JPS6144909B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cathode ray tubes, and more particularly to high resolution cathode ray tubes.

It is desired to use high-resolution cathode ray tubes in terminal display devices for computers, display devices for aircraft control systems, etc. that display detailed characters and graphics. A known method for improving the resolution of a cathode ray tube is to reduce the frame frequency of the cathode ray tube. In other words, the frame frequency of ordinary cathode ray tubes such as television cathode ray tubes is around 55Hz, but by lowering this frame frequency to around 30Hz, the signal frequency band can be expanded to about twice that of ordinary cathode ray tubes. Alternatively, the video frequency band can be selected to be approximately 1/2 that of a normal cathode ray tube, thereby increasing resolution. The reason why it is possible to increase the resolution of a cathode ray tube by reducing its frame frequency is that the video frequency band of the cathode ray tube drive circuit is determined by the product of the frame frequency and the signal frequency band. be.

The phosphor film of the high-resolution cathode ray tube needs to be composed of a phosphor with long afterglow properties. The reason for this is that when the phosphor film of the cathode ray tube is composed of a short afterglow phosphor that composes the phosphor film of an ordinary cathode ray tube, the phosphor film scanning speed is slow, causing flickering on the screen. This is because In general, the phosphor that makes up the phosphor film of the above-mentioned high-resolution cathode ray tube has a 10% afterglow time (the time required for the luminance to drop to 10% of the excitation brightness after stopping excitation) compared to that of a normal cathode ray tube. It needs to be several tens to hundreds of times longer than the short afterglow phosphor that makes up the film.

Conventionally, as long-afterglow phosphors that can be used in the above-mentioned high-resolution cathode ray tubes, manganese-activated zinc silicate green-emitting phosphors (Zn ₂ SiO ₄ :Mn), manganese- and arsenic-activated zinc silicate green-emitting phosphors have been used. body (Zn ₂ SiO ₄ :Mn,
As), manganese-activated zinc/magnesium orthophosphate red-emitting phosphor [(Zn, Mg) ₃ (PO ₄ ) ₂ :Mn],
Manganese-activated zinc orthophosphate red-emitting phosphor [Zn ₃ (PO ₄ ) ₂ :Mn], manganese-activated magnesium silicate red-emitting phosphor (MgSiO ₃ :Mn), manganese- and lead-activated calcium silicate orange-emitting phosphor Phosphor (CaSiO ₃ : Mn, Pb), manganese-activated cadmium chloride phosphate orange-emitting phosphor [3Cd ₃ (PO ₄ ) ₂・CdCl ₂ :
Mn], europium and dysprosium activated rare earth oxide red-emitting phosphor (Ln ₂ O ₃ : Eu, Dy,
However, Ln is at least one of Y, Gd, La, and Lu), manganese-activated potassium fluoride/magnesium fluoride orange-emitting phosphor (KMgF ₃ :Mn), manganese-activated magnesium fluoride red-emitting phosphor (MgF ₂ :Mn), etc. are known. As is well known, the phosphor film of a black-and-white cathode ray tube is a film of a white-emitting mixed phosphor, which is a mixture of a red-emitting component phosphor, a green-emitting component phosphor, and a blue-emitting component phosphor in an appropriate ratio. In addition, the phosphor film of a color cathode ray tube consists of a trio of light-emitting elements (generally known as Each light-emitting element is composed of regular repetitions of dot-like or striped-like light emitting elements. Alternatively, it can be used as a green-emitting component phosphor and a red-emitting component phosphor of a color cathode ray tube.

As mentioned above, there are several known phosphors with long afterglow properties that can be used as red-emitting component phosphors and green-emitting component phosphors that make up the phosphor film of high-resolution cathode ray tubes. A long-afterglow phosphor that can be used as a blue-emitting component phosphor constituting a phosphor film of a resolution cathode ray tube, that is, a long-afterglow blue-emitting phosphor has not been known at all. For this purpose, silver, which is used in cathode ray tubes for black-and-white televisions, cathode ray tubes for color televisions, etc., is used as an activator, and at least one of chlorine, bromine, iodine, fluorine, and aluminum is co-activated. The above-mentioned long afterglow green color is added to the short afterglow blue light emitting zinc sulfide phosphor (ZnS:Ag, where X is at least one of chlorine, bromine, iodine, fluorine and aluminum) as an agent. A light-emitting phosphor and an orange to red-emitting phosphor are mixed in a specific ratio, and this mixed phosphor (called a light blue phosphor) is used as the blue color that makes up the phosphor film of a high-resolution cathode ray tube. One method is to use it as a luminescent component phosphor to make it appear to the human eye as if the blue luminescence had an afterglow. However, the above-mentioned light blue phosphor has a very short 10% afterglow time of its main component, ZnS:Ag, A conventional high-resolution cathode ray tube that produces color shift and therefore uses the light blue phosphor as a blue-emitting component phosphor together with the long-afterglow red-emitting component phosphor and the green-emitting component phosphor. The fluorescent film causes a color shift in the emission color after excitation stops. For example, the phosphor of a conventional high-resolution black and white cathode ray tube that uses the above-mentioned light blue phosphor as a blue-emitting component phosphor emits white light during excitation, but after excitation stops, the emission color changes from white to red-emitting component phosphor. The emitted light color of the light body and the emitted light color of the green light emitting component phosphor change over time in the direction of an additive color mixture (yellow). Furthermore, since the light blue phosphor is a mixture of phosphors that emit light of different colors, color unevenness tends to occur in the emitted light.
Furthermore, the color purity of the luminescent color (blue) is also poor. Therefore, especially in the phosphor film of a high-resolution color cathode ray tube that uses the above-mentioned light blue phosphor as a blue-emitting component phosphor, color unevenness is likely to occur in the luminescent color of the blue-emitting component phosphor (blue-emitting element). , and the color purity of the emitted light is also poor.

As mentioned above, no long-lasting blue-emitting phosphor that can be used as a blue-emitting component phosphor in high-resolution cathode ray tubes has been known, and this has hindered the spread of high-resolution cathode ray tubes. This is a major cause.

The present invention was made under the above circumstances, and provides a high-resolution cathode ray tube using a novel long-afterglow blue-emitting phosphor as a blue-emitting component phosphor constituting a phosphor film. The purpose is to provide

In the high-resolution cathode ray tube of the present invention, at least one of the following four types of long-afterglow blue-emitting sulfide phosphors is used as the blue-emitting component phosphor constituting the phosphor film.

