JPH11228952A - Phosphor material, production thereof, and plasma display panel and apparatus prepared by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To cause an energy ray to be surely incident into a phosphor, improve the luminescent efficiency in the visible range, and provide a phosphor material which can maintain contrast on a display screen. SOLUTION: A light absorber 102 is caused to be present concentratively inside a phosphor 101 constituting a phosphor material 100, thus making sure the penetration of ultraviolet rays into the phosphor 101 and simultaneously causing the light absorber 102 to absorb unnecessary external light. Thus, the luminescent efficiency of the phosphor material 100 is enhanced and a plasma display apparatus excellent in contrast is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor for a color display device, and more particularly, to a phosphor material used for a plasma display device (hereinafter, referred to as a PDP), a method of manufacturing the same, a PDP constituted by using the same, and P
It relates to a DP device.

[0002]

2. Description of the Related Art Conventionally, when displaying a color image,
For example, CRT (Cathode Ray Tube) or PDP (Plasma Display Panel)
Various types of so-called self-luminous display devices have been realized. Such a self-luminous display device is, for example, a CRT.
A desired color image is displayed by irradiating some kind of energy ray, such as an electron beam if it is a PDP, or an ultraviolet ray if it is a PDP, into a phosphor layer corresponding to the three primary colors of light to obtain light emission in the visible light range. It has been made to be.

Further, red (R) forming the phosphor layer,
Phosphor materials used for green (G) and blue (B) emission are as follows:
In order to suppress the reflection of light incident from the outside, a light absorber (pigment) of the same color as the emission color of the phosphor is included, so that the light of a color other than the same color as the phosphor is not affected without affecting the emission of the phosphor. And its reflection is substantially suppressed.

FIG. 15 shows, for example, Japanese Patent Application Laid-Open No. 61-24364.
FIG. 1 is a diagram showing a phosphor material used for a conventional CRT described in Japanese Patent Application Publication No. 0-205. In the drawing, reference numeral 1 denotes a phosphor, and 2 denotes a pigment having the same color and a fine particle size as the phosphor 1 covering the surface of the phosphor 1. The phosphor 1 and the pigment 2 constitute a phosphor material.

FIG. 16 is a view showing another phosphor material described in the publication. In the figure, 1 is a phosphor of the same material as that shown in FIG. 15, 3 is a pigment included (mixed) at random positions in the phosphor 1, and the phosphor 1 and the pigment 3 Is configured. The pigment 3 is also mixed near the surface of the phosphor 1.

In the case of a CRT, these FIG.
A phosphor material as shown in FIG. 16 is provided as a phosphor layer on the inner surface of the display surface of the CRT, and an electron beam accelerated by an electron gun is projected on the phosphor 1 in the phosphor layer, thereby forming a phosphor material. A desired image display is performed by light emission (fluorescence) from the camera.

A case where a conventional phosphor material is used for, for example, a PDP will be described. First, a predetermined voltage is applied between a pair of electrodes called so-called display electrodes corresponding to discharge cells to emit light. Then, by exciting a discharge gas (mixed gas of neon and xenon) sealed in the discharge cell, ultraviolet rays are generated from the discharge gas. Ultraviolet light generated from the discharge gas is incident on the phosphor 1 in a phosphor layer provided at a position facing the display electrode, for example, and is converted into light in a visible light region to become light for image display.

In addition, light incident from the outside is absorbed by the pigments 2 and 3 having a function as a light absorber, and the reflection of the light is suppressed to improve the contrast so that the displayed image can be easily viewed. .

[0009]

However, when the phosphor material having the structure shown in FIG. 15 is used for a CRT or a PDP or the like, an energy ray (excitation light, in this case) for causing the phosphor 1 to emit light. Represents an electron beam or an ultraviolet ray.) Is the pigment 2 existing on the outer surface of the phosphor 1.
Part of the energy ray is reflected by the pigment 2 before the energy ray reaches the phosphor 1 or the energy ray reaches the phosphor 1, and eventually the luminous efficiency of the phosphor material (from the energy ray to the light in the visible light region) Conversion efficiency).

In particular, when applied to a PDP, the absorption and excitation of ultraviolet light generated from the discharge gas by the phosphor 1 and the generation of light in the visible light region are relatively few hundred angstroms from the outer surface of the phosphor 1. Occurs at short distances,
The presence of the pigment 2 on the outer surface of the phosphor 1 greatly affects the conversion efficiency of ultraviolet light into visible light.

