JPH0645784B2 - Color cathode ray tube manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color CRT. More specifically, the present invention relates to a method for producing a color cathode ray tube for forming a phosphor slurry for forming a phosphor film, which gives a phosphor film with little color mixture and has high exposure sensitivity.

[0002]

2. Description of the Related Art As is well known, in a phosphor screen of a color television cathode ray tube, blue, green and red light emitting dots or stripes made up of blue, green and red light emitting component phosphors are repeatedly and regularly arranged on a face plate. It is a thing. The fluorescent film of this color television picture tube is produced by an optical printing method. That is,
First, the first luminescent component phosphor is dispersed in a photosensitive resin solution such as an aqueous solution of polyvinyl alcohol activated with dichromate to prepare a phosphor slurry. The obtained phosphor slurry is applied to the entire face plate by an appropriate application method such as spin coating (slurry application), and then the application surface is irradiated with energy rays such as ultraviolet rays in a predetermined pattern to irradiate energy rays. The resin in the exposed area is cured to make it insoluble (exposure). Then, the energy ray non-irradiated portion (resin uncured portion) is dissolved and removed by a solvent or the like (development) to form dots or stripes of the first luminescent component phosphor. With respect to the second and third luminescent component phosphors, the same series of slurry coating, exposure and development operations as described above are sequentially repeated to form dots or stripes composed of the second and third luminescent component phosphors. In this case, the dots or stripes of the first, second, and third light-emitting component phosphors do not overlap with each other, and the energy beam irradiation must be controlled so that they are repeatedly and regularly arranged on the face plate. It goes without saying that it will not happen. Next, the fluorescent film containing the resin component obtained as described above is baked at an appropriate temperature to decompose and volatilize the resin component to obtain the target fluorescent film.

In forming a fluorescent film for a color television cathode ray tube by an optical printing method using the above-mentioned phosphor slurry, (1) forming dots or stripes having a sufficient thickness and (2) ) Forming dots or stripes of a predetermined shape on the face plate at a predetermined position, (3) One emission component phosphor is not mixed with another emission component phosphor, that is, no color mixture occurs.
(4) It is required that the phosphor slurry has high exposure sensitivity and good workability. Conventionally, for the purpose of satisfying the above-mentioned matters, various compositions of phosphor slurries, preparation methods, etc. Research has been conducted. The existing phosphor slurry satisfies the above items to some extent. However, since a higher quality fluorescent film is always required commercially, it is desired to further improve the above items.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for manufacturing a color cathode ray tube, which further improves the above items (3) and (4).

That is, an object of the present invention is to provide a method for manufacturing a color cathode ray tube which provides a fluorescent film with little color mixture.

Another object of the present invention is to provide a method of manufacturing a color cathode ray tube for forming a phosphor slurry for forming a phosphor film having high exposure sensitivity.

Conventionally, in order to improve the dispersibility relating to the above item (1), the surface of the phosphor is treated with a silicic acid compound such as metasilicate in an aqueous solution containing potassium water glass and zinc ions such as zinc sulfate. The method was known (Japanese Patent Publication 50-157)
47, USP. 2704726). However,
This surface treatment method differs from the treatment used in the present invention in structure and effect.

[0008]

The method of manufacturing a color cathode ray tube according to the present invention which achieves the above object, is a method for producing blue, green and red light emitting dots or stripes of fluorescent material of blue, green and red light emitting components on a face plate. In the method of manufacturing a color cathode ray tube for forming a film,
Using the phosphor film as the blue-emitting component phosphor, silver activated zinc sulfide phosphor (ZnS: Ag), silver and aluminum activated zinc sulfide phosphor (ZnS: Ag, Al), and blue pigment particles for these phosphors, respectively. At least one of the pigmented phosphors to which is attached, Zn as the green light emitting component phosphor
S: Cu, Al phosphor and ZnS: Au, mixed phosphor of Al phosphor, ZnS: Cu, Al phosphor, gold, copper and aluminum activated zinc sulfide phosphor (ZnS: Au, Cu,
Al), at least one of copper- and aluminum-activated zinc cadmium sulfide phosphor [(Zn, Cd) S: Cu, Al], and europium-activated yttrium oxysulfide phosphor (Y ₂ O) as the red light-emitting component phosphor. ₂ S: Eu), europium-activated yttrium oxide phosphor (Y ₂ O ₃ : E)
u), and at least one of the pigmented phosphors having red pigment particles attached to these phosphors,
In addition, a phosphor having a surface-treating substance containing zinc hydroxide attached to at least one of these phosphors is used, and the phosphor film is formed by an optical printing method comprising coating a slurry of these phosphors, exposing and developing the slurry. The feature is that they are sequentially formed.

In addition, phosphors such as silicon dioxide, magnesium, zinc, calcium, aluminum and the like are attached to conventional phosphors for color television to improve the dispersibility of the phosphor for color television in the phosphor slurry. (A substance that improves the dispersibility of these phosphors for color television will be referred to as a "dispersant" in the present specification), and it is known that a good fluorescent film can be obtained by this. The surface treatment with the dispersant can be used in combination with the phosphor used in the above.