(i) Zinc sulfide is used as a matrix, silver is used as an activator, gallium is used as a first co-activator, and at least one of chlorine, bromine, iodine, fluorine and aluminum is used as a second co-activator. and the amounts of the activator, first co-activator and second co-activator are 5×10 ^-4 to 10 ^-1 % by weight and 10 ^-6 to 5×10 of the zinc sulfide matrix, respectively. ^-1 % by weight and from 5×10 ⁻⁶ to 5×10 ⁻² % by weight of a zinc sulfide phosphor (hereinafter referred to as “phosphor”).

(ii) Zinc sulfide is used as a matrix, silver is used as an activator, gallium is used as a first co-activator, and at least one of chlorine, bromine, iodine, fluorine and aluminum is used as a second co-activator. and the amounts of the activator, first co-activator and second co-activator are 5×10 ^-4 to 10 ^-1 % by weight and 10 ^-6 to 5×10 of the zinc sulfide matrix, respectively. Zinc sulfide phosphor ( ^{hereinafter referred to as "} fluorophore).

(iii) zinc sulfide as a matrix, silver as an activator, gallium as a first co-activator, at least one of gold and copper as a second co-activator, chlorine,
At least one of bromine, iodine, fluorine, and aluminum is used as a third coactivator, and the above activator, the first coactivator, the second coactivator, and the third coactivator The amount of the agent is 5×10 ⁻⁴ to 10 ⁻¹ % by weight and 10 ⁻⁶ to 5× of the zinc sulfide matrix, respectively.
^10-1 % by weight, 1.5× ^10-2 % by weight or less and 5×
Zinc sulfide phosphor (hereinafter referred to as "phosphor") having a content of 10 ^-6 to 5 x 10 ^-2 % by weight.

(iv) zinc sulfide as a matrix, silver as an activator, gallium as a first co-activator, at least one of gold and copper as a second co-activator, chlorine,
At least one of bromine, iodine, fluorine and aluminum is used as a third co-activator, and the above-mentioned activator, first co-activator, second co-activator and third co-activator are combined. The amount is 5×10 ⁻⁴ to 10 ⁻¹ % by weight and 10 ⁻⁶ to 5×10 ⁻¹ of the above zinc sulfide matrix, respectively.
Weight%, 1.5×10 ^-2 weight% or less and 5×10 ^-6
A zinc sulfide phosphor (hereinafter referred to as "phosphor") containing sulfur in an amount of 10 ^-5 to 8 x 10 ^-1 % by weight based ^on the zinc sulfide matrix.

The above phosphors -, , and are all based on the short afterglow ZnS:Ag, Furthermore, by activating gallium, the phosphor has a long afterglow property. 10 of these phosphors
Both percent afterglow times vary within the range of 5 to 300 milliseconds, depending primarily on the amount of gallium activation and the current density of the electron beam.

However, if the afterglow time of the phosphor used in the high-resolution cathode ray tube of the present invention is 5 milliseconds or less, the screen will flicker, and the afterglow time will be 150 milliseconds or less.
The inventors have found through research that afterimages occur on the screen when the duration is longer than milliseconds, so the afterglow time of the phosphor used in the high-resolution cathode ray tube of the present invention is determined by the afterglow time of the electron beam. A period of 5 to 150 milliseconds is required depending on the current density.

Therefore, the blue light-emitting component phosphor constituting the phosphor film of the high-resolution cathode ray tube of the present invention is the above-mentioned phosphor.
The phosphor may consist of at least one of the following, or may be a mixture of an appropriate amount of a short afterglow blue-emitting phosphor of at least one of the above phosphors, , and. However, the 10% afterglow time should be 5 to
Must be 150ms.

Further, the green-emitting component phosphor constituting the phosphor film of the high-resolution cathode ray tube of the present invention has a 10% afterglow time of at least 5 milliseconds, such as the above-mentioned conventionally known long-afterglow green-emitting phosphor. Composed of long-afterglow green-emitting phosphor. The green emitting component phosphor may consist solely of a long persistence green emitting phosphor with a 10% afterglow time of at least 5 milliseconds, or alternatively the green emitting component phosphor may consist of a long persistence green emitting phosphor with a 10% afterglow time of at least 5 milliseconds. It may be a mixture of an appropriate amount of a long afterglow green emitting phosphor and a short afterglow green emitting phosphor, but 10%
The afterglow time needs to be 5 to 150 milliseconds, similar to the blue light emitting component phosphor described above.

Further, the red light emitting component phosphor that constitutes the phosphor film of the high resolution cathode ray tube of the present invention together with the blue light emitting component phosphor and the green light emitting component phosphor has the above-mentioned conventionally known long afterglow orange to red light emission. like a phosphor
Constructed by a long afterglow orange to red emitting phosphor with a 10% afterglow time of at least 5 milliseconds. The red emitting component phosphor may consist solely of a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 milliseconds, or alternatively may consist solely of a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 ms. It may be a mixture of an appropriate amount of a millisecond long afterglow orange to red emitting phosphor and a short afterglow orange to red emitting phosphor; As with the component fluorescer and the green-emitting component phosphor, it should be between 5 and 150 milliseconds.

That is, the high-resolution cathode ray tube of the present invention comprises () a blue-emitting component phosphor which has at least one of the above phosphors as a main component and has a 10% afterglow time of 5 to 150 milliseconds; () a green-emitting component phosphor comprising a long-afterglow green-emitting phosphor having a 10% afterglow time of at least 5 milliseconds;
and () a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 ms, and a phosphor comprising a red emitting component phosphor with a 10% afterglow time of 5 to 150 ms. It is characterized by having a light film.

The present invention will be explained in detail below.

As mentioned above, the phosphors used as the blue-emitting component of the phosphor film of the high-resolution cathode ray tube of the present invention, and the blue-emitting component of the cathode ray tube for black-and-white and color television. The above-mentioned short afterglow properties are widely used as component phosphors, etc.
ZnS:Ag,X A blue-emitting phosphor is made into a long-afterglow phosphor by further activating gallium, and is a novel phosphor. For phosphor and phosphor, the required amount of each predetermined phosphor raw material is weighed and mixed, and the obtained phosphor raw material mixture is heated at a temperature of 600 to 1200°C in a sulfidic atmosphere to 0.5
It can be produced by baking for 7 hours, washing the obtained baked product with water, drying, and sieving (see JP-A-58-83085 and JP-A-58-83085).
(See No. 83084). The luminance of the phosphor is improved by adding a small amount of sulfur to the phosphor. Also, fluorescent material
The luminance of the phosphor is improved by further activating the phosphor with an appropriate amount of gold and/or copper. Furthermore, the luminance of the phosphor is improved by containing a small amount of sulfur in the phosphor and activating an appropriate amount of gold and/or copper. It is. Therefore, when comparing phosphors that have the same silver activation amount, gallium activation amount, and activation amount of at least one of chlorine, bromine, iodine, fluorine, and aluminum, shows higher luminance than fluorescent material. Incidentally, a necessary amount of an appropriate gold compound or copper compound, or both, is added to the phosphor raw material mixture used in the production of the phosphor and the phosphor, respectively, and this is used as the phosphor raw material mixture. The phosphor is manufactured in the same manner as the phosphor described above except for the following. When gold is used alone as the second co-activator in the phosphor ^and
Preferably, the amount is from 1.5 x 10 -4 to 8 x 10 ^-3 % by weight, and when copper is used alone, the activation amount is from 1.5 x 10 ^-4 to 8 x 10 ^-4 weight % of the zinc sulfide matrix. is preferred.