When a phosphor material having the structure shown in FIG. 16 is used for a CRT, a PDP, or the like, the pigment 3 is randomly present inside the phosphor 1 so that the phosphor material shown in FIG.
Although the pigment 3 is also present in the vicinity of the surface of the phosphor 1 although the number is smaller than the case where the structure shown in FIG. 5 is used, the same problem as that described in the structure shown in FIG. The reflection and absorption of ultraviolet rays by the pigment 3 could not be completely prevented.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problem, and it is possible to improve the luminous efficiency of light in a visible light region by ensuring that energy rays are incident on a phosphor. It is an object of the present invention to obtain a phosphor material that can maintain the contrast of a display screen.

[0013]

According to a first aspect of the present invention, there is provided a phosphor material which emits light in a visible light range when an energy ray is incident thereon, and a light absorbing member provided intensively inside the phosphor. It consists of a body.

[0014] The phosphor material according to the second invention is characterized in that the light absorber is provided substantially at the center of the outer shape of the phosphor surrounding the light absorber.

[0015] The phosphor material according to a third aspect of the present invention is characterized in that the light absorber is surrounded by a plurality of phosphor particles.

The phosphor material according to the fourth invention is characterized in that the light absorber is a pigment made of an inorganic material.

The phosphor material according to the fifth invention is characterized in that the light absorber has the same color as the emission color of the phosphor.

The phosphor material according to the sixth aspect of the present invention is characterized in that the phosphor material contains a light absorber so that the luminous efficiency does not become 70% or less as compared with a case where no light absorber is contained. .

According to a seventh aspect of the present invention, there is provided a plasma display panel comprising: a pair of display electrodes extending in a line direction for each display line on an inner surface of a front or back substrate in a pair of substrates sandwiching a discharge space; The discharge gas sealed in the discharge space and the light absorber that is provided intensively inside the phosphor that emits light in the visible light region by the incidence of ultraviolet light generated from the discharge gas based on the discharge between the display electrode pair. And a phosphor layer made of a phosphor material.

According to an eighth aspect of the present invention, in the plasma display panel, the light absorber of the phosphor material is located substantially at the center of the outer shape of the phosphor surrounding the periphery.

According to a ninth aspect of the present invention, in the plasma display panel, the light absorber of the phosphor material is surrounded by a plurality of phosphor particles.

The plasma display panel according to the tenth aspect is characterized in that the light absorber in the phosphor material is a pigment made of an inorganic material.

In a plasma display panel according to an eleventh aspect of the present invention, the light absorber in the phosphor material has the same color as the emission color of the phosphor.

The twelfth aspect of the present invention is the plasma display panel, wherein the phosphor material contains a light absorber so that the luminous efficiency does not become 70% or less as compared with a case where the light absorber is not contained. It is assumed that.

According to a thirteenth aspect of the present invention, in the method for producing a phosphor material, a phosphor which emits light in a visible light range when an energy ray is incident is grown around the light absorber, and the light absorber is surrounded by the phosphor. And a phosphor forming step for forming the phosphor.

In a fourteenth aspect of the present invention, the method of manufacturing a phosphor material is characterized in that the phosphor forming step is performed in a liquid containing a predetermined component.

In a fifteenth aspect of the present invention, the method of manufacturing a phosphor material is characterized in that the step of forming the phosphor includes a step of increasing the hydrogen ion exponent in the liquid.

According to a sixteenth aspect of the present invention, in the method for manufacturing a phosphor material, the inorganic pigment is dispersed in a predetermined dispersion medium according to the type of the inorganic pigment, and then the dispersion medium contains a metal component constituting the phosphor. A first step of obtaining a solution having a salt soluble therein, a second step of obtaining a precipitate by increasing the hydrogen ion exponent in the solution obtained by the first step, and a second step A third step of filtering and drying the obtained precipitate, and then firing it under predetermined conditions.

The method for producing a phosphor material according to the seventeenth aspect is the method according to the sixteenth aspect, wherein in the first step, iron oxide is used as an inorganic pigment, water is used as a dispersion medium, and yttrium soluble in this dispersion medium is contained. Salt and a salt containing europium, and ammonia in the second step, respectively, are used, and the calcination in the third step is as follows: (A) 1250-1300 degrees Celsius in an oxygen atmosphere
Or (B) in an oxygen atmosphere under any of the conditions of 1200 degrees Celsius to form a red phosphor material.