When a color television Braun tube fluorescent film is produced by an optical printing method using the manufacturing method of the present invention, the resulting fluorescent film has very little color mixture. Further, the phosphor slurry used in the present invention has a high exposure sensitivity, so that the ultraviolet irradiation time (exposure time) for curing can be shortened and the work efficiency can be increased.

The present invention will be described in detail below.

The method of manufacturing a color cathode ray tube of the present invention comprises the following steps, for example.

First, the phosphor is put in pure water and sufficiently suspended. Next, an appropriate amount of an aqueous solution containing zinc ions is added to this suspension, and then an alkali is added to the suspension containing zinc ions to adjust the pH value of the suspension to 7.5 to 11, and zinc hydroxide is added. A surface treatment substance containing [hereinafter abbreviated as Zn (OH) ₂ ] is deposited. Precipitated fine particles of Zn (OH) ₂
Are adsorbed on the phosphor surface. The suspension is allowed to stand and Zn (O
H) _{2 The} fluorescent substance to which fine particles are attached is allowed to settle, and then the supernatant is removed by decantation. Washing with water is repeated several times to remove residual ions, followed by dehydration and drying.
After drying, the obtained lumpy phosphor is loosened through a sieve to obtain the phosphor used in the present invention.

Aqueous solutions containing zinc ions include water-soluble zinc compounds such as zinc sulfate (ZnSO ₄ ), zinc acetate [Zn (CH ₃ COO) ₂ ], zinc nitrate [Zn (N
O ₃ ) ₂ ], zinc halide (ZnX ₂ , where X is a halogen excluding fluorine) and the like are used. Alkali hydroxide is used as the alkali for adjusting the pH value. For example, sodium hydroxide (NaOH) and potassium hydroxide (KO) are used.
H), ammonium hydroxide (NH ₄ OH) and the like are used as an aqueous solution. When NH ₄ OH is used, if it is added in excess, a soluble ammine complex ion is produced and Zn (OH) ₂
Since it does not precipitate, it is necessary to take care that the pH value does not exceed 10.

Drying is performed at a temperature of 250 ° C. or lower, preferably 200
It is carried out at a temperature below ℃. When drying is performed at a temperature higher than 250 ° C., all the Zn (OH) ₂ attached to the phosphor is changed to a zinc oxide compound (hereinafter abbreviated as ZnO), so that the phosphor used in the present invention cannot be obtained. 200 to
When drying at 250 ° C, part of Zn (OH) ₂ is Zn
Although it changes to O (naturally, the higher the temperature becomes, the higher the rate of conversion to ZnO), the ZnO produced does not have any adverse effect on the phosphor slurry characteristics. When drying at a temperature below 200 ° C, conversion to ZnO hardly occurs,
Zn (OH) ₂ remains almost as it is.

In the present invention, the amount of Zn (OH) ₂ attached to the color television phosphor is preferably more than 0 parts by weight and 0.7 parts by weight or less based on 100 parts by weight of the color television phosphor. The amount of Zn (OH) ₂ attached is 0.
When the amount is more than 7 parts by weight, the dispersibility of the obtained phosphor in the phosphor slurry gradually deteriorates, and when the phosphor film is formed, color mixing remarkably occurs, which is not preferable. The more preferable Zn (OH) ₂ deposition amount is 0.1.
01 to 0.5 parts by weight. Zn attached to the phosphor
It is convenient to use concentrated aqueous ammonia to quantify (OH) ₂ . Concentrated ammonia water does not react with phosphors for color televisions, which are mainly sulfides or oxides, or ZnO generated when a high drying temperature is adopted, but selectively reacts with Zn (OH) ₂ . This produces soluble ammine complex ions. Therefore, by treating the phosphor of the present invention with concentrated ammonia water to dissolve and separate Zn (OH) ₂ as an ammine complex ion, and quantifying this ammine complex ion, the amount of Zn (OH) ₂ attached can be known.

When a dispersant is used in combination in the phosphor used in the present invention, the dispersant is first attached to the phosphor for color television by a conventional method, and then Zn (OH) 2 is added by the above-mentioned method. ₂ may be attached or vice versa. Examples of the dispersant include silicon dioxide (SiO ₂ ), ortho, meta, or pyrophosphates such as magnesium, zinc, calcium, aluminum [Mg
₃ (PO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , Ca ₃ (P
O ₄ ) ₂ , AlPO ₄ , Mg (PO ₃ ) ₂ , Zn (PO
₃ ) ₂ , Ca (PO ₃ ) ₂ , Al (PO ₃ ) ₃ , Mg ₂
P ₂ O ₇ , Zn ₂ P ₂ O ₇ , Ca ₂ P ₂ O _{7 and the} like] are used, but it is particularly preferable to use SiO ₂ . The dispersant is applied to the phosphor by methods known in the art.
For example, in the case of SiO ₂ , the phosphor is first suspended in a water glass aqueous solution, and then an aqueous solution of zinc sulfate, aluminum sulfate, etc. is added to this suspension to precipitate SiO ₂ fine particles and at the same time. A method of adsorbing on the surface of the phosphor is adopted.

