain a strongly adhered pigmented phosphor with high brightness and high contrast. As described above, the present invention prevents the adhesive from rotting in the slurry state of a pigmented phosphor using a mixture of gelatin and gum arabic as an adhesive, and thereby prevents peeling of pigment particles. Therefore, its industrial utility value is extremely large. Next, the present invention will be explained with reference to Examples. Practical Example 1 0.8 parts by weight of alkali-treated gelatin was dissolved in warm water at 40°C to prepare a 0.3% gelatin aqueous solution.

Europium-activated yttrium oxysulfide red light-emitting phosphor (Y2O2S:Eu) was added to this 0.3% gelatin aqueous solution.
0 parts by weight was added and sufficiently uniformly dispersed using a stirrer until primary particles were obtained. In this way, a phosphor dispersion liquid was obtained. Meanwhile, 0.5 parts by weight of gum arabic was dissolved in water and 0.3 parts by weight of gum arabic was dissolved in water.
% gum arabic aqueous solution was prepared.

To this 0.3(f) gum arabic aqueous solution, 0.5 parts by weight of Ben B3 red pigment particles (Fe2O3) and 0.1 parts by weight of phenyl salicylate particles as organic preservative particles were added, and the primary particles were mixed using a stirrer. It was sufficiently uniformly dispersed. In this way, a dispersion of pigment particles and organic preservative particles was obtained. Next, the above phosphor dispersion and the pigment particle and organic preservative particle dispersions were mixed without stirring, and the pH value of the mixed solution was adjusted to 4.

After standing, the supernatant liquid was removed by decantation, and the precipitate was washed with water and separated and concentrated in a continuous decanter to obtain a pigmented phosphor cake with a solid content of B3 of about 85%. A pigmented phosphor was obtained by air-flow drying this cake.
This pigmented phosphor is 0.5 parts by weight per 100 parts by weight of the phosphor.
Part by weight of pigment particles and 0.1 part by weight of organic preservative particles t)3 are deposited. Furthermore, when we observed this pigmented phosphor using an electron microscope, we found that the pigment particles and organic preservative particles were uniformly attached to the phosphor surface! l) 3 confirmed. Next, 1 part by weight of the pigmented phosphor described above was dispersed in a solution containing 2 parts by weight of pure water, 1 part by weight of 10(f) polyvinyl alcohol aqueous solution, and 0.015 part by weight of 5% ammonium dichromate aqueous solution. After rolling the phosphor slurry for 10 days, the adhesion strength of the pigmented phosphor to the pigment particles was measured.

As shown in Table 1 below, the adhesion strength of the pigment particles after rolling for 10 days is not much different from the initial adhesion strength of the pigment particles (at the time of slurry preparation). The adhesion strength of the pigment particles was significantly superior to that of the pigmented phosphor attached to the surface of the phosphor.

Practical Example 2 A pigmented phosphor was obtained in the same manner as in Practical Example 1, except that 0.1 part by weight of n-butyl p-hydroxybenzoate was used instead of 0.1 part by weight of phenyl salicylate particles.

This pigmented phosphor is 0.5 parts by weight per 100 parts by weight of the phosphor.
Part by weight of pigment particles and 0.1 part by weight of organic preservative particles are deposited. Further, when this pigmented phosphor was observed under an electron microscope, it was confirmed B3 that the pigment particles and organic preservative particles were uniformly attached to the surface of the phosphor. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the pigmented phosphor described above, and the adhesion strength of the pigment particles was measured after rolling for 10 days.

As shown in Table 1 below, the adhesion strength of pigment particles after rolling for 10 days was not much different from the initial adhesion strength of pigment particles, and only pigment particles without organic preservative particles were attached to the phosphor surface. This was significantly superior to the pigment particle adhesion strength of the pigmented phosphor. Practical Example 3 0.05 parts by weight of n-butyl p-hydroxybenzoate and p
A pigmented phosphor was obtained in the same manner as in Example 1, except that 0.05 parts by weight of -1-propyl-hydroxybenzoate was used.