10 after cessation of excitation of fluorophore-, , and
The % afterglow time varies within the range of 5 to 300 milliseconds, depending primarily on the activation amount of gallium and the current density of the electron beam. In this way, the phosphor-
, and exhibit a long afterglow unlike conventional ZnS:Ag, Gallium also affects the luminance of the emitted light and the purity of the emitted color. That is, in any of the phosphors -, , and, the emission brightness gradually decreases as the amount of gallium activation increases, and the purity of the emitted light color decreases as the amount of gallium activation increases significantly.

As already mentioned for the phosphors, the phosphors, and the phosphors are prepared by heating a predetermined phosphor raw material mixture in a sulfuric atmosphere to
It is produced by firing at a temperature of 1200°C, but if the firing temperature is higher than 1050°C, a phosphor with a hexagonal system as the main crystal phase is obtained; In this case, a phosphor having a cubic crystal system as the main crystal phase can be obtained. In other words, the phosphor-
, , and all have phase transition points around 1050°C. When comparing a phosphor whose main crystal phase is a cubic system and a phosphor whose main crystal phase is a hexagonal system, the former has a higher luminance than the latter. For phosphors with a relatively low amount of gallium activation, which is about 1.3 to 2 times higher and has higher emission brightness and emission color purity, the former has a 10% longer afterglow time than the latter.
From these points of view, it is preferable that the phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention has a cubic crystal system as its main crystal phase. In both of the phosphors -, , and, the emission spectrum of the phosphor whose main crystal phase is cubic is slightly longer than that of the phosphor whose main crystal phase is hexagonal. It's on the side.

Note that all values of afterglow time in the examples described below are values when the current density of the stimulating electron beam is 1 μA/cm ² .

FIG. 1 illustrates the emission spectrum of the phosphor. In Figure 1, curves a and b
are ZnS whose main crystal phases are cubic and hexagonal, in which the activation amounts of silver, gallium, and chlorine are respectively 10 ^-2 %, 10 ^-2 % and 10 ^-4 % by weight of the zinc sulfide matrix. :Emission spectra of Ag, Ga, Cl phosphors, curve c shows the cubic system in which the activation amounts of silver and chlorine are the same as above, and the gallium activation amount is ¹ % by weight of the phosphor based on zinc sulfide. Main crystal phase
This is the emission spectrum of ZnS: Ag, Ga, Cl phosphor.

As illustrated in FIG. 1, the phosphor emits blue light. As is clear from the comparison of curves a and c, when the amount of gallium activation in the phosphor increases significantly, the half-width of the emission spectrum becomes wider and the color purity of the emitted color decreases. However, even when the gallium activation amount is 5 x 10 ^-1 % by weight, which is the upper limit, the phosphor is still lower than the light blue phosphor that has been used as the blue-emitting component phosphor of high-resolution cathode ray tubes. It also emits blue light with much higher color purity. In particular, the amount of gallium activation shown by curve a is
The emission spectrum of the phosphor, which is 10 ^-2 % by weight, is the main component of the light blue phosphor, ZnS:Ag,
The half width is narrower than the emission spectrum of the X phosphor,
Therefore, a phosphor having a gallium activation amount of at least 10 ^-2 % by weight or less emits blue light with higher color purity than a ZnS:Ag,X phosphor. Furthermore, as is clear from the comparison between curve a and curve b, the phosphor (curve a) has a cubic system as its main crystal phase.
has an emission spectrum slightly on the longer wavelength side than the phosphor (curve b) whose main crystal phase is hexagonal system.

The changes in the emission spectrum (changes in the color purity of the emitted light) due to changes in the amount of gallium activation in the phosphors and are similar to those in the case of the phosphors explained in Fig. 1. Almost the same.
Like the phosphor, both the phosphor and the phosphor emit blue light with much higher color purity than the light blue phosphor. In particular, the gallium activation amount is 10 ^-2
The phosphor, which is less than 1% by weight, emits blue light with higher color purity than the ZnS:Ag,X phosphor, which is the main component of the light blue phosphor. Also, in phosphors and phosphors, phosphors with a cubic crystal system as their main crystal phase have an emission spectrum slightly on the longer wavelength side than phosphors with a hexagonal system as their main crystal phase. .

Figure 2 shows the amount of gallium activation in the phosphor and
It is a graph illustrating the relationship with 10% afterglow time.
In Figure 2, curve a shows activation amounts of silver and chlorine of 10 ^-2 and 10 ^-4 by weight of the zinc sulfide matrix, respectively.
ZnS with cubic system as main crystal phase in weight%:
The above relationship in Ag, Ga, Cl phosphor, curve b is the above relationship in ZnS:Ag, Ga, Cl phosphor whose main crystal phase is hexagonal system with the same activation amount of silver and chlorine as above. It is.

As illustrated in Figure 2, phosphors with a gallium activation amount in the range of 10 ^-6 to 5 x 10 ^-1 % by weight of the zinc sulfide matrix have a cubic or hexagonal crystal phase. In either case, the 10% afterglow time is extremely long. In Figure 2, the 10% afterglow time of the phosphor varies within a range of 5 to 55 milliseconds depending on the amount of gallium activation; In particular, the upper limit of the 10% afterglow time varies considerably depending on the conditions at the time of manufacturing the phosphor. So far, it has been confirmed that the maximum 10% afterglow time of the phosphor is approximately 80 milliseconds.

As illustrated in FIG. 2, among the phosphors, phosphors having a gallium activation amount in the range of 5×10 ^-4 to 10 ^-1 % by weight have a particularly long 10% afterglow time. However, as explained above, the luminance of the phosphor gradually decreases as the amount of gallium activation increases, and the purity of the luminescent color decreases as the amount of gallium activation increases significantly. Taking into consideration the emission brightness and emission color purity, the phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention has a gallium activation amount in the range of 10 ^-6 to 10 ^-2 % by weight. However, it is preferable.