From a practical point of view, the phosphors used in the present invention include silver-activated zinc sulfide phosphor (ZnS: Ag) as a blue-emitting component phosphor, silver- and aluminum-activated zinc sulfide phosphor (ZnS: Ag). , Al), ZnS: Ag phosphor with cobalt aluminate blue pigment particles, ZnS: Ag with cobalt aluminate blue pigment particles, at least one of Al phosphors, and ZnS: Cu, A as a green light emitting component phosphor.
l Phosphor and ZnS: Au, Al phosphor mixed phosphor, Z
nS: Cu, Al phosphor, gold, copper and aluminum activated zinc sulfide phosphor (ZnS: Au, Cu, Al), copper and aluminum activated zinc sulfide / cadmium phosphor [(Zn, Cd) S: Cu, At least one of Al],
Europium-activated sulfide yttrium phosphor as the red-emitting component phosphor _{(Y 2 O 2 S: Eu} ), europium-activated yttrium oxide phosphor _{(Y 2 O 3: Eu)} , Y with red iron oxide red pigment particles ₂ O ₂ S : Eu phosphor, red iron oxide pigment Y ₂ O ₃ : Eu phosphor, cadmium sulphate red pigment particle Y ₂ O ₂ S: Eu phosphor, cadmium sulphate red pigment particle Y ₂ O ₃ : Those containing at least one kind of Eu phosphor are preferable.

[0019]

The effects of the present invention will be described with reference to the case of a phosphor slurry using a ZnS: Ag blue light emitting component phosphor.

There are two types of color mixing between the phosphors of the light emitting components in the color television cathode ray tube phosphor film.
One is that when the first light emitting component phosphor or the second light emitting component phosphor is slurry-coated, exposed, and developed to form dots or stripes on the face plate, other light emission that is formed thereafter. This is the case where the phosphor remains at the positions of the dots or stripes of the component phosphor, which causes color mixing, and such residue of the phosphor is called “haze”. The other is that when the second luminescent component phosphor or the third luminescent component phosphor is slurry-coated, exposed and developed to form its dots or stripes, the other luminescent component phosphors already formed are Phosphor adheres and remains on dots or stripes, and such color mixture is "cross contamination."
Called. The haze occurs depending on the characteristics of the phosphor slurry used, but the cross contamination occurs depending on both the characteristics of the phosphor slurry used and the characteristics of the underlying dots or stripes already formed. It is a thing.

The phosphor slurry used in the production method of the present invention remarkably improves color mixing due to any of the above-mentioned haze and cross contamination.

FIG. 1 shows that when a phosphor slurry of ZnS: Ag phosphors (including a deposition amount of 0) having Zn (OH) ₂ is used,
It is a graph which shows the relationship between Zn (OH) ₂ adhesion amount and haze. The graph of FIG. 1 was obtained as follows. First, 0.15 parts by weight of S is added to 100 parts by weight of ZnS: Ag phosphor.
ZnO using ZnS: Ag phosphor with iO ₂ attached
7 types of Zn (O) _{2 with} different amounts of (OH) ₂
H) ₂ -attached ZnS: Ag phosphor was manufactured. Zn (OH) ₂ -attached ZnS: Ag phosphor and Zn (O)
H) ₂ -free ZnS: Ag phosphor (0.15 wt%
SiO ₂ of using eight phosphor attached) as a sample. The eight types of phosphor samples were also used to obtain the graphs of FIGS. 2 to 5 described later. Next, using these phosphor samples, stripes were formed on the face plate as follows.

First, a phosphor slurry was prepared by an ordinary method using a conventionally used ammonium dichromate-containing polyvinyl alcohol aqueous solution and each phosphor sample. Next, each phosphor slurry obtained is spin-coated on the face plate of a 16-inch cathode ray tube, dried, and then irradiated with ultraviolet rays from a high-pressure mercury lamp through a shadow mask to expose the coated surface in a stripe shape,
Developed with warm water to form stripes. The stripe forming method was also applied to the case of obtaining the graphs of FIGS. Using a magnifying projection microscope, a part of the face plate with stripes formed as described above
Magnify it 100 times and copy it on the screen, and then on the screen in the unexposed area, that is, the area between stripes
20mm × 20mm (0.2mm × 0.2mm on face plate)
The number (haze) of the phosphor particles remaining inside was counted.
For each phosphor slurry sample, the number of phosphor particles was counted at two locations, and the average value was used to determine the Zn (OH) ₂ attachment amount of each phosphor sample (parts by weight relative to 100 parts by weight of ZnS: Ag phosphor). To obtain the graph of FIG.

As is apparent from FIG. 1, Zn (OH) ₂
It can be seen that the haze decreases as the adhesion amount increases. Especially when the amount of Zn (OH) ₂ deposited is up to 0.5 parts by weight, Zn
The decrease in haze with an increase in the amount of (OH) ₂ adhered is remarkable,
When the amount of Zn (OH) ₂ deposited is 0.5 parts by weight, the haze is Zn
It becomes about 1/10 of the case where the amount of (OH) ₂ attached is 0.