This pigmented phosphor is 0.5 parts by weight per 100 parts by weight of the phosphor.
Part by weight of pigment particles and 0.1 part by weight of organic preservative particles t)3 are deposited. Further, when this pigmented phosphor was observed under an electron microscope, it was confirmed B3 that the pigment particles and organic preservative particles were uniformly attached to the surface of the phosphor. Next, a phosphor slurry was prepared in the same manner as in Practical Example 1 using the pigmented phosphor described above, and the adhesion strength of the pigment particles was measured after rolling for 10 days. As shown in Table 1 below, the adhesion strength of pigment particles after rolling for 10 days was not much different from the initial adhesion strength of pigment particles, and only pigment particles without organic preservative particles were attached to the phosphor surface. This was significantly superior to the pigment particle adhesion strength of the pigmented phosphor.

[Brief explanation of drawings]

Figure 1 is a graph showing the relationship between the number of low links and the adhesion strength of pigment particles when a pigmented phosphor using a mixture of gelatin and gum arabic as an adhesive is rolled in a slurry state for a long period of time. In the case of the pigmented phosphor of the present invention in which organic preservative particles are attached to the surface of the phosphor along with pigment particles, curve b is for the case of a pigmented phosphor in which only pigment particles are attached to the phosphor surface.

Claims (1)