As explained above, the luminance of a phosphor having a cubic crystal system as its main crystal phase is about 1.3 to 2 times higher than that of a phosphor having a hexagonal system as its main crystal phase. Furthermore, as is clear from FIG. 2, in the preferred range of gallium activation amount (10 ^-6 to 10 ^-2 % by weight), a phosphor having a cubic system as its main crystal phase has a hexagonal system as its main crystal phase. The afterglow time is 10% longer than that of the fluorescent material. From these points of view, the phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention preferably has a cubic system as its main crystal phase, and has a gallium activation amount of 10 ^-6 to 10 ^- It is particularly preferred that the main crystal phase is a cubic system in the range of ² % by weight.

The afterglow characteristics of the phosphor have been explained above with reference to FIG. 2.
It shows almost the same afterglow characteristics. In other words, the phosphor-
The 10% afterglow time of , and is approximately 5 to 80 minutes depending on the amount of gallium activation and the conditions during phosphor manufacturing.
When comparing phosphors that vary within a millisecond range and have the same gallium activation amount and the same phosphor manufacturing conditions, the 10% afterglow time of phosphor -, and phosphor - This is almost the same as the 10% afterglow time.
As explained above, the luminance of the phosphor and the phosphor gradually decreases as the amount of gallium activation increases, and the purity of the luminescent color decreases as the amount of gallium activation increases significantly. . Taking into account the emission brightness and emission color purity, the gallium activation amount is 10 ^-6 to 10, similar to the phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention. ^-2 % by weight is preferred. Furthermore, as explained above, phosphors and phosphors whose main crystal phase is cubic have a luminance of about 1.3 to 2 twice as expensive. Therefore,
The phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention preferably has a cubic crystal system as its main crystal phase, similar to the phosphor, and has a gallium activation amount. Fluorescent material ⁶ to fluorescent material ²
Particularly preferred are those having a cubic crystal system as the main crystal phase within the range of % by weight. Both phosphors and phosphors have improved luminance. Therefore, the degree of decrease in luminance of the phosphor as the amount of gallium activation increases is lower than that of the phosphor.

Although the phosphors -, , and are described above, in these phosphors, a part of the first co-activator gallium may be replaced with indium, scandium, or both. Further, the fluorescent material may be further activated with an activator such as divalent europium, bismuth, or antimony. Furthermore, in order to shift the emission wavelength to a slightly longer wavelength side, some of the zinc constituting the matrix is replaced by cadmium, or a part of the sulfur constituting the matrix is replaced by selenium. You can leave it there.

In addition, in FIGS. 1 and 2, the phosphor -
Of those expressed as ZnS:Ag, GaX, only examples where X is Cl are shown, but when X is Al,
Similar results can be obtained in the case of I, Br, and F.

The blue light-emitting component phosphor constituting the phosphor film of the high-resolution cathode ray tube of the present invention is composed of at least one of the above-mentioned phosphors. The blue-emitting component phosphor is the above-mentioned phosphor.
It may consist only of at least one of the following, or the above-mentioned fluorescent material -
, , and may be mixed with an appropriate amount of a short afterglow blue-emitting phosphor in order to adjust afterglow characteristics and luminance. The 10% afterglow time of the above phosphors -, , and is 5 to 80 milliseconds at a current density of 1 μA/cm ² of the stimulating electron beam, but up to 300 milliseconds when the current density of the electron beam is lowered. In such cases, 10% of the blue-emitting component phosphor constituting the phosphor film of the high-resolution cathode ray tube of the present invention may
The afterglow time is preferably 10% afterglow time, i.e. 5~
A 10% afterglow time of 5 milliseconds is obtained by mixing at least one short afterglow blue-emitting phosphor of phosphors, , and an appropriate amount ratio so that the afterglow time is 150 milliseconds. It must not be less than 150 milliseconds or more than 150 milliseconds. Specific examples of the short afterglow blue-emitting phosphor to be mixed with at least one of the phosphors include ZnS:Ag and X phosphors.

As mentioned above, the blue-emitting component phosphor is a phosphor-
, , and, or at least one of the fluorescers, , and the phosphors,
, and a short afterglow blue-emitting phosphor with similar colors, there is no or almost no color shift in the emission color after excitation is stopped. Furthermore, even if the blue-emitting component phosphor is a mixture of two or more types of phosphors, it does not emit light because it is not a mixture of phosphors with different emission colors like the conventional light blue phosphor. There will be no unevenness in color. Furthermore, as explained earlier, phosphors -, , and phosphors all emit blue light with much higher color purity than light blue phosphors, so blue-emitting component phosphors are Of course, when it consists of at least one of the following, the phosphor-,
, , and a suitable amount of a short afterglow blue-emitting phosphor having a similar color to these phosphors - , , and , even if phosphors with different emission colors are mixed. It emits blue light with much higher color purity than light blue phosphors.

The green-emitting component phosphor constituting the phosphor film of the high-resolution cathode ray tube of the present invention is constituted by a long-persistence green-emitting phosphor with a 10% afterglow time of at least 5 milliseconds. Specific examples of such long-afterglow green-emitting phosphors include conventionally known Zn ₂ SiO ₄ :Mn phosphors;
Zn ₂ SiO ₄ :Mn, As fluorophores, etc. can be mentioned. The green-emitting component phosphor may consist solely of long-afterglow green-emitting phosphors with a 10% afterglow time of at least 5 ms, or alternatively, a 10% long-glow time of at least 5 ms. It may be a mixture of a long afterglow green emitting phosphor and an appropriate amount of a short afterglow green emitting phosphor in order to adjust the afterglow characteristics and luminance, but the 10% afterglow time is between 5 and 150 milliseconds. Therefore, when a long afterglow green emitting phosphor with a 10% afterglow time of longer than 150 milliseconds is used, an appropriate amount of a short afterglow green emitting phosphor is mixed with the phosphor. The 10% afterglow time must be adjusted to 150 milliseconds or less. In addition, when a long afterglow green emitting phosphor is mixed with a short afterglow green emitting phosphor to form a green emitting component phosphor, the 10% afterglow time of the resulting green emitting component phosphor is Both must be mixed in such a proportion that the time is not less than 5 milliseconds. A specific example of a short afterglow green emitting phosphor mixed with a long afterglow green emitting phosphor is copper and aluminum activated zinc sulfide phosphor (ZnS:Cu,
Al), copper, gold and aluminum activated zinc sulfide phosphor (ZnS: Cu, Au, Al), silver activated zinc sulfide/cadmium phosphor [(Zn, Cd)S:Ag] copper activated zinc sulfide phosphor Cadmium phosphor [(Zn, Cd)S:Cu],
Copper and chlorine activated zinc sulfide phosphor (ZnS:Cu,
Cl), copper and aluminum activated zinc sulfide/cadmium phosphor [(Zn,Cd)S:Cu,Al], silver and aluminum activated zinc sulfide/cadmium phosphor [(Zn,Cd)S:Ag, Al], terbium-activated rare earth oxysulfide phosphor (Ln ₂ O ₂ S: Tb, where Ln is Y,
at least one of Gd, La, and Lu), and the like.