2 to 3 show Zn (OH) ₂ attached ZnS:
6 is a graph showing the relationship between the amount of Zn (OH) ₂ adhered and the cross-contamination of other phosphors of the luminescent component of the phosphor when using a phosphor slurry of Ag phosphor (including the adhered amount 0). There are two possible cases of cross contamination. One is cross-contamination that adheres to the luminescent component phosphor that has already been applied (this is called "cross-contamination with the pre-coated luminescent component phosphor"), and the other is applied after that. This is cross-contamination to which the luminescent component phosphor adheres (referred to as "cross-contamination with the post-coated luminescent component phosphor"). Figure 2 shows Zn (OH) ₂
Adhering ZnS: Ag phosphor (including an adhering amount of 0) Zn (O
H) ₂ Adhesion amount and pre-coating of the phosphor ZnS: Cu, A
1 is a graph showing a relationship of cross contamination with a green light emitting component phosphor, and FIG. 3 shows Zn (OH) ₂ attached Z
ZnS (OH) _{2 of} nS: Ag phosphor (including 0 attached amount)
6 is a graph showing the relationship between the amount of adhesion and cross-contamination between the phosphor and the post-applied Y ₂ O ₂ S: Eu red light-emitting component phosphor. 2 to 3, the cross contamination (vertical axis) is represented by the values of blue output / green output and red output / blue output, respectively, and these values were measured as follows.

Referring to FIG. 2, first, ZnS: Cu, Al.
A phosphor slurry sample was applied onto a face plate on which stripes of a green light emitting component phosphor [Zn (OH) ₂ untreated] were previously formed, dried, and then developed with warm water without exposure. After performing the above work (obviously, the stripe of ZnS: Ag phosphor is not formed), the stripe of ZnS: Cu, Al phosphor is 3650.
It is excited by angstrom ultraviolet rays, the emitted light is split by a half mirror, and the split two lights are received by Photomal through the green and blue Ratten filters respectively, and the output of each is measured to determine the blue output / green output. The value was calculated. The value of blue output / green output of each phosphor sample was obtained, and the value of Zn (OH) ₂ deposition amount of 0 was standardized as 1, and the Zn (OH) ₂ deposition amount of each phosphor sample (ZnS: A
g by weight relative to 100 parts by weight of phosphor).

As for FIG. 3, first, a phosphor slurry sample was applied, exposed and developed to form stripes. Next, a Y ₂ O ₂ S: Eu red light emitting component phosphor [Zn
(OH) ₂ untreated] was applied as a slurry, dried, and then developed with warm water without exposure. After performing the above-mentioned work (obviously, no stripe of Y ₂ O ₂ S: Eu phosphor was formed), the stripe of the sample was excited by 3650 angstrom ultraviolet rays, the light emission was split by the half mirror, and the two split Light was received by Photomul through the blue and red Ratten filters, respectively, and the respective outputs were measured to obtain the values of red output / green output. The red output / green output value was calculated for each phosphor sample, and Zn (O
The H) ₂ deposition amount of 0 was standardized as 1 and plotted against the Zn (OH) ₂ deposition amount of each phosphor slurry sample (parts by weight relative to 100 parts by weight of ZnS: Ag phosphor).

2 to 3, as the values of blue output / green output and red output / blue output increase, ZnS: A increases.
It means that there is a lot of cross-contamination of pre-coated ZnS: Cu and Al phosphors of g phosphor and post-coated Y ₂ O ₂ S: Eu phosphor of ZnS: Ag phosphor.

As is clear from FIG. 2, Zn (OH) ₂
It can be seen that the cross-contamination to the pre-coated luminescent component phosphor decreases as the amount of adhesion increases. Especially when the amount of Zn (OH) ₂ attached is up to 0.5 parts by weight, Zn (OH) _2
2 The decrease of cross contamination with the increase of the adhered amount is remarkable.

As is clear from FIG. 3, the cross-contamination with the post-coated light emitting component phosphor is Zn (O).
H) ₂ Zn (OH) _{2 up} to 0.2 to 0.3 parts by weight
₂ It decreases as the amount of Zn (OH) ₂ increases, but it begins to increase on the contrary when the amount of Zn (OH) ₂ further increases.
_{When the} amount of ₂ attached is about 0.7 parts by weight, it becomes the same as when the amount of attached Zn (OH) ₂ is 0. In the present invention, Zn (O
The upper limit of the amount of H) ₂ adhered is preferably 0.7 parts by weight based on this finding.

As described above, one of the reasons why the increase in the amount of Zn (OH) ₂ adhered is to increase the cross-contamination with the post-coated luminescent component phosphor is that the amount of Zn (OH) ₂ adhered is increased. It is considered that when the value exceeds a certain value, the dispersibility of the phosphor deteriorates.
That is, when the dispersibility is poor, when a stripe is formed, unevenness is likely to occur on the back surface of the stripe (the surface on which the post-coating is performed), and thus cross-contamination with the post-coating luminescent component phosphor is likely to occur. Zn (O
H) ₂ Z of ZnS: Ag phosphor (including 0 attached)
FIG. 4 shows the relationship between the amount of n (OH) ₂ attached and the dispersibility of the phosphor.