The method for producing a phosphor material according to the eighteenth aspect of the present invention is the method according to the sixteenth aspect, wherein in the first step, cobalt green is used as the inorganic pigment, water is used as the dispersion medium, and zinc soluble in the dispersion medium is contained. Alkoxide, an alkoxide containing silicic acid, a salt of an alkoxide containing manganese, and ammonia in the second step are used, and the calcination in the third step is as follows: (A1) 850-degree Celsius in an oxygen atmosphere; 900 degree (A2) Further, in a reducing atmosphere, 1250 degrees Celsius
(B1) 800 ° C. in an oxygen atmosphere, (B2) further performed in a reducing atmosphere under a condition of 1200 ° C. to form a green phosphor material. Is what you do.

According to a nineteenth aspect of the present invention, in the method of the sixteenth aspect, in the first step, in the first step, cobalt aluminate is used as an inorganic pigment, urea is dissolved in water as a dispersion medium, Barium-containing salt, magnesium-containing salt, aluminum-containing salt and europium-containing salt are used, respectively. In the second step, the solution obtained in the first step is stirred while The hydrogen ion index is increased by increasing the temperature, and the firing in the third step is performed by: (A1) 850 to 900 degrees Celsius in an oxygen atmosphere; (A2) 1250 to 900 degrees Celsius in a reducing atmosphere.
1300 ° C. or (B1) 800 ° C. in an oxygen atmosphere, (B2) further performed in a reducing atmosphere under a condition of 1200 ° C. to form a blue phosphor material. Is what you do.

The method for producing a phosphor material according to the twentieth invention is characterized in that, in the second step of the sixteenth invention, the value of the attained hydrogen ion exponent is in the range of pH 9 to 12. Things.

According to a twenty-first aspect of the present invention, there is provided a plasma display device comprising: a pair of display electrodes extending in a line direction for each display line between a pair of display electrodes and a pair of substrates; Discharge gas sealed in the discharge space, fluorescent light including a light absorber intensively provided inside a fluorescent material that emits light in the visible light region due to the incidence of ultraviolet light generated from the discharge gas based on the discharge between the display electrode pairs The plasma display panel includes each of the phosphor layers made of a body material, and a drive control unit for driving the plasma display panel.

[0034]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Part 1 Common to First and Second Embodiments) In the following, an embodiment of the present invention will be described with an example of an apparatus using a plasma display panel (hereinafter referred to as a PDP apparatus). Will be described.

FIG. 1 shows one embodiment according to the present invention.
FIG. 2 is a block diagram illustrating an overall configuration of a PDP device 1000. As shown in FIG. 1, this apparatus 1000 is a PDP 5
00 and a drive control unit 2 that applies drive signals such as a priming pulse, a write pulse, and a sustain pulse to the PDP 500. The drive control unit 2 includes an analog-to-digital converter (hereinafter, referred to as an A / D) 12.
0, frame memory 130, scan control unit 110, X
It comprises an electrode drive circuit 141, a Y electrode drive circuit 142 and an A electrode drive circuit 143.

As will be described later, the PDP 500
An X electrode serving as a first display electrode or a first electrode, a Y electrode serving as a second display electrode or a second electrode provided on the front substrate (first substrate) side, and a back substrate (a first electrode) facing the first substrate. A third electrode or an A electrode as an address electrode disposed on the (2 substrate) side so as to intersect at right angles with a pair of X and Y electrodes (these electrodes are collectively referred to as a pair of display electrodes). This is an AC3 electrode surface discharge type panel.

The operation of the plasma display device 1000 will be described. Plasma display device 1000
Comprises a PDP 500 and a drive control unit 2 electrically connected to the X, Y, A electrodes of the PDP 500 via a flexible printed wiring board (not shown).

In the drive controller 2, first, an input signal VIN for providing image data is converted from analog to digital by the A / D 120, and the digital data output from the A / D 120 is stored in the frame memory 130. After that, the scan control unit 110
, And various control signals for controlling the driving of the X-electrode drive circuit 141, the Y-electrode drive circuit 142, and the A-electrode drive circuit 143 based on those signals, respectively. Output to the driving circuits 141 to 143.