The red light emitting component phosphor that constitutes the phosphor film of the high resolution cathode ray tube of the present invention together with the blue light emitting component phosphor and the green light emitting component phosphor has a long afterglow with a 10% afterglow time of at least 5 milliseconds. It is composed of a phosphor that emits orange to red light. Specific examples of such long afterglow orange to red emitting phosphors are conventionally known (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphors, Zn ₃ (PO ₄ ) ₂ :
Mn phosphor, MgSiO ₃ : Mn phosphor, CaSiO ₃ :
Mn, Pb phosphor, 3Cd ₃ (PO ₄ ) ₂・CdCl ₂ : Mn phosphor, Ln ₂ O ₃ : Eu, Dy phosphor (however, Ln is Y, Gd,
is at least one of La and Lu),
Examples include KMgF ₃ :Mn phosphor, MgF ₂ :Mn phosphor, and the like. The red emitting component phosphor may consist solely of a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 milliseconds, or alternatively may consist solely of a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 milliseconds. It may be a product in which an appropriate amount of a short afterglow orange to red emitting phosphor is mixed with a long afterglow orange to red emitting phosphor to adjust afterglow characteristics and luminance. the
The 10% afterglow time is 5 to 150 milliseconds. Therefore, if a long afterglow orange to red emitting component phosphor with a 10% afterglow time of more than 150 milliseconds is used, the phosphor may also contain a short afterglow orange to red emitting component phosphor. The 10% afterglow time must be adjusted to 150 milliseconds or less, and the long afterglow orange to red emitting phosphor must be mixed with the short afterglow orange to red emitting phosphor to produce red. When forming the luminescent component phosphor, both must be mixed in such a proportion that the 10% afterglow time of the resulting red luminescent component phosphor is not shorter than 5 milliseconds. A specific example of a short afterglow orange to red emitting phosphor to be mixed with a long afterglow orange to red emitting phosphor is a europium-activated rare earth oxysulfide phosphor (Ln ₂ O ₂ S: Eu, but Ln is at least one of Y, Gd, La and Lu), europium-activated rare earth oxide phosphor (Ln ₂ O ₃ :Eu, where Ln has the same definition as above), europium-activated Examples include rare earth vanadate phosphors (LnVO ₄ :Eu, where Ln has the same definition as above), gold and aluminum activated zinc sulfide phosphors (ZnS: Au, Al), and the like.

When the high-resolution cathode ray tube of the present invention is a black and white cathode ray tube, its phosphor film includes the above-mentioned blue light emitting component phosphor,
This is a film of a white light-emitting mixed phosphor made by mixing a green light-emitting component phosphor and a red light-emitting component phosphor in an appropriate ratio. The fluorescent film is formed on the face plate by a precipitation coating method, a spin coating method, etc., which have been generally employed for forming a fluorescent film in black-and-white cathode ray tubes. Generally, a metal vapor-deposited film (metal back) made of aluminum or the like is provided on the back surface (electron beam incident surface) of the fluorescent film to prevent charge up during excitation. The configuration or structure of the high-resolution black-and-white cathode ray tube of the present invention other than the phosphor film is the same as that of the conventional black-and-white cathode ray tube, so a description thereof will be omitted.

As explained above, the blue-emitting component phosphor used in the phosphor film of the high-resolution cathode ray tube of the present invention has a sufficiently long 10% afterglow time, and there is no color shift in the emission color after excitation is stopped. It rarely or never occurs. Therefore, the phosphor film of the high-resolution black-and-white cathode ray tube of the present invention emits white light even after excitation is stopped, and the phosphor film of the high-resolution black-and-white cathode ray tube of the present invention emits white light even after excitation is stopped, and the phosphor film of the conventional high-resolution black-and-white cathode ray tube that uses a light blue phosphor as a blue-emitting component phosphor exhibits white light emission. Unlike membranes, there is no noticeable color shift in the emission color after excitation stops.

When the high-resolution cathode ray tube of the present invention is a color cathode ray tube, the phosphor film includes a blue light emitting element made of the above blue light emitting component phosphor, a green light emitting element consisting of the above green light emitting component phosphor, and the above red light emitting component. It is composed of a regular repetition of a trio of red light emitting elements made of phosphor. Each light emitting element is formed in the form of a dot or a stripe like a conventional color cathode ray tube, but it is more preferable to form it in the form of a dot. Each light emitting element is formed on the face plate by a conventionally known method such as optical printing. Generally, a metal vapor-deposited film made of aluminum or the like is provided on the back surface (electron beam incident surface) of the fluorescent film, as in the case of the black-and-white cathode ray tube described above. Additionally, a shadow mask is generally installed between the fluorescent film and the electron guns (generally there are three). The configuration or structure of the high resolution color cathode ray tube of the present invention other than the fluorescent film is the same as that of the conventional color cathode ray tube. Therefore, detailed explanation thereof will be omitted here.

As explained above, the blue light-emitting component phosphor (blue light-emitting element) constituting the phosphor film of the high-resolution color cathode ray tube of the present invention causes no or almost no color shift in the emission color after excitation is stopped. . In addition, since the 10% afterglow time of this blue-emitting component phosphor is sufficiently long, the phosphor film of the high-resolution color cathode ray tube of the present invention emits light in almost the same color as during excitation even after excitation is stopped, resulting in light blue light. Unlike conventional high-resolution color cathode ray tubes that use a phosphor as a blue-emitting component phosphor, there is no noticeable color shift in the emission color after excitation is stopped. Furthermore, as explained above, the blue light-emitting component phosphor constituting the phosphor film of the high-resolution color cathode ray tube of the present invention does not cause color unevenness in the emitted light color unlike the conventional light blue phosphor. Furthermore, the color purity of its emitted light color is much higher than that of conventional light blue phosphors.

As explained above, the present invention provides a high-resolution cathode ray tube that improves the drawbacks of conventional high-resolution cathode ray tubes that use a light blue phosphor as a blue-emitting component phosphor, such as the color shift of the emitted light after excitation is stopped. It provides pipes, and its industrial utility value is extremely large.

The invention will now be described by way of an example particularly relating to a black and white cathode ray tube.