In FIG. 4, dispersibility (vertical axis) is represented by sedimentation volume. The value of this settling volume is the same as that of phosphor sample 5.
g was put in 30 g of an aqueous solution of polyvinyl alcohol containing ammonium dichromate, and the mixture was allowed to settle in a settling tube for 24 hours, the volume was read, and converted into volume per 1 g. The larger the sedimentation volume value, the worse the dispersibility.

As is clear from FIG. 4, the dispersibility is Zn
(OH) up to ₂ adhesion amount of about 0.5 parts by weight Zn (OH) ₂
Almost the same as when the amount of deposition is 0, but Zn (OH) ₂
It can be seen that when the amount of deposition is more than 0.5 parts by weight, it becomes worse as the amount of Zn (OH) ₂ deposition increases. As described above, the upper limit of the amount of Zn (OH) ₂ adhered in the present invention is preferably 0.7 in view of cross-contamination with the post-coated luminescent component phosphor, but considering this dispersibility, Zn The amount of (OH) ₂ adhered is more preferably 0.5 part by weight or less. The dispersibility can be improved to some extent by adding a surfactant to the phosphor slurry or selecting the surfactant.

The phosphor slurry used in the present invention remarkably enhances the exposure sensitivity.

[0035] Figure 5 is Zn (OH) ₂ deposited ZnS: Ag phosphor and Zn (OH) ₂ adhesion amount (adhesion amount including 0), a certain width using a phosphor slurry using that phosphor (2
It is a graph showing the relationship with the exposure time required to form a stripe of 30 μm). As is clear from FIG.
Zn (OH) 2 up to about 1.2 parts by weight of n (OH) _{2
2 The} same stripe can be obtained with a shorter exposure time than when the amount of adhesion is 0. That is, when the amount of Zn (OH) ₂ attached is more than 0 parts by weight and about 1.2 parts by weight, the exposure sensitivity of the phosphor slurry is improved. Especially Zn (OH) ₂
When the adhesion amount is 0.05 to 1.0 part by weight, the exposure sensitivity is remarkably improved. Therefore, by using the phosphor slurry having such improved exposure sensitivity, the exposure time can be shortened and the work efficiency can be increased. Further, when the exposure time is the same as when the Zn (OH) ₂ deposition amount is 0, the light amount of the light source can be reduced to obtain the same stripe, and therefore the light source life can be extended. As described above, it is not clear why the exposure sensitivity of a phosphor slurry using a phosphor to which an appropriate amount of Zn (OH) ₂ is attached is improved, but Zn (OH) ₂ or partially dissolved Zn ⁺⁺ causes fluorescence. It is considered that this is because it acts as a catalyst in the body slurry and accelerates the photopolymerization of the photosensitive resin.

Although the effect of the present invention has been described above by taking the case of the ZnS: Ag phosphor as an example, it was confirmed that the same effect can be obtained in the case of other phosphors for color television. It was also confirmed that the same effect can be obtained in the case of the color television phosphor that has been subjected to the dispersant treatment or the color television phosphor that has not been subjected to the dispersant treatment.

As described above, the manufacturing method of the present invention provides a color television CRT fluorescent film having a remarkably little color mixture, and significantly enhances the exposure sensitivity of the phosphor slurry, and its industrial utility value. , Is a very big one.

[0038]

EXAMPLES The present invention will now be described with reference to examples.

Example 1 Green light-emitting component phosphor obtained by mixing ZnS: Cu, Al phosphor and ZnS: Au, Al phosphor in a weight ratio of 7: 3.
1000 g was suspended in 2 liters of pure water. To this suspension was added 15 g of water glass (Okaseal A made by Tokyo Ohka, containing 20% by weight of SiO ₂ ) and stirred, and 10% of zinc sulfate was added.
90 g of aqueous solution was added. After stirring for 10 minutes, the stirring was stopped, the phosphor was allowed to settle, and the supernatant was removed by decantation. Then, the phosphor was washed twice with 5 liters of pure water.
In this way, the surface treatment with SiO ₂ is completed, and Si
A phosphor having O ₂ attached was obtained.

Next, the SiO ₂ -attached phosphor obtained as described above was suspended in 2 liters of pure water, 28 g of a 10% aqueous solution of zinc sulfate was added to this suspension, and then the mixture was stirred. The pH value of the suspension was adjusted to 10.0 with aqueous NaOH solution.
After adjusting the pH, stirring was continued for another 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decantation, and the phosphor was washed once with 5 liters of pure water.
Then, the phosphor was suction-dehydrated and dried at 150 ° C. for 3 hours.
After drying, the phosphor was sieved with a 250 mesh sieve.

The phosphor was subjected to surface treatment with a surface treatment and Zn (OH) ₂ by SiO ₂ as described above, and SiO ₂ and Zn (OH) ₂ is attached, Zn
The amount of (OH) ₂ deposited was 0.14 parts by weight with respect to 100 parts by weight of the mixed green light emitting component phosphor.