In response to the control signal, the driving circuits 141 to 143 operate as follows: a priming pulse 121, a write scan pulse 122 (hereinafter, referred to as a scan pulse), an address pulse 124, and a sustaining pulse as shown in FIG. The driving pulse signals of 123-1, 123-2, etc. are applied to the corresponding electrodes of the PDP 500 to which the respective driving pulse signals are to be applied, thereby driving the PDP 500.

Now, the A electrodes A1 to A3 in FIG.
Assuming that each of the A electrodes A1 to A3 is disposed under each of the phosphor layers that emit red (R), green (G), and blue (B) fluorescence, respectively, an X electrode and a Y electrode Due to the presence of a discharge gas containing neon or xenon gas in a portion defined based on the position intersecting with, a unit of visible light emission based on discharge generated between the electrodes (hereinafter, referred to as a discharge cell) None, an area EG surrounded by a broken line gives one pixel.

The wiring configuration of the X, Y, and A electrodes in the PDP 500 is schematically shown in the plan view of FIG.
That is, the X electrode XE is a signal line common to all the discharge cells, and the X electrode XE and each of the Y electrodes YE1 to YEn.
Constitute a plurality of electrode pairs, and the X electrode XE and the Y electrode YEi
(I = 1 to n), each electrode pair (corresponding to the above-mentioned pair of electrodes) intersects with each A electrode Aj (j = 1 to m), and (mxn) discharge cells are formed. It is configured.

Note that any one of Y from 1 to n
A display line on the PDP screen is constituted by a pair of electrodes, an electrode YEi and an X electrode XE that generates a discharge for display between the Y electrode Yi (the direction in which the display line extends). Line direction).

The priming pulse 121 output from the X electrode driving circuit 141, the first sustain pulse 123-1, the scanning pulse 122 output from the Y electrode driving circuit 142, the second sustain pulse 123-2, and the output from the A electrode driving circuit 143 are output. FIGS. 3A to 3E show timing charts for each pulse and signal of the address signal 124 to be applied.

FIG. 4 shows a PDP 500 as described above,
It is a schematic cross section which shows an example of the principal part structure seen from the extending direction of the electrode Aj, In the figure, 5 is a front substrate,
50 is a Y electrode (or X electrode) provided on the front substrate.
In the following description, the Y electrode 50 will be described unless otherwise specified), 51 is a dielectric layer, 52 is provided on the dielectric layer 51, protects the dielectric layer 51 from ion bombardment, and discharges electrons during discharge. A protection layer 6 made of MgO for smoothing radiation and stabilizing discharge, 6 a back substrate arranged in parallel to the front substrate 5, 9 a discharge cell, 60 an A electrode,
Reference numeral 7 denotes a partition provided on the back substrate 6 for partitioning the discharge cells 9 along the direction of the A electrode 60.

Reference numeral 8 denotes a discharge cell 9 partitioned by a partition wall 7.
This is a phosphor layer formed by attaching a phosphor material to the inside rear substrate 6, the A electrode 60, and the side surfaces of the partition walls 7. The discharge cell 9 is filled with a discharge gas containing neon or xenon as described above.

The operation will be described below with reference to FIG. A protective layer 5 is formed on the pair of display electrodes described above.
A priming discharge and an erasing discharge are realized by applying a priming pulse 121 to the X electrode.
The wall charges accumulated (residual) on the entire upper surface (actually, on the protective layer 52) are once erased (priming operation period in FIG. 3).

Thereafter, the scanning pulse 122 is sequentially applied to the Y electrodes YE1 to YEn (50 in FIG. 4), and A
The address signal 1 is applied to one of the electrodes Aj (60 in FIG. 4).
24 is applied to perform a selective write discharge, and a pair of discharge cells (9 in FIG. 4) corresponding to positions of discharge cells (9 in FIG. 4) to be subjected to a discharge for display in a form induced by the write discharge. Wall charges having different polarities are selectively accumulated on the dielectric layer (51 in FIG. 4; actually, the protective layer 52) on each of the display electrodes (address operation period in FIG. 3).

After the selective writing discharge is completed in all the discharge cells, the first sustain pulse 123- is applied between the pair of display electrodes.
1. When the second sustain pulse 123-2 is applied as shown in FIG. 3, a discharge for display is performed in the discharge cells (9 in FIG. 4) in which the above-described write discharge has been performed, The above two sustain pulses 12 are provided for the number of times necessary for expressing the gradation.
By alternately applying 3-1 and 123-2 between the pair of display electrodes, the discharge is maintained (sustain discharge; the period of the sustain operation in FIG. 3).