Example 1 As a blue light emitting component phosphor, the activation amounts of silver, gallium and chlorine are respectively 10 ^-2 % by weight, 1.5×10 ^-3 % by weight and 10 ^-4 % by weight of the zinc sulfide matrix,
ZnS: Ag, Ga, Cl phosphor (phosphor-
) 40% by weight, 10% as green emitting component phosphor Zn ₂ SiO ₄ with an afterglow time of 65 ms: Mn, As
30% by weight of phosphor, and 10% red emitting component as phosphor (Zn, Mg) with an afterglow time of 133 ms ₃
A white-emitting mixed phosphor was obtained by uniformly mixing these phosphors using 30% by weight of (PO ₄ ) ₂ :Mn phosphor. This mixed phosphor was uniformly coated on a face plate by a precipitation coating method to form a phosphor film, and then a black and white cathode ray tube of the present invention was manufactured according to a general method for manufacturing a black and white cathode ray tube.

Apart from this, the above ZnS: The activation amount of silver and chlorine instead of Ag, Ga, Cl phosphor is
A black-and-white cathode ray tube was manufactured in the same manner as above except for using a ZnS:Ag, Cl phosphor with a short afterglow property whose main crystal phase is the same cubic system as the Ag, Ga, Cl phosphor. (This cathode ray tube is made by mixing the above-mentioned ZnS:Ag, Cl phosphor, the above-mentioned Zn ₂ SiO ₄ :Mn, As phosphor, and the above-mentioned (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor. (This corresponds to a black-and-white cathode ray tube that uses a light blue phosphor as a blue-emitting component phosphor.Hereinafter referred to as a "conventional cathode ray tube.") The phosphor films of the above two cathode ray tubes emit light under electron beam excitation. All spectra showed white light emission as shown by curve a in Figure 3. However, the phosphor film of the cathode ray tube of the present invention stops excitation15
In contrast, the fluorescent film of conventional cathode ray tubes emitted yellow-green light 15 milliseconds after excitation stopped, and yellow light 30 milliseconds later. It emitted light, and a color shift occurred in the emitted light color. Curves b and c in FIG. 3 are the emission spectra 15 milliseconds and 30 milliseconds after the excitation of the phosphor film of the cathode ray tube of the present invention is stopped, respectively.
Curves d and e in the figure are the emission spectra of the phosphor film of a conventional cathode ray tube 15 milliseconds and 30 milliseconds after excitation is stopped, respectively. As is clear from these emission spectra, the phosphor film of the cathode ray tube of the present invention emits light in the blue region even 30 milliseconds after excitation stops, whereas the phosphor film of the conventional cathode ray tube emits light in the blue region even after excitation stops. After 15 seconds, the luminescence in the blue region has already disappeared.

Figure 4 shows the emission chromaticity points of the phosphor films of the above-mentioned cathode ray tubes of the present invention and the conventional cathode ray tube under electron beam excitation, and the emission chromaticity points of the phosphor films 15 milliseconds and 30 milliseconds after the electron beam excitation has stopped. It is shown on the CIE color system chromaticity coordinates along with the emission chromaticity point of the phosphor that makes up the phosphor. In FIG. 4, point A indicates long afterglow ZnS that constitutes the phosphor film of the cathode ray tube of the present invention: Ag, Ga, Cl phosphor and short afterglow ZnS that constitutes the phosphor film of the conventional cathode ray tube. : Emission chromaticity point of Ag, Cl phosphor, point B is Zn ₃ SiO ₄ that constitutes the phosphor film of both cathode ray tubes:
The emission chromaticity point of the Mn, As phosphor, point C, constitutes the phosphor film of both cathode ray tubes (Zn, Mg) ₃ (PO ₄ ) ₂ :
This is the emission chromaticity point of Mn phosphor.

The phosphor film of the cathode ray tube of the present invention and the phosphor film of conventional cathode ray tubes both emit white light whose emission chromaticity point is represented by point D (corresponding to curve a in Figure 3) under electron beam excitation. shows. The emission chromaticity point of the phosphor film of the cathode ray tube of the present invention is point E 15 milliseconds after excitation is stopped.
(corresponding to curve b in Figure 3), and after another 30 milliseconds it reaches point F (corresponding to curve b in Figure 3). However, both point E and point F are within the white region, and therefore, the color shift of the emitted light after excitation is stopped in the fluorescent film of the cathode ray tube of the present invention is slight. On the other hand, the emission chromaticity point of the phosphor film of a conventional cathode ray tube becomes point G (corresponding to curve d in Figure 3) in the yellow-green region 15 milliseconds after excitation stops;
After 30 milliseconds, point H in the yellow area (curve e in Figure 3)
). As described above, the color shift of the emitted light after excitation is stopped in the phosphor film of the conventional cathode ray tube is significant.

Example 2 ZnS of Example 1 as a blue-emitting component phosphor:
Ag, Ga, Cl phosphor 40% by weight, green emitting component phosphor Zn ₂ SiO ₄ :Mn, As phosphor 33 of Example 1
% by weight and short afterglow ZnS: 7% by weight of Cu, Al phosphor, and 12% by weight of (Zn,Mg) ₃ (PO ₄ ) ₂ :Mn phosphor of Example 1 as the red-emitting component phosphor. A black-and-white cathode ray tube was manufactured in the same manner as in Example 1 using 8% by weight of Y ₂ O ₂ S:Eu phosphor having a short afterglow property. Note that the green light-emitting component phosphor is composed of the above Zn ₂ SiO ₄ :Mn phosphor and the above ZnS:Cu, Al phosphor, and the above (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor. light body and above
The 10% afterglow time of the red light-emitting component phosphor composed of Y ₂ O ₂ S:Eu phosphor is 30 milliseconds.

The resulting phosphor film of the cathode ray tube emitted white light under electron beam excitation, but its chromaticity point did not change at all even 15 milliseconds after excitation was stopped.

Example 3 ZnS of Example 1 as a blue-emitting component phosphor:
40% by weight Ag, Ga, Cl phosphor, 10% as green emitting component phosphor Zn ₂ SiO ₄ :Mn with afterglow time 28 ms
3Cd ₃ (PO ₄ ) ₂ with 40% by weight phosphor and 10% red emitting component phosphor with an afterglow time of 36 ms.
CdCl ₂ :Using 20% by weight of Mn phosphor, Example 1
A black and white cathode ray tube was manufactured in the same manner as above.

The phosphor film of the obtained cathode ray tube emits white light having the same chromaticity point as the phosphor film of the cathode ray tube of Example 2 under electron beam excitation, and the emission chromaticity point changes 15 milliseconds after excitation is stopped. Even after that time, there was almost no change.