Next, a phosphor slurry is prepared by a usual method using the phosphor obtained as described above and an ordinary aqueous solution of ammonium dichromate-containing polyvinyl alcohol, and a coating test is conducted using the obtained phosphor slurry. Then, the color mixture (haze and cross contamination) and the exposure sensitivity (exposure time) were examined. The results are shown in Table 1 above as S.
The results are shown in comparison with the case of the mixed phosphor (only the values in parentheses in Table 1) in which only the surface treatment with iO ₂ was performed and the surface treatment with Zn (OH) ₂ was not performed. Cross-contamination is ZnS: Ag phosphor as a blue light emitting component phosphor,
Post-coated Zn when Y ₂ O ₂ S: Eu phosphor is used as the red light emitting component phosphor [all untreated with Zn (OH) ₂ ], green, blue and red light emitting component phosphors are applied in this order.
S: Ag Cross-contamination (blue output / green output) with the blue light emitting component phosphor and post-coating Y ₂ O ₂ S:
The cross contamination (red output / green output) with the Eu red light emitting component phosphor was measured.

As is clear from Table 1, Zn (OH) ₂
The phosphor which had been surface-treated with (1) had less color mixture in the phosphor film and higher exposure sensitivity of the phosphor slurry than the phosphor which had not been surface-treated with Zn (OH) ₂ .

Example 2 1000 g of ZnS: Au, Cu, Al green light emitting component phosphor was suspended in 2 liters of pure water, and 23.6 g of a 20% aqueous solution of zinc chloride was added to this suspension, followed by stirring. While NH ₄
The pH value of the suspension was adjusted to 8.0 with an aqueous OH solution. After adjusting the pH, stirring was continued for another 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decantation, and the phosphor was washed twice with 5 liters of pure water. Then, the phosphor was suction-dehydrated and dried at 100 ° C. for 8 hours. After drying, the phosphor was sieved with a 250 mesh sieve.

Zn (OH) ₂ adheres to the ZnS: Au, Cu, Al phosphors which have been surface-treated with Zn (OH) ₂ as described above, and the amount of Zn (OH) ₂ adhered. Was 0.26 parts by weight with respect to 100 parts by weight of the ZnS: Au, Cu, Al phosphor.

Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry to obtain mixed colors (haze and cross contamination). Nation) and exposure sensitivity (exposure time). The results are shown in Table 1 above.
ZnS: A without surface treatment with (OH) ₂
It is shown in comparison with the case of u, Cu and Al phosphors (values in parentheses in Table 1). For cross contamination, ZnS: Ag phosphor was used as the blue light emitting component phosphor, and Y ₂ O ₂ S: Eu phosphor was used as the red light emitting component phosphor [both Zn
(OH) ₂ untreated], the green, blue, and red light-emitting component phosphors are applied in this order, and then cross-contamination with the ZnS: Ag blue light-emitting component phosphor (blue output /
(Green output) and post-coating Y ₂ O ₂ S: Eu cross-contamination (red output / green output) with the red light emitting component phosphor was measured.

As is clear from Table 1, Zn (OH) ₂
The ZnS: Au, Cu, Al phosphors whose surface was treated with ZnS: Au, C were not subjected to this treatment.
The color mixture in the phosphor film was smaller than that of the u and Al phosphors, and the exposure sensitivity of the phosphor slurry was high.

Example 3 1000 g of ZnS: Ag blue light emitting component phosphor was suspended in 2 liters of pure water and surface-treated with SiO _{2 in the same} manner as in Example 1 to obtain a phosphor with SiO ₂ attached. Obtained.

Next, the phosphor having SiO ₂ obtained as described above was suspended in 2 liters of pure water, and 18.7 g of a 10% aqueous solution of zinc acetate was added to the suspension, followed by stirring. While adjusting the pH value of the suspension to 9.0 with aqueous NaOH solution. After adjusting the pH, stirring was continued for another 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decantation, and further washed with 5 liters of pure water twice. Then, the phosphor was suction-dehydrated and dried at 200 ° C. for 3 hours. After drying, the phosphor was sieved with a 250 mesh sieve.

Zn surface-treated with SiO ₂ and Zn (OH) ₂ as described above
SiO ₂ and Zn (OH) ₂ were attached to the S: Ag phosphor, and the amount of Zn (OH) ₂ attached was 0.08 parts by weight with respect to 100 parts by weight of the ZnS: Ag phosphor.