In this sustain discharge, the discharge gas sealed in the discharge cell 9 is a predetermined voltage between the pair of display electrodes (a voltage of a polarity for energizing the wall voltage generated by the wall charge described above, (Referred to as voltage), and is excited by a discharge generated by applying a voltage to generate ultraviolet rays having a wavelength of 147 nm. The generated ultraviolet light enters the phosphor layer 8 provided so as to face the pair of display electrodes, is converted into light in the visible light region, and an image displayed by the viewer through the front substrate 5 is displayed. Will be Of course, when displaying a color image, red (R), green (G) and blue (B)
In order to emit light corresponding to the three primary colors, a phosphor layer corresponding to each light emission color is provided on the PDP corresponding to each color and each discharge cell, and a full color image display is performed by combining the light emission of each color. Is performed.

(Part 2 Common to First and Second Embodiments)
The above-described phosphor layer 8 is configured in a state where the phosphor material is sintered as shown as an example in FIG. That is, FIG.
Is a phosphor layer 8 surrounded by a dotted frame A shown in FIG.
2 is an enlarged view of a main part, in which 8 is a main part enlarged view, in which 8 is a phosphor layer, 600 is a phosphor material constituting the phosphor layer 8,
Reference numeral 601 denotes a phosphor in the phosphor material 600, and 602 denotes a light absorber made of a pigment provided intensively inside the phosphor material 600.

As described above, the phosphor layer 8 is provided so as to face the pair of display electrodes, and the ultraviolet light generated between the pair of display electrodes is directed to the phosphor layer 8 to form the phosphor layer 8. And is converted into light in the visible light region.

Here, since the light absorber 602 is provided intensively inside the phosphor material 600, the ultraviolet light incident on the phosphor material 600 is not blocked by the light absorber 602, and It penetrates to a few hundred angstroms from the surface and is absorbed. The ultraviolet light absorbed here excites the phosphor 601 and is converted into fluorescence (emission in the visible light region) when the excited state returns to the prescribed state.

Accordingly, the efficiency of conversion of energy rays such as ultraviolet rays and electron beams into visible light in the phosphor material 600 is improved as in the prior art, and particularly, the absorption in the phosphor 601 such as ultraviolet rays used for PDP is improved. When the length is short, the light is blocked by the light absorber 602 (the light absorber 602).
Reflection and absorption in the light emitting element), and thus has a great effect on improving the luminous efficiency.

Further, since the light absorber 602 is provided inside the phosphor material 600, external light incident on the discharge cells from the front substrate is reflected by the phosphor layer 8, and is again transmitted through the front substrate. Since the amount of light reflected to the outside is reduced, it is possible to suppress the reflection of external light in a state where the display discharge is not performed, and it is possible to improve the contrast at the time of displaying an image.

As described above, the light absorber 602 is disposed inside the phosphor material 600, in other words, the phosphor 601 which emits light in the visible light range when an energy ray is incident thereon is replaced with the light absorber 602. Around the surface of the phosphor material 600 in a liquid of a predetermined component by growing the hydrogen ion exponent by increasing the hydrogen ion exponent and forming the light absorber 602 so as to be surrounded by the phosphor 601. The basic manufacturing method will be described with reference to the flowchart shown in FIG.

In FIG. 8, S1 is a dispersion of an inorganic pigment in a predetermined dispersion medium according to the type of the inorganic pigment, and then contains a metal component or metal ion constituting the phosphor, and the inorganic pigment is dispersed. In the first step of obtaining a solution in which a salt soluble in a dispersion medium is dissolved, S2 is a step in which an inorganic pigment is dispersed,
The second step of obtaining a precipitate from the solution by increasing (making alkaline) a hydrogen ion index (hereinafter referred to as pH or pH) in a solution in which a salt soluble in a dispersion medium is dissolved, S3 is a second step. This is a third step in which the precipitate obtained in the step is filtered, dried, and fired.

First, a liquid in which fine powder of an inorganic pigment is mixed and dispersed in a dispersion medium such as water is obtained. At this time, when using an inorganic pigment that is not easily dispersed in the dispersion medium, for example, a dispersant containing a polycarboxylic acid is mixed into the dispersion medium together with the inorganic pigment, and the inorganic pigment is uniformly dispersed in the dispersion medium. It is good to do so. Thereafter, a salt containing metal ions (which vary depending on the emission color) necessary for constituting the phosphor and being soluble in the dispersion medium is dissolved in a liquid in which the inorganic pigment is dispersed, and the dispersed inorganic pigment becomes fluorescent. A state in which a salt containing a metal ion necessary for constituting the body is dispersed in a solution in which the salt is dissolved (first step).