Example 4 As a blue emitting component phosphor, the activation amount of silver, gallium and chlorine and the sulfur content were respectively ¹⁰ % by weight, 1.5×10 ^-3 % by weight and 10 ^-4 based on the zinc sulfide matrix.
Sulfur-containing ZnS:Ag, ^Ga , Cl phosphor (phosphor- 37% by weight of the Zn 2 SiO ₄ :Nn, As phosphor of Example 1 as the green-emitting component phosphor, 34% by weight of the Zn ₂ SiO 4 :Nn, As phosphor of Example 1 and 8 of the short afterglow ZnS:Cu, Al phosphor of Example 2. % by weight, and (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor of Example 1 as the red emitting component phosphor 13% by weight and short afterglow Y ₂ O ₂ S of Example 2: Eu A black and white cathode ray tube was manufactured in the same manner as in Example 1 using 9% by weight of the phosphor. Note that the above Zn ₂ SiO ₄ :Mn, As phosphor and the above
A green-emitting component phosphor composed of ZnS:Cu and Al, the above (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor, and the above Y ₂ O ₂ S:Eu phosphor. The 10% afterglow time of the red light-emitting component phosphor thus constructed is 30 milliseconds.

The phosphor film of the obtained cathode ray tube emits white light having the same chromaticity point as the phosphor film of the cathode ray tube of Example 2 under electron beam excitation, and its luminance is equal to that of Example 2.
It was 3% higher than the phosphor film of a cathode ray tube. Furthermore, the emission chromaticity point of the fluorescent film did not change at all even after 15 milliseconds had passed after the excitation was stopped.

Example 5 The activation amount of silver, gallium, copper, and chlorine and the sulfur content of the blue light-emitting component phosphor were 10 ^-2 % by weight, 1.5×10 ^-3 % by weight, and 10 ^-4 respectively based on the zinc sulfide matrix.
wt%, 10 ^-4 wt% and 10 ^-4 wt%, 10
Sulfur-containing ZnS with cubic crystalline main crystal phase with afterglow time of 30 milliseconds: Ag, Ga, Cu, Cl phosphor (included in phosphor) 32% by weight, green luminescent component fluorescein As a light body, 36% by weight of Zn ₂ SiO ₄ :Mn,As phosphor of Example 1 and short afterglow ZnS:Cu of Example 2 were used.
8% by weight of the Al phosphor, and 14% by weight of the (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor of Example 1 as the red emitting component phosphor and the short afterglow Y 2 of Example 2 _. A black and white cathode ray tube was manufactured in the same manner as in Example 1 using 10% by weight of O ₂ S:Eu phosphor. Note that the above Zn ₂ SiO ₄ :Mn,
A green-emitting component phosphor composed of an As phosphor and the above ZnS:Cu, Al phosphor, the above (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor and the above Y ₂ O _2S :
The 10% afterglow time of the red light-emitting component phosphor composed of the Eu phosphor and the Eu phosphor is 30 milliseconds.

The phosphor film of the obtained cathode ray tube emits white light having the same chromaticity point as the phosphor film of the cathode ray tube of Example 2 under electron beam excitation, and its luminance is equal to that of Example 2.
It was 7% more expensive than the phosphor film of a cathode ray tube. Furthermore, the emission chromaticity point of the fluorescent film did not change at all even after 15 milliseconds had passed after the excitation was stopped.

Example 6 The activation amount of silver, gallium, gold, and chlorine and the sulfur content as a blue-emitting component phosphor were 10 ^-2 % by weight, 1.5×10 ^-3 % by weight, 10 ^-3 % by weight, based on zinc sulfide base.
Sulfur-containing ZnS: Ag, Ga ^{, Au} , Cl phosphor (fluorescent light body
) 32% by weight of the green-emitting component phosphor, 36% by weight of the Zn ₂ SiO ₄ :Mn,As phosphor of Example 1 and the short afterglow ZnS:Cu,Al phosphor of Example 2. 8
% by weight, and (Zn, Mg) ₃ (PO ₄ ) ₂ :Mn phosphor of Example 1 as the red emitting component phosphor 14% by weight and short afterglow Y ₂ O ₂ S of Example 2: Eu Fluorescent material 10% by weight
A black and white cathode ray tube was manufactured in the same manner as in Example 1. Note that the green-blue light-emitting component phosphor is composed of the above Zn ₂ SiO ₄ :Mn, As phosphor and the above ZnS: Cu, Al phosphor, and the above (Zn, Mg) ₃
The 10% afterglow time of the red light-emitting component phosphor composed of the (PO ₄ ) ₂ :Mn phosphor and the above-mentioned Y ₂ O ₂ S:Eu phosphor is 30 milliseconds.

The phosphor film of the obtained cathode ray tube emits white light having the same chromaticity point as the phosphor film of the cathode ray tube of Example 2 under electron beam excitation, and its luminance is equal to that of Example 2.
It was 7% more expensive than the phosphor film of a cathode ray tube. Furthermore, the emission chromaticity point of the fluorescent film did not change at all even after 15 milliseconds had passed after the excitation was stopped.

Example 7 As a blue-emitting component phosphor, the activation amounts of silver, gallium, and aluminum were respectively different from those of the zinc sulfide matrix.
10 ^-2 wt%, 1.5 × 10 ^-3 wt% and 10 ^-4 wt%, and the main crystalline phase of ZnS is cubic with a 10% afterglow time of 30 ms: Ag, Ga, Cl. 40% by weight of the phosphor (contained in the phosphor), 30% by weight of the Zn ₂ SiO ₄ :Mn, As phosphor of Example 1 as the green emitting component phosphor
wt% and short afterglow ZnS:9 wt% Cu, Cl phosphor, and long afterglow as red emitting component phosphor.
Zn ₃ (PO ₄ ) ₂ : 3% by weight of Mn phosphor and short afterglow.
Y ₂ O ₂ S: Using 8% by weight of Eu phosphor, Example 1
A black and white cathode ray tube was manufactured in the same manner as above. Furthermore, the above
A green light-emitting component phosphor composed of a Zn ₂ SiO ₄ :Mn phosphor and the above ZnS:Cu,Cl phosphor, and the above Zn ₃ (PO ₄ ) ₂ :Mn phosphor and the above Y ₂ O ₂ S: 10 of the red emitting component phosphor composed of Eu phosphor and
The % afterglow time is 30 milliseconds in all cases. The phosphor film of the resulting cathode ray tube emitted white light under electron beam excitation, but the chromaticity of the emitted light did not change at all even 15 milliseconds after excitation was stopped.