[Claims] 1. A pigmented phosphor comprising a phosphor, pigment particles and organic preservative particles adhered to the surface of the phosphor by a mixture film of gelatin and gum arabic. 2 The organic preservative particles have a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a methyl group, ethyl group, n-propyl group, i
- Pigmented according to claim 1, characterized in that the pigment is at least one p-hydroxybenzoic acid ester represented by a propyl group, an n-butyl group, an i-butyl group, or a benzyl group. phosphor. 3. The amount of the pigment particles attached is 15 parts by weight or less based on 100 parts by weight of the phosphor, and the amount of the organic preservative particles attached is 0.01 part by weight to 1 part by weight based on 100 parts by weight of the phosphor. The pigmented phosphor according to claim 1, characterized in that: 4 The amount of the pigment particles attached is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the phosphor, and the amount of the organic preservative particles attached is also 0.02 parts by weight to 0.5 parts by weight. The pigmented phosphor according to claim 3, characterized in that: 5. The phosphor is a europium-activated yttrium oxysulfide phosphor, the pigment particles are cadmium selenide sulfide or iron oxide, and the amount of the pigment particles attached is 0.1 parts by weight per 100 parts by weight of the phosphor. 5. The pigmented phosphor according to claim 4, wherein the amount of the pigmented phosphor is 2 to 2 parts by weight. 6 The phosphor is a silver activated zinc sulfide phosphor or a silver and aluminum activated zinc sulfide phosphor, the pigment particles are cobalt blue or ultramarine blue, and the amount of the pigment particles attached is 100 parts by weight of the phosphor. 5. The pigmented phosphor according to claim 4, wherein 0.5 parts by weight to 10 parts by weight of pigment particles are attached to the pigment particles. 7. Uniformly disperse the phosphor in either the gelatin aqueous solution or the gum arabic aqueous solution to obtain a phosphor dispersion,
On the other side, pigment particles and organic preservative particles are uniformly dispersed to form a pigment particle and organic preservative particle dispersion liquid, and the phosphor dispersion liquid and the pigment particles and organic preservative particle dispersion liquid are mixed and applied to the surface of the phosphor. A method for producing a pigmented phosphor, which comprises adhering pigment particles and organic preservative particles. 8 Organic preservative particles have a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a methyl group, ethyl group, n-propyl group, i
- Pigmented according to claim 7, characterized in that the pigment is at least one p-hydroxybenzoic acid ester represented by a propyl group, an n-butyl group, an i-butyl group, or a benzyl group. Method of manufacturing phosphor. 9 A phosphor dispersion is obtained by uniformly dispersing a phosphor in an aqueous gelatin solution, and a dispersion of pigment particles and organic preservative particles is obtained by uniformly dispersing pigment particles and organic preservative particles in an aqueous gum arabic solution. A method for producing a pigmented phosphor according to claim 7. 10 The amount of the pigment particles attached is 15 parts by weight or less with respect to 100 parts by weight of the phosphor, the amount of the organic preservative particles attached is also 0.01 part by weight to 1 part by weight, and the amount of the attached pigment particles is 0.01 part by weight to 1 part by weight, and 8. The method for producing a pigmented phosphor according to claim 7, wherein the amounts are the same in each case from 0.01 parts by weight to 1.2 parts by weight. 11 The amount of the pigment particles attached is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the phosphor, and the amount of the organic preservative particles attached is also 0.02 parts by weight to 0.5 parts by weight. 11. A method for producing a pigmented phosphor according to claim 10. 12 The phosphor is a europium-activated yttrium oxysulfide phosphor, the pigment particles are cadmium selenide sulfide or iron oxide, and the amount of the pigment particles attached is 0.1 parts by weight per 100 parts by weight of the phosphor. 12. The method for producing a pigmented phosphor according to claim 11, wherein the amount is from 2 parts by weight to 2 parts by weight. 13 The phosphor is a silver activated zinc sulfide phosphor or a silver and aluminum activated zinc sulfide phosphor, the pigment particles are cobalt blue or ultramarine blue, and the amount of the pigment particles attached is 100 parts by weight of the phosphor. 12. The method for producing a pigmented phosphor according to claim 11, wherein the amount is 0.5 parts by weight to 10 parts by weight. 14 Disperse the phosphor uniformly in either gelatin aqueous solution or gum arabic aqueous solution to obtain a phosphor dispersion liquid, and uniformly disperse pigment particles and organic preservative particles in the other to obtain pigment particle and organic preservative particle dispersion. The phosphor dispersion liquid is mixed with the pigment particle and organic preservative particle dispersion liquid, and after the mixed liquid is cooled, a curing agent is added thereto to form the pigment particles and organic preservative particles on the surface of the phosphor. A method for producing a pigmented phosphor, which comprises adhering the pigment to the phosphor. 15 The organic preservative particles have a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a methyl group, ethyl group, n-propyl group, i
- Pigmented according to claim 14, characterized in that it is at least one p-hydroxybenzoic acid ester represented by a propyl group, an n-butyl group, an i-butyl group, or a benzyl group. Method of manufacturing phosphor. 16 A phosphor dispersion liquid is obtained by uniformly dispersing a phosphor in an aqueous gelatin solution, and a dispersion liquid of pigment particles and organic preservative particles is obtained by uniformly dispersing pigment particles and organic preservative particles in an aqueous gum arabic solution. A method for producing a pigmented phosphor according to claim 14. 17 The amount of the pigment particles attached is 15 parts by weight or less with respect to 100 parts by weight of the phosphor, the amount of the organic preservative particles attached is also 0.01 part by weight to 1 part by weight, and gelatin and gum arabic The amount of both is the same 0.01
15. The method for producing a pigmented phosphor according to claim 14, wherein the amount is from 1.2 parts by weight to 1.2 parts by weight. 18 The amount of the pigment particles attached is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the phosphor, and the amount of the organic preservative particles attached is also 0.02 parts by weight to 0.5 parts by weight. A method for producing a pigmented phosphor according to claim 17, characterized in that: 19 The phosphor is a europium-activated yttrium oxysulfide phosphor, the pigment particles are cadmium selenide sulfide or iron oxide, and the amount of the pigment particles attached is 0.1 parts by weight per 100 parts by weight of the phosphor. 18. The method for producing a pigmented phosphor according to claim 17, wherein the amount is from 2 parts by weight to 2 parts by weight. 20 The phosphor is a silver activated zinc sulfide phosphor or a silver and aluminum activated zinc sulfide phosphor, the pigment particles are cobalt blue or ultramarine blue, and the amount of the pigment particles attached is 100 parts by weight of the phosphor. 18. The method for producing a pigmented phosphor according to claim 17, wherein the amount is 0.5 parts by weight to 10 parts by weight. 21. The method for producing a pigmented phosphor according to claim 14, wherein the curing agent is formalin. 22. The method for producing a pigmented phosphor according to claim 14, wherein the curing agent is glutaraldehyde.