Next, the pH of the solution obtained in the first step is increased to a range of 9 to 12, so that the phosphor adheres around the dispersed inorganic pigment. By this operation, a granular precipitate is obtained in which the above-described pigment as the light absorber is wrapped by the phosphor (second step).

In this case, if the attained value of the pH is lower than pH 9, the adhesion of the phosphor to the periphery of the inorganic pigment becomes insufficient, and the amount of the obtained precipitate tends to decrease (the phosphor becomes a phosphor in the solution). When the reached value of pH is higher than pH 12, the alkaline component becomes strong, and the alkaline component tends to cause re-dissolution of the precipitate (adhesion around the inorganic pigment). Phosphor that has melted out). Accordingly, in the second step, it is effective to use a dispersion medium whose pH has been adjusted in advance so that the ultimate value of the pH falls within the range of pH 9 to 12, or to adjust the pH by adding an alkaline solution. And the amount of sediment obtained is high.

Further, after the precipitate obtained in the second step is filtered and dried, a residue such as a dispersant adhered inside or around the granular precipitate is decomposed and eliminated. Alternatively, baking is performed to promote the solid phase reaction of the phosphor to finally obtain a phosphor material usable for PDP (third step). The atmosphere, temperature and time for firing are appropriately selected depending on the phosphor material to be used. In particular, the firing time depends on the reaction rate, amount or temperature rising rate in the decomposition or solid phase reaction of the raw material of the phosphor to be used. It is set appropriately.

Embodiment 1 The above-described phosphor layer 8 is made of a phosphor material as shown in FIGS. That is, in the figure, 100 is a phosphor material, 10
Reference numeral 1 denotes a phosphor that emits light upon receiving ultraviolet light, and 102 denotes a phosphor 1
01, a light absorber (in other words, the light absorber 102 is surrounded by the fluorescent material 101 around the light absorber 102) and is formed of a pigment made of an inorganic material having the same color as the emission color of the fluorescent material 101. And is provided substantially at the center of the outer shape of the phosphor 101).

FIG. 5A shows a case where the light absorber 102 has a plurality of minute particles gathered.
(B) shows a case where the light absorber 102 is constituted by a single particle. Although the configuration of the light absorber 102 is different in FIGS. 5A and 5B, since the functions and effects of each are the same, the following description will be made.
The description will be made without particularly distinguishing between FIGS. 5A and 5B.

The phosphor material 100 is composed of a phosphor 101 and a light absorber 102. The light absorber 102 has a light emission efficiency of 70 compared to a case where the light absorber 102 is not contained.
It is contained in the phosphor material 100 to such an extent that it does not become less than the percent, that is, it does not become too dark. Since the light absorber 102 is made of an inorganic material, it can be manufactured at a high temperature.

As the pigment used in the light absorber 102 described here, for example, a red light absorber is iron oxide,
Cobalt green is used for the green light absorber, and cobalt aluminate is used for the blue light absorber.

The phosphor material 100 shown in FIG. 5 has a particle size of about 3 μm. Then, the light absorber 102
Are intensively provided (included) at a position substantially at the center of the phosphor material 100 having a particle size of about 3 μm.

As described above, when ultraviolet rays enter the phosphor 101, absorption, excitation, and emission are performed up to about several hundred angstroms from the surface of the phosphor 101, so that the light absorber 102 as shown in FIG. Is the phosphor 10
1 does not interfere with the absorption of UV light.

For this reason, the pigment as the light absorber does not reflect or absorb energy rays such as ultraviolet rays and electron beams, so that the luminous efficiency of the phosphor material can be prevented from being impaired as in the prior art. . Therefore, the conversion efficiency of energy rays such as ultraviolet rays and electron beams into visible light is improved,
In particular, when the absorption length of the phosphor 101 is short, such as ultraviolet light used in a PDP, a tremendous effect can be exhibited in improving the luminous efficiency.