[Brief explanation of the drawing]

FIG. 1 is a graph illustrating the emission spectrum of a long-afterglow zinc sulfide phosphor used as the blue-emitting component phosphor of the phosphor film of the high-resolution cathode ray tube of the present invention. Figure 2 shows the amount of gallium activation and the amount of 10
It is a graph illustrating the relationship with % afterglow time. FIG. 3 is a graph illustrating the emission spectra of the phosphor films of the present invention and conventional high resolution black and white cathode ray tubes under electron beam excitation, and the emission spectra 15 milliseconds and 30 milliseconds after the electron beam excitation has stopped. Figure 4 shows the emission chromaticity points of the phosphor films of the present invention and conventional high-resolution black and white cathode ray tubes under electron beam excitation, and the emission chromaticity points 15 milliseconds and 30 milliseconds after the electron beam excitation has stopped. It is shown on the CIE color system chromaticity coordinates along with the emission chromaticity point of the phosphor that makes up the light film.

Claims (1)

[Claims] 1 ()(i) Zinc sulfide is used as a matrix, silver is used as an activator, gallium is used as a first co-activator, chlorine,
At least one of bromine, iodine, fluorine and aluminum is used as a second co-activator, and the amounts of the above-mentioned activator, first co-activator and second co-activator are respectively the above-mentioned zinc sulfide. Maternal 5×
(ii) a blue-emitting zinc sulfide phosphor that is from 10 ^-4 to 10 ^-1 % by weight, from 10 ^-6 to 5×10 ^-1 % by weight, and from 5×10 ^-6 to 5×10 ^-2 % by weight; (ii) zinc sulfide; as a matrix, silver as an activator, gallium as a first co-activator, chlorine, bromine,
At least one of iodine, fluorine and aluminum is used as a second co-activator, and the amounts of the above-mentioned activator, the first co-activator and the second co-activator are determined respectively based on the zinc sulfide matrix. 5 x 10 ^-4 to 10 ^-1 weight %, 10 ^-6 to 5 x 10 ^-1 weight %, and 5 x 10 ^-6 to 5 x 10 ^-2 weight %, and the sulfur is 10 ^- of the zinc sulfide matrix. ⁵ to 8×10 ^-1
(iii) a blue-emitting zinc sulfide phosphor containing zinc sulfide as a host, silver as an activator, gallium as a first co-activator, and at least one of gold and copper as a second co-activator; an activator, at least one of chlorine, bromine, iodine, fluorine, and aluminum as a third coactivator; the above activator, the first coactivator, and the second coactivator; and the amount of the third co-activator is 5 x 10 ^-4 to 10 ^-1 weight %, 10 ^-6 to 5 x 10 ^-1 weight %, 1.5 x 10 ^-2 weight % or less of the zinc sulfide matrix, and 5 x 10 ^-6 to 5 x 10 ^-2 weight percent of a blue-emitting zinc sulfide phosphor, and (iv) zinc sulfide as the host, silver as the activator, and gallium as the first co-activator. , at least one of gold and copper is used as a second co-activator; at least one of chlorine, bromine, iodine, fluorine and aluminum is used as a third co-activator; The amounts of the co-activator, the second co-activator and the third co-activator are 5×10 ^-4 to 10 ^-1 % by weight and 10 ^-6 to 5×10 ^-1 of the zinc sulfide matrix, respectively. % by weight, 1.5 x 10 ^-2 weight % or less and 5 x 10 ^-6 to 5 x 10 ^-2 weight %, and a blue color containing 10 ^-5 to 8 x 10 ^-1 weight % of sulfur based on the zinc sulfide matrix. A blue-emitting component phosphor containing at least one type of luminescent zinc sulfide phosphor as a main component and having a 10% afterglow time of 5 to 150 milliseconds; a green-emitting component phosphor comprising a long-afterglow green-emitting phosphor and having a 10% afterglow time of 5 to 150 milliseconds;
and () a long persistence orange to red emitting phosphor with a 10% afterglow time of at least 5 ms, and a phosphor comprising a red emitting component phosphor with a 10% afterglow time of 5 to 150 ms. A high resolution cathode ray tube characterized by having a light film. 2 The amount of the first co-activator in the blue-emitting zinc sulfide phosphor in (i) above, the amount of the first co-activator in the blue-emitting zinc sulfide phosphor in (ii) above, and the amount in (iii) above. ) The amount of the first co-activator in the blue-emitting zinc sulfide phosphor and the amount of the first co-activator in the blue-emitting zinc sulfide phosphor in (iv) above are both 10 ^-6 to 10 ^-2 % by weight of the high-resolution cathode ray tube according to claim 1. 3 The main crystal phase of the blue-emitting zinc sulfide phosphor of (i) above, the main crystal phase of the blue-emitting zinc sulfide phosphor of (ii) above, the main crystal of the blue-emitting zinc sulfide phosphor of (iii) above. 3. The high-resolution cathode ray tube according to claim 1 or 2, wherein both the phase and the main crystal phase of the blue-emitting zinc sulfide phosphor (iv) are cubic systems. 4 The long-afterglow green-emitting phosphor is a manganese-activated zinc silicate phosphor (Zn ₂ SiO ₄ :Mn) and a manganese- and arsenic-activated zinc silicate phosphor (Zn ₂ SiO ₄ :Mn,
As), and the long afterglow orange to red emitting phosphor is a manganese-activated zinc/magnesium orthophosphate phosphor [(Zn, Mg) ₃
(PO ₄ ) ₂ :Mn], manganese-activated zinc orthophosphate phosphor [Zn ₃ (PO ₄ ) ₂ :Mn], manganese-activated magnesium silicate phosphor (MgSiO ₃ :Mn), manganese and lead activated Calcium silicate phosphor ( _CaSiO3 :
Mn, Pb), manganese activated cadmium chloride phosphate phosphor [3Cd ₃ (PO ₄ ) ₂・CdCl ₂ :Mn], europium and dysprosium activated rare earth oxide phosphor (Ln ₂ O ₃ : Eu, Dy, However, Ln is Y, Gd, La and
at least one kind of manganese-activated potassium fluoride/magnesium fluoride phosphor (KMgF ₃ :Mn) and manganese-activated magnesium fluoride phosphor (MgF ₂ :Mn). Claim 1 characterized in that
A high-resolution cathode ray tube according to any one of items 1 to 3. 5 The high resolution cathode ray tube is a high resolution black and white cathode ray tube, and the phosphor film is a mixture of the blue light emitting component phosphor, the green light emitting component phosphor and the red light emitting component phosphor in an appropriate ratio. A high-resolution cathode ray tube according to any one of claims 1 to 4, characterized in that it is a film of a white-emitting mixed phosphor. 6 The high-resolution cathode ray tube is a high-resolution color cathode ray tube, and the phosphor film includes a blue light-emitting element comprising the blue light-emitting component phosphor, a green light-emitting element comprising the green light-emitting component phosphor, and the red light-emitting component. 5. A high-resolution cathode ray tube according to any one of claims 1 to 4, characterized in that the cathode ray tube is constructed by regularly repeating a trio of light emitting elements of red light emitting elements made of phosphor.