Next, using the phosphor obtained as described above, a phosphor slurry was prepared in the same manner as in Example 1, and a coating test was conducted using the obtained phosphor slurry to obtain mixed colors (haze and cross contamination). Nation) and exposure sensitivity (exposure time). The results are shown in Table 1 above.
_This is shown in comparison with the case of the ZnS: Ag phosphor (only the values in parentheses in Table 1) in which only the surface treatment with ₂ was performed and the surface treatment with Zn (OH) ₂ was not performed. The cross contamination is ZnS: C as a green light emitting component phosphor.
u, Al phosphor, Y ₂ O as a red light emitting component phosphor
Pre-coated ZnS: Cu, Al green light emitting component phosphor when ₂ S: Eu phosphor is used [all untreated with Zn (OH) ₂ ] and green, blue and red light emitting component phosphors are applied in this order. Contamination (blue output / green output) and post-coating Y ₂ O ₂ S: Eu Red cross-contamination with red light emitting component phosphor (red output / blue output)
Was measured.

As is clear from Table 1, Zn (OH) ₂
The surface treated ZnS: Ag phosphor had less color mixture in the phosphor film and higher exposure sensitivity of the phosphor slurry than the ZnS: Ag phosphor not subjected to this treatment.

Example 4 1000 g of ZnS: Ag, Al blue light-emitting phosphor was suspended in 2 liters of pure water, 67 g of 20% aqueous solution of zinc nitrate was added to this suspension, and then KOH aqueous solution was added with stirring. The pH value of the suspension was adjusted to 11.0. After adjusting the pH, stirring was continued for another 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decantation, and the phosphor was washed once with 5 liters of pure water. Then, the phosphor was suction-dehydrated and dried at 150 ° C. for 3 hours. After drying, the phosphor was sieved with a 250 mesh sieve.

The ZnS: Ag, Al phosphor, which has been surface-treated with Zn (OH) ₂ as described above, contains Zn
(OH) ₂ was attached, and the amount of Zn (OH) ₂ attached was 0.51 parts by weight with respect to 100 parts by weight of the ZnS: Ag and Al phosphors.

Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry to obtain mixed colors (haze and cross contamination). Nation) and exposure sensitivity (exposure time). The results are shown in Table 1 above.
ZnS: A without surface treatment with (OH) ₂
g, shown in comparison with the case of Al phosphor (value in parentheses in Table 1). For cross contamination, ZnS: Cu, Al phosphor was used as the green light emitting component phosphor, and Y ₂ O ₂ S: Eu phosphor was used as the red light emitting component phosphor [both Zn
(OH) ₂ untreated], pre-coating when green, blue and red light emitting component phosphors are applied in this order. Cross-contamination (blue output / green output) and post coating with ZnS: Cu, Al green light emitting component phosphor. The cross contamination (red output / blue output) with the Y ₂ O ₂ S: Eu red light emitting component phosphor was measured.

As is clear from Table 1, Zn (OH) ₂
The ZnS: Ag, Al phosphor that had been subjected to the surface treatment with 1. had less color mixture in the phosphor film and higher exposure sensitivity of the phosphor slurry than the ZnS: Ag, Al phosphor that had not been subjected to this treatment.

Example 5 1000 g of the Y ₂ O ₂ S: Eu red light-emitting component phosphor was suspended in 2 liters of pure water, and 112 g of a 10% aqueous solution of zinc sulfate was added to this suspension, which was then stirred. The pH value of the suspension was adjusted to 9.0 with an aqueous NH ₄ OH solution. 5 more after pH adjustment
Stirring was continued for a minute. After stopping stirring and allowing the phosphor to settle,
The supernatant was removed by decantation, and the phosphor was washed with 5 liters of pure water three times. Then, the phosphor was suction-dehydrated and dried at 130 ° C. for 6 hours. After drying the phosphor 2
Sifted through a 50 mesh screen.

For the Y ₂ O ₂ S: Eu phosphor which has been surface-treated with Zn (OH) ₂ as described above, Zn
(OH) ₂ was attached, and the amount of Zn (OH) ₂ attached was 0.57 parts by weight with respect to 100 parts by weight of the Y ₂ O ₂ S: Eu phosphor.

Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry to obtain mixed colors (haze and cross contamination). Nation) and exposure sensitivity (exposure time). The results are shown in Table 1 above.
Y ₂ O not surface-treated with (OH) _2
2 Shown in comparison with the case of S: Eu phosphor (values in parentheses in Table 1). The cross contamination is ZnS: Ag phosphor as a blue light emitting component phosphor, ZnS: Cu, Al phosphor as a green light emitting component phosphor [both are Zn (OH)
₂ untreated], pre-coated ZnS: Cu when green, blue, and red light-emitting component phosphors are applied in this order, cross-contamination with Al green light-emitting component phosphor (red output / green output), and pre-coated ZnS: Ag Cross contamination with blue light emitting component phosphor (red output / blue output)
Was measured.

As is clear from Table 1, Zn (OH) ₂
The surface-treated Y ₂ O ₂ S: Eu phosphor is
This treatment was not carried out Y ₂ O ₂ S: Eu less color mixture in the fluorescent film than phosphor, also had a higher exposure sensitivity of the phosphor slurry.

Example 6 1000 g of Y ₂ O ₂ S: Eu red light emitting component phosphor with red iron oxide red pigment particles was suspended in 2 liters of pure water, and surface treatment with SiO ₂ was performed in the same manner as in Example 1. , Si
A phosphor having O ₂ attached was obtained.

The SiO ₂ -attached phosphor obtained as described above was suspended in 2 liters of pure water, and 56 g of a 10% aqueous solution of zinc sulfate was added to this suspension, which was then stirred. The pH value of the suspension was adjusted to 8.0 with aqueous NaOH solution.
After adjusting the pH, stirring was continued for another 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant was removed by decantation, and further washed with 5 liters of pure water twice. After that, the phosphor was suction-dehydrated and dried at 200 ° C. for 3 hours. After drying, the phosphor was sieved with a 250 mesh sieve.

For the Y ₂ O ₂ S: Eu phosphor with red iron oxide red pigment particles which have been surface-treated with SiO ₂ and Zn (OH) ₂ as described above, SiO
₂ and Zn (OH) ₂ are attached to the Zn (OH) _2.
The amount of ₂ attached was 0.30 part by weight with respect to 100 parts by weight of the Y ₂ O ₂ S: Eu phosphor with red iron oxide pigment particles.

Next, using the phosphor obtained as described above, a phosphor slurry was prepared in the same manner as in Example 1, and a coating test was conducted using the obtained phosphor slurry to obtain a mixture of colors (haze and cross contamination). Nation) and exposure sensitivity (exposure time). The results are shown in Table 1 above.
Performed only _two due to the surface treatment, Zn (OH) ₂ red iron was not performed to a surface treatment using red pigment particles with Y ₂
It is shown in comparison with the case of O ₂ S: Eu phosphor (values in parentheses in Table 1). For the cross contamination, ZnS: Ag phosphor was used as the blue light emitting component phosphor, and ZnS: Cu, Al phosphor was used as the green light emitting component phosphor [both Zn
(OH) ₂ untreated], pre-coating when green, blue and red light emitting component phosphors are applied in this order: cross contamination (red output / green output) and pre-coating with ZnS: Cu, Al green light emitting component phosphor The cross contamination (red output / blue output) with the ZnS: Ag blue light emitting component phosphor was measured.

As is clear from Table 1, Zn (OH) ₂
Red iron oxide with red pigment particles surface-treated with Y ₂
The O ₂ S: Eu phosphor had less color mixture in the phosphor film and a higher exposure sensitivity of the phosphor slurry than the Y ₂ O ₂ S: Eu phosphor with red red pigment particles not subjected to this treatment.

[0066]

[Table 1]

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the Zn (OH) ₂ attached amount of Zn (OH) ₂ attached ZnS: Ag phosphor (including an attached amount of 0) and haze.

[2] Zn _{(OH) 2} deposited ZnS: and Zn (OH) ₂ coating weight of Ag phosphor (adhesion amount including 0), before application ZnS of phosphor slurry: Cu, and Al green-emitting component phosphor Graph showing the relationship of cross contamination

[Figure 3] Zn (OH) ₂ deposited ZnS: Ag phosphor and Zn (OH) ₂ adhesion amount (adhesion amount including 0), coated Y ₂ O ₂ S after the phosphor slurry: Eu red emitting component phosphor Graph showing the relationship of cross contamination with the body

FIG. 4 is a graph showing the relationship between the Zn (OH) ₂ deposition amount of Zn (OH) ₂ -attached ZnS: Ag phosphors (including a deposition amount of 0) and the dispersibility of the phosphor.

FIG. 5: Zn (OH) ₂ adhering ZnS: Ag phosphor (including adhering amount 0) of Zn (OH) ₂ adhering amount and a phosphor slurry using the phosphor having a constant width (230 μm). Graph showing the relationship with the exposure time when forming stripes

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication H01J 29/20 8326-5E // H01J 9/227 C 7161-5E

Claims (1)

[Claims] 1. A method for manufacturing a color cathode ray tube, comprising forming a blue, green and red light emitting dot or stripe fluorescent film made of a blue, green and red light emitting component phosphor on a face plate, wherein the fluorescent film is the blue light emitting component. As a phosphor, silver activated zinc sulfide phosphor (ZnS: A
g), silver and aluminum activated zinc sulfide phosphor (Zn
S: Ag, Al), and at least one kind of pigmented phosphor in which blue pigment particles are attached to these phosphors, and ZnS: Cu, Al phosphor and ZnS: Au, Al phosphor as the green emission component phosphor. Mixed phosphor of ZnS: C
u, Al phosphor, gold, copper and aluminum activated zinc sulfide phosphor (ZnS: Au, Cu, Al), copper and aluminum activated zinc sulfide / cadmium phosphor [(Zn, C
d) S: Cu, Al], europium-activated yttrium oxysulfide phosphor (Y ₂ O ₂ S: Eu) as the red light-emitting component phosphor, europium-activated yttrium oxide phosphor (Y ₂ O ₃₎ : Eu) and at least one pigmented phosphor having red pigment particles attached to each of these phosphors, and at least one of these phosphors having a surface treatment substance containing zinc hydroxide attached thereto: A method for manufacturing a color cathode ray tube, characterized in that the phosphor film is sequentially formed by an optical printing method comprising applying a slurry of these phosphors, exposing, and developing the phosphor.