On the other hand, the PDP,
Light incident on the inside of the discharge cell 9 from the outside (hereinafter, referred to as external light) reaches the light absorber 102 at the center of the phosphor 101, and the light absorption wavelength of the phosphor 101 by the light absorber 102. Other light is absorbed and captured. Accordingly, the amount of light that reaches the inside of the discharge cell 9 and is reflected to the outside of the folded discharge cell 9, particularly to the outside through the front substrate 5, is reduced (reflection is suppressed). Discharge cell 9 due to external light in a state where it is not performed
By suppressing the reflection from the light, the contrast of the image display can be increased.

In this case, the content of the light absorber 102 with respect to the entire phosphor material 100 can be arbitrarily set. However, as the content of the light absorber 102 increases, the conversion efficiency of ultraviolet light into visible light becomes relatively low. , And conversely, light absorber 1
When the content of 02 decreases, the ratio of reflection of external light from the discharge cells 9 relatively increases.

As a result of repeated studies by the inventors, the light absorber 1
02 is adjusted so that the luminance obtained by incorporating 02 in the phosphor material 100 does not become 70% or less of the luminance obtained by the phosphor material 100 not including the light absorber 102. In this way, they have found that the effect of improving contrast can be maximized while suppressing a decrease in luminance.

That is, from a practical point of view, when the luminous efficiency and the luminance are in a proportional relationship, if the luminous efficiency is lower than 70% as described above, the effect of improving the luminance is more than the effect of improving the contrast. The effect of the degradation is more pronounced on the display screen, and the entire display screen is perceived as being dark, and the image quality is also reduced.

Next, an example of a method for manufacturing a phosphor material having a structure as shown in FIG. 5 will be described for each color. (Method of Manufacturing Red Phosphor Material) FIG. 9 is a flowchart showing a method of manufacturing a red phosphor material, which will be described below with reference to FIG. First, a red pigment (light absorber for red light) having a particle size of 10 to 100 nmφ made of iron oxide Fe ₂ O ₃ is dispersed in water, and either yttrium nitrate or yttrium chloride is used as a salt containing yttrium. (Yttrium nitrate in FIG. 9) and either europium nitrate or europium chloride (Europium nitrate in FIG. 9) as a salt containing europium are dissolved (first step: SR11).

To form a red phosphor material, iron oxide Fe ₂ O ₃ is used as a red pigment, and water is used as a dispersion medium for dispersing the same. Such as a dispersant when using water as the dispersion medium, includes a polycarboxylic acid,
For example, if Poise 532A (manufactured by Kao Corporation; main component: ammonium polycarboxylate) is used, a more uniform dispersion state of the red pigment in the dispersion medium can be realized, and the uniformity of the particle size of the phosphor material can be maintained.

Next, the pH was adjusted to pH 9 by dropwise addition of ammonia.
Raise to In the process of increasing the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the red pigment as a nucleus (second step: SR1
2). Thereafter, the precipitate of the composite hydroxide is filtered and dried (third step: SR13).

Further, the temperature is changed from 1250 ° C. to 1300 ° C.
For example, firing is performed in the air (in an oxygen atmosphere) for 10 hours to form a composite oxide. At this time, a phosphor material having a structure as shown in FIG. 5 is obtained by grain growth of the phosphor during firing.
Red phosphor Y containing red pigment (Fe ₂ O ₃ ) in the center
₂ O ₃ : Eu is formed (fourth step: SR14).
Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The first step SR11 is the first step described above, the second step SR12 is the second step, the third step SR13 and the fourth step SR13.
R14 corresponds to the third step, respectively.

(Method of Manufacturing Green Phosphor Material) FIG. 10 is a flowchart showing a method of manufacturing a green phosphor material, which will be described below with reference to FIG. First, a green pigment (light absorber of green light) composed of cobalt green TiO ₂ —Cr ₂ O ₃ —CoO—Al ₂ O ₃ is dispersed in water, and then an alkoxide containing zinc and silicic acid are contained therein. Dissolve each alkoxide of the alkoxide and the alkoxide containing manganese (first step: SG1
1).

The above-mentioned alkoxide is an alcohol group (C
_n H _m ) to which a metal ion (M having a valence a) is added to a general chemical formula (C _n H _m ) _a -M, which is a material (salt);
For example, methoxide when n = 1, m = 3, n = 2, m =
In the case of No. 5, ethoxide and the like are included. In the first step, an alkoxide having any chemical formula may be used.

In forming a green phosphor material,
Cobalt green TiO ₂ —Cr ₂ O ₃ — as a green pigment
Using CoO-Al ₂ O _3, using water containing alcohol as a dispersion medium for dispersing them. Such a dispersant when water containing an alcohol is used as a dispersion medium includes, for example, homogenol L-1 containing a polycarboxylic acid.
When 8 (manufactured by Kao Corporation; main component: polycarboxylate) is used, a more uniform dispersion state of the green pigment in the dispersion medium can be realized, and the particle size of the phosphor material can be kept uniform.

Next, the pH was adjusted to pH 9 by dropwise addition of ammonia.
Raise to In the step of increasing the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the green pigment as a nucleus (second step: SG1
2). Thereafter, the precipitate of the composite hydroxide is filtered and dried (third step: SG13).

Further, for example, for 10 hours in the atmosphere (in an oxidizing atmosphere) at 850 to 900 degrees Celsius,
For example, firing is performed in a reducing atmosphere at 50 to 1300 degrees for 30 hours to form a composite oxide. At this time, a phosphor material having a structure shown in FIG. 5 is obtained by grain growth of the phosphor during firing, and a green phosphor containing a green pigment (TiO ₂ —Cr ₂ O ₃ —CoO—Al ₂ O ₃ ) in the center. Zn ₂ SiO ₄ : Mn is formed (fourth step: SG14). Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The above-mentioned first step SG11 is the first step described above, the second step SG12 is the second step, the third step SG13 and the fourth step SG13.
G14 corresponds to the third step, respectively.

(Production Method of Blue Phosphor Material) FIG. 11 is a flowchart showing a production method of a blue phosphor material, which will be described below with reference to FIG. First, an aqueous solution in which urea is dissolved is formed, and cobalt aluminate CoO—Al ₂ O ₃ as a blue pigment is dispersed therein (first step: SB11).

When forming a blue phosphor material, cobalt aluminate CoO—Al ₂ O ₃ is used as a blue pigment in the same manner as in forming a red phosphor material. Water in which urea is dissolved is used as a medium.
Such a urea is dissolved, but as a dispersing agent when water is basically used as a dispersion medium, the polydispersing agent containing, for example, the above-mentioned Pois 532A is used. A more uniform dispersion state can be realized, and uniformity of the particle size of the phosphor material can be maintained.

Next, any of barium acetate, barium chloride and barium nitrate (barium acetate in FIG. 11) as a barium-containing salt, and any of magnesium nitrate and magnesium chloride as a magnesium-containing salt (FIG. 11) Magnesium nitrate), either aluminum nitrate or aluminum chloride as a salt containing aluminum (aluminum nitrate in FIG. 11), and either europium nitrate or europium chloride as a salt containing europium (europium chloride in FIG. 11) The solution is constantly stirred during this dispersion and dissolution, and the temperature of the solution is set to 40 ° C. or lower (second step: SB12).

Further, the liquid temperature is increased to 80 degrees Celsius while stirring. At this time, the pH in the liquid increases due to the ammonia formed by the decomposition of urea. In the step of increasing the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the blue pigment as a nucleus (third step: SB13). Thereafter, the precipitate of the composite hydroxide is filtered and dried (fourth step: SB14).

Further, for example, for 30 hours in the air (in an oxygen atmosphere) at 850 to 900 degrees Celsius,
250 to 1300 degrees for 50 hours, for example, nitrogen 9
Calcination is performed in a reducing atmosphere of a mixed gas of 6% and 4% of hydrogen to form a composite oxide. At this time, a phosphor material having a structure shown in FIG. 5 is obtained by grain growth of the phosphor during firing, and is finally washed with water, and a blue phosphor BaMgAl ₁₀ O containing a blue pigment (CoO—Al ₂ O ₃ ) at its center. ₁₇ : Eu
(Fifth step: SB15). Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The first step SB11 and the second step SB12 are the first step described above, the third step SB13 is the second step, and the fourth step SB13 is the fourth step SB13.
B14 and the fifth step SB15 correspond to the third step, respectively.

Embodiment 2 FIGS. 6A and 6B are views showing a phosphor material according to a second embodiment of the present invention. In the drawing, reference numeral 200 denotes a phosphor material, 201 denotes a phosphor which emits light by receiving ultraviolet rays similar to that shown in FIG. 5, and 202 denotes a plurality of granular phosphors 201 provided intensively at substantially the center of the outer shape S of the phosphors 201. A light absorber composed of a pