JPS6039311B2 - color cathode ray tube - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color television cathode ray tube having a phosphor film using a cerium-activated multi-component sulfide blue-emitting phosphor as a blue-emitting component phosphor.

The phosphor film of conventional color television cathode ray tubes (hereinafter referred to as color cathode ray tubes) contains copper- and aluminum-activated zinc sulfide phosphor (ZnS:
Cu, AI) or steel and aluminum activated zinc sulfide cadmium phosphor {(Zn,Cd)S:Cu,AI}, silver-activated zinc sulfide phosphor (Z
nS:Ag) or silver- and aluminum-activated zinc sulfide nacophore (ZnS:Ag,AI), europium-activated yttrium oxysulfide nacophore (Y2) as a red-emitting component crabophore (Y2
QS:Eu), europium-activated yttrium oxide photoreceptor (Y203:Eu), or europium-activated yttrium vanadate photoreceptor (YV04:Eu) is used.

Recent color cathode ray tubes have a higher current density due to higher applied voltages and improvements in cathodes, getters, electron guns, etc., and current densities have become significantly higher than in the past. However, among the light emitting components of each color used in the conventional color cathode ray tubes mentioned above, Y20 is a red light emitting component.
Bu: Eu crab photoreceptor, Y203: Eu saddle photoreceptor or YV0
4: ZnS, which is a blue light-emitting component crab light body compared to Eu light body
:Ag crab photon or ZnS:Ag,Ai crab photon, ZnS:Cu,AI crab photon which is a green emitting component crab photon, and (Zn,Cd)S:Cu,AI crab photon has a high There is a drawback that the luminance of the emitted light becomes saturated due to current stimulation. Therefore, there is a strong desire for blue and green light-emitting components whose luminance is difficult to saturate due to high current stimulation, and the white luminance is low for the stimulation current density when such blue and green light-emitting components are used. A color cathode ray tube having a light film that does not exhibit saturation is strongly desired. The present invention is based on the conventional ZnS
:Ag or ZnS:Ag, compared to the wild-colored light-emitting crab light, the luminance is saturated by increasing the stimulation current density. By using the blue light-emitting crab light as the blue light-emitting component crab light, the stimulation The object of the present invention is to provide a color cathode ray tube having a rear light film in which white luminance does not show saturation with respect to current density.

The blue-emitting crab phosphor used in the color cathode ray tube of the present invention has a compositional formula of SrS. It is a cerium-activated multi-component sulfide crab photoresist expressed by 1×10-1 (a number that satisfies the condition of 1×10−1).

This crab light body is obtained by the manufacturing method described below. First, the raw materials for the crab photoreceptor are 1. Strontium compounds, including strontium sulfide (SrS), such as sulfates, nitrates, carbonates, oxides, and chlorides, which can be easily converted to SrS by heating at high temperatures in a sulfidic atmosphere. 2 Gallium compounds, including gallium sulfide (Ga2S3), which can be easily converted to Ga2S3 by heating in a sulfidic atmosphere at high temperatures, such as oxides, chlorides, sulfates, and nitrates, and 3 Including cerium sulfide (Ce2S3). Cerium compounds such as oxides, chlorides, sulfates, and nitrates that can be easily converted to Ce2S3 by heating at high temperatures in a sulfidic atmosphere are used.

The above three crab photomaterial raw materials are stoichiometrically SrS/XGa2
S3: yCe30 (where x and y are numbers that satisfy the conditions of 0.8 x SI.4 and 4 x 10-4≦y≦1 x 10-1, respectively). Thoroughly mix using a grinding mixture such as , ball mill, mixer mill, etc.

The more preferable range of x and y values of the above mixed composition formula is 0.8 mi x SI.
4 and 4×10-4≦y≦1×10-1. It should be noted that an appropriate amount of a compound known as a fluxing agent currently used in the production of crab photons, such as sodium carbonate, ammonium chloride, sodium chloride, etc., may be added to the above crab photon raw material mixture. Needless to say. The cerium compound serving as the additive may be mixed as a solution such as an aqueous solution of the compound. Although they may be mixed directly as a solid, generally more favorable results are often obtained when mixed as a solution. Next, the light-receiving body mixture is filled into a heat-resistant container such as a quartz tube and fired.

Firing is performed in a reducing sulfidic atmosphere such as a hydrogen sulfide atmosphere, a sulfur vapor atmosphere, or a carbon disulfide atmosphere. The firing temperature is suitably in the range of 700 qo to 1100 qo, particularly preferably in the range of 800 qo to 1000 qo. The firing time varies somewhat depending on the filling amount of the raw material compound, the firing temperature, etc., but within the above firing temperature range, 3 to 7 hours is appropriate. In addition, in order to improve luminance, promote solid-state reactions, and make particle protrusions uniform, the crab-phosphor raw material mixture is fired under the above-mentioned firing conditions to once produce crab-photons, and then further heated under the above-mentioned firing conditions. It may be refired once or twice or more under the same conditions. In this case, it is advisable to crush the phosphor after each firing, and if necessary, a fluxing agent may be used. After firing, the resulting fired product is washed with water, dried, and sieved to obtain the desired multi-component sulfide crab light body. This CeIJium compound is expressed by the composition formula SrS. The emitted light color of active polysulfide crab photophores is due to gallium sulfide (G), which is one of the parent compositions.
a2S3) amount, that is, the x value of the above compositional formula, and the amount of cerium added, that is, the y value of the above compositional formula, and has an emission spectrum as shown in Figure 1 (without spectral sensitivity correction of photomal). However, the emission color is similar to the emission spectrum of the conventionally used ZnS:Ag all-photon material shown in FIG. 1 (without spectral sensitivity correction).

Also, the excitation spectrum (
(without spectral sensitivity correction) is also unaffected by the x and y values, as shown in FIG. The luminance of the cerium-activated multi-component sulfide crab photoreceptor is determined by the amount of gallium sulfide (Ga2S3), which is one of the host compositions, i.e., the x value of the above compositional formula, and the amount of cerium activation, i.e., the y value of the above compositional formula. . Figures 3 and 4 show the relationship between the amount of gallium sulfide (x value) and the luminance, and the amount of cerium added (y value) in the cerium-activated multi-component sulfide luminescent material used in the color cathode ray tube of the present invention, respectively. This shows the relationship between and luminance. The range of gallium sulfide amount (x value) and cerium activation amount (y value) in the cerium-activated multi-component sulfide photoreceptor used in the color cathode ray tube of the present invention is 0.8 mi x SI. 4 and 4×10-4≦y≦1×10
-1. When the x and y values are each outside the above ranges, the luminance of the emitted light decreases significantly, which is not preferable. A more preferred x and y value range is 0.9SxSI. 3 and 1×10-3≦y≦5×10-2. FIG. 5 is a graph showing the relationship between current density and luminance in the cerium-activated multi-component sulfide light material used in the color cathode ray tube of the present invention and the ZnS:Ag light material in practical use. SrS.Ga2S3:0.007Ce3 light body, curve 2 is ZnS:Ag crab light body (Ag activation amount is 1×10-4 light body for ZnS base body 1).

As is clear from Figure 5, the stimulation current density for both is 10
The light emission brightness of the conventional ZnS:Ag crab light body shows a tendency to saturate when the current density increases.
In the case of Ce3 decaphotophores, it increases linearly. Therefore, when this blue-emitting crab phosphor is used as the blue-emitting component phosphor of a color cathode ray tube, it is possible to obtain significantly higher blue luminance than the secondary ZnS:Ag phosphor, especially at high stimulation current densities. It is. Note that curve 1 in Figure 5 is SrS・0
ab3: 0.007Ce3 This is the current density-emission brightness characteristic of the Ce3 decada photoreceptor.
a2S3: 0.007Ce3 Same as Zn
It was confirmed that the S:Ag light material exhibited better current density-luminance characteristics than the crab light material. As the blue light-emitting component crab light body constituting the crab light film of the color cathode ray tube of the present invention, the above-mentioned SrS x Ga2S3:yCe3 deca light body (where x and y have the same definitions as above) is used. However, the green light-emitting component crab light body and the red light-emitting component crab light body used are the green light-emitting component crab light body and the red light-emitting component crab light body, which have been used in the crab light film of a conventional color cathode ray tube.

That is, ZnS:Cu, AI as a green luminescent component
At least one of the crab photons and (Zn,Cd)S:Cu,AI crab photons also includes Y202S:Eu crab photons, Y203:Eu photons, and YV04:Eu crab photons as red light emitting component crab photons. At least one of the light bodies is used. The activation amount of Cu and AI of the ZnS:Cu,N photomaterial used as the green light emitting component of the color cathode ray tube of the present invention is 10-5 for that of the ZnS matrix 1.
The range is from 1 to 10-3 days, preferably 5 to 10 days.
It ranges from ×10-5 ta to 3 × 10-4 ta. Also(
The Cu and AI activation amounts of the (Zn,Cd)S:Cu,AI crab photoreceptor are both 5× relative to that of the (Zn,Cd)S matrix 1.
The range is from 10-6 ta to 10-3 ta, preferably from 1×10-5 ta to 1×10-4 ta. This (Zn,Cd)S:Cu,N matrix (Zn
, Cd) The amount of CdS in mol of SI is 0.11 mol or less, preferably in the range of 0.03 mol to 0.07 mol. Moreover, Y20 is used as a red light-emitting component crab light body of the color cathode ray tube of the present invention: Eu crab light body, Y203
The Eu activation amount of the :Eu crab photoreceptor and the YV04:Eu crab photoreceptor is in the range of 10-2 to 1.5 x 10-1 per night for Y202S, Y203 and YV04 parent bodies in each case. Yes, especially Y202S: Eu crab photophores and Y
203: 5×10-2 ta to 6× for Eu crab photons
10-2 evening range, YV04: 7 for Eu crab photons
A range of 1.times.10-2 to 8.times.10-2 is preferred.

The above-mentioned blue light-emitting component crab light, green light-emitting component crab light, and red light-emitting component crab light are coated on the face plate by an optical printing method, which is generally adopted as a method for forming a crab light film on color cathode ray tubes. It is considered to be the waist. Figure 6 is S
rS・1.10a2S3: 0.007Ce3 jutsu luminous body,
ZnS with an activation amount of Cu and AI of 1.2×10-4 t/t: Cu, an AI crab photon and an activation amount of Eu of 5×1
0-2 evening/evening Y202S: A graph showing the relationship between white luminance and current density of a color cathode ray tube of the present invention having a crab light film in which Eu crab light bodies are used as blue, green, and red light emitting component crab light bodies, respectively. (The white brightness on the vertical axis is the Ag activation amount Z.
ZnS:A which is 1 × 10-4 times per nS matrix 1
G The white light brightness of a conventional color cathode ray tube with a crab light film using the same crab light body as above is set to 100%. (expressed as a relative value as a percentage).

As is clear from Fig. 6, the white light brightness increases as the current density increases, and at 65 A/m, the white light brightness is equivalent to that of the conventional color cathode ray tube mentioned above, and even after that, the white light brightness does not show a tendency to saturate. The white light brightness of the color cathode ray tube of the invention shows an increasing trend. The present invention will be explained below with reference to Examples. Example 1 Strontium sulfate (SrS04) 1 mol Gallium oxide (Ga203) 1 mol Cerium oxide (Ce203) 0.007 mol The above-mentioned fluorescent material raw materials were thoroughly mixed using a ball mill, which also served as pulverization, and then placed in a quartz tube. It was then fired at 850 oo for 5 hours while blowing in hydrogen sulfide.

In this way, SrS・Ga2S3:0.007Ce3
Obtained Ten Crabs of Light. This crab photon has an emission spectrum shown by curve 1 in FIG. 1 and an excitation spectrum shown in FIG. 2. In addition, the luminescence brightness of the ZnS:Ag light body is determined under the stimulation condition of current density 10A/acceleration voltage 17KV, Ag activation amount is 1 × 10-4 days per Z ship mother body 1 day. When the brightness is 100% (same as Example 2 and below)
100%, and showed excellent current density-emission brightness characteristics as shown by line 1 in FIG. Next, the above SrS・Ga
2S3: 0.007Ce3 decaphotometer is a blue-emitting component isophore, Cu and AI activation amount are both 1.2×10-4
The ZnS:Cu, AI crab photoreceptor with a green luminescent component nectarium and the Y with an Eu activation amount of 5 × 10-2 e/e
202S: A color cathode ray tube having a crab light film using Eu crab light as a red light-emitting component crab light was manufactured by a conventional manufacturing method.

The white light brightness of this color cathode ray tube is a current density of 10 French A'
83.3% under the stimulation condition of acceleration voltage 17KV, 103.5% under the stimulation condition of current density 100 A/ground and acceleration voltage 17KV (Ag activation power average nS matrix 1.
×10-4 color ZnS:Ag crab light body is used as a blue light emitting component crab light body, and the green light emission component crab light body and the red light emission component crab light body have a honeycomb film using the same crab light body as above. When the white light brightness of a color cathode ray tube is set to 100%. Example 2
and 3). Example 2 Strontium sulfate (SrS04) 1 mol Gallium oxide (Ga2Q) 1.1 mol Cerium oxide (Ce203) 0.007 mol The above raw materials for the crab phosphor were thoroughly mixed using a ball mill, which also served as pulverization, and then mixed with quartz. It was packed in a tube and fired at 950 qo for 5 hours while blowing hydrogen sulfide.

In this way, S[S. 1.10a2S3:0.007
A Ce3 deca-photon was obtained. This nectar has an emission spectrum shown by curve 1 in FIG. 1 and an excitation spectrum shown in FIG. In addition, its luminance is at a current density of 10 French A.
/ 104% under stimulation conditions of an acceleration voltage of 17 KV, and exhibited excellent current density-emission brightness characteristics as shown in curve 1 of FIG. Next, the above SrS・1.1Ga layer 3:
0.007Ce3 Deca photobody is used as a blue light emitting component Crab photobody,
A color cathode ray tube having a transparent film was manufactured using the same nectarium as in Example 1, using the same nectarium as the green luminescent component and the red luminescent component, using a conventional manufacturing method.

The white brightness of this color cathode ray tube is at a current density of 10 μA/
was 85.5% under the stimulation condition of an accelerating voltage of 17 KV, and 104.8% under the stimulating condition of an accelerating voltage of 17 KV and a current density of 100 wA/. Example 3 Strontium carbonate (S08) 1 mol Gallium oxide (Ga203
) 1.1 mole cerium oxide (Ce2Q)
0.005 mol The above raw materials for each crab photoreceptor were thoroughly mixed using a ball mill, which also served as pulverization, and then placed in a quartz tube and heated to 9,000 mol while blowing carbon disulfide vapor.
0 for 4 hours.

In this way, SrS・1.1Ga2S3:0.00K
An e3 decanopophore was obtained. This crab photon has an emission spectrum shown by curve 1 in FIG. 1 and an excitation spectrum shown in FIG. 2. In addition, its luminance is a current density of 10 French A/
103% under the stimulation condition of an accelerating voltage of 17 KV, and exhibited excellent current density-emission brightness characteristics as shown in curve 1 in FIG. Next, the above SrS・1.1Ga2S3
:0.00$e3 The crab light body is a blue light emitting component crab light body,
A color cathode ray tube having a saddle light film using the same crab light body as in Example 1 was manufactured using a conventional manufacturing method for the green light-emitting component crab light body and the red light-emitting component crab light body. The white brightness of this color cathode ray tube is at a current density of 10 French A' and an accelerating voltage of 17 KV.
84.4% under stimulation conditions of 100 mA/current density,
It was 104.5% under stimulation conditions with an accelerating voltage of 17 KV. Example 4 SrS of Example 2 1.1Ga2S3:0
．． 007Cey crab photophores are blue-emitting component fin photophores, Cu, and Z whose peak activity is 1.2 × 10-4 evening/event.
nS: Cu, AI crab photophores and green emitting component crab photophores and E
A color cathode ray tube having a crab light film having a Y203:Eu light material with a u activation amount of 5×10-2 ta as a red light-emitting component crab light material was manufactured by a conventional manufacturing method. The white luminance of this color cathode ray tube is 84.5% under stimulation conditions of current density 10 A' and accelerating voltage 17 KV, and 100% (A) under stimulation conditions of current density 103 A' and accelerating voltage 17 KV.
A ZnS:Ag crab photon whose g activation amount is 1 x 10-49 for the ZnS matrix 1 is used as a blue light emitting component crab photon, and a green light emitting component crab photon and a red light emitting component crab photon are the same as above. (assuming the white luminance of a color cathode ray tube with a crab light film using the same crab light body to be 100%). Example 5 The SrS 1.10a 3:0.007Ce3 luminescent body of Example 2 was replaced with a blue light-emitting component phosphor, and the Cu and N activation amounts were both 1.2 x 10-4 1/2. Some ZnS: Cu, AI
The green light-emitting component crab photon and Eu activation amount are 5 x 1.
0-2 evening/evening YV04: A color cathode ray tube having a crab light film using Eu crab light as the red light emitting component crab light was manufactured by a conventional manufacturing method.

The white brightness of this color cathode ray tube is a current density of 10 French A/
91.8% under the stimulation condition of an accelerating voltage of 17 KV, and 1 under the stimulation condition of an accelerating voltage of 17 KV with a current density of 100 A/
02.0% (Amount of Ag added is 1x for ZnS matrix 1)
10-4, the ZnS:Ag crab light body is used as a blue light-emitting component crab light body, and the green light-emitting component crab light body and the red light-emitting component crab light body are the same crab light bodies as above. (assuming the white luminance of the cathode ray tube to be 100%).
Example 6 SrS of Example 3 1.10a2S3×0.
The 005Ce3 Decropole has a blue-emitting component, Cu, and mountain-activated activity of 1.2×10-4 t/t (
Zno. 95, Cd.

．． . 5) S:C↓Y202S:E with green light-emitting component crab photon and Eu activation amount of 5 × 10-2 t/t
A color cathode ray tube having a crab light film in which the u light emitter is a red light-emitting component was manufactured by a conventional manufacturing method.

The white brightness of this color cathode ray tube is a current density of 10 A/
ground, 81.5% under stimulation conditions of acceleration voltage 17KV, current density 110AA/, 101% under stimulation conditions of acceleration voltage 17KV (Ag activation amount is 1 × 1 for ZnS matrix 1)
A color cathode ray tube with a crab light shade using the same crab light body as above for the blue light emitting component crab light body and the green light emitting component crab light body and the red light emitting component crab light body, which is 0-4 evening. (assuming the white luminance of 100%).

[Brief explanation of the drawing]

Figure 1 shows the emission spectrum of the ZnS:Ag light emitter, which is the blue light emitting light body of a conventional color cathode ray tube, and the Sr light emitter, which is the blue light emitting light body of the color cathode ray tube of the present invention.
S.Ga2S3:0.007Ce3 is the emission spectrum of the photon, and curve 1 is SrS.Ga2S3:0.00.
7Ce3 crab photon, curve 2 is a ZnS:Ag crab photon. FIG. 2 shows the excitation spectrum of the SrS.Ga2S3:0.00 and e3 decaphores, which are the blue light-emitting component of the color cathode ray tube of the present invention. Figure 3 shows SrS x Ga2S, which is the blue light emitting component of the color cathode ray tube of the present invention.
3:007Ce3 It is a graph showing the relationship between the amount of gallium sulfide (x value) and the luminance in the Ce3 Deca photon. Fourth
The figure is a graph showing the relationship between the cerium activation amount (y value) and the luminance in the SrS.Ga2S3:yCe3 decada photoreceptor, which is the blue light emitting component deca photon member of the color cathode ray tube of the present invention. Figure 5 shows the blue light emitting component of the color cathode ray tube of the present invention, SrS.
This is a graph showing the relationship between current density and luminance in a ZnS:Ag light body, which is a blue light emitting component light body of a conventional color cathode ray tube, and curve 1 is Sr.
S・Ga2S3: e3 Jusaka light body at 0.00, curve 2 is Z
nS: Ag crab photoreceptor. FIG. 6 is a graph illustrating the relationship between white luminance and current density of the color cathode ray tube of the present invention. Figure l Figure 2 Figure 3 Figure 4 Figure 5 Figure 6

Claims (1)

[Claims] 1. The compositional formula is SrS・_xGa_2S_3:_yCe^3^+ (where x and y are respectively 0.8≦x≦1.4 and 4×1
A cerium-activated multi-component sulfide phosphor expressed as 0^-^4≦y≦1×10^-^4) is used as a blue-emitting component phosphor, and the activation amount of copper and aluminum is Copper and aluminum activated zinc sulfide phosphor whose activation amount is in the range of 10^-^5g to 10^-^3g per 1g of zinc sulfide base, and copper and aluminum activated amount per 1g of zinc sulfide cadmium base. Both are 5×10
It is in the range of ^-^6g to 10^-^3g, and the amount of cadmium sulfide in 1 mole of zinc cadmium sulfide matrix is 0.11
At least one of the copper- and aluminum-activated zinc cadmium sulfide phosphors is used as a green-emitting component phosphor, and the amount of europium activation is In the case of 10^-^2g to 1.5 x 10^
-^1 g of at least one of a europium-activated yttrium oxysulfide phosphor, a europium-activated yttrium oxide phosphor, and a europium-activated yttrium vanadate phosphor as a red-emitting component phosphor. A color television cathode ray tube characterized in that it has a fluorescent film. 2 x and y of the composition of the cerium-activated multi-component sulfide phosphor are 0.9≦x≦1.3 and 1×10^, respectively
-^3≦y≦5×10^-^2, and the copper and aluminum activation amounts of the copper and aluminum activated zinc sulfide phosphor are both 5×10^-5g to 3×1
The activation amount of copper and aluminum of the copper and aluminum activated zinc sulfide cadmium phosphor is in the range of 0^-^4g, and the copper and aluminum activation amounts of the copper and aluminum activated zinc sulfide cadmium phosphor are all in the range of 1x10^-^5g to 1x10^-
^4g and the amount of cadmium sulfide is 0.03
The amount of europium activation in the europium-activated yttrium oxysulfide phosphor and the europium-activated yttrium oxide phosphor ranges from 5 x 10^-^2 g to 6 x. The europium activation amount of the europium-activated yttrium vanadate phosphor is in the range of 10^-^2g.
A color television cathode ray tube according to claim 1, wherein the color television cathode ray tube has a weight in the range of 8×10^-^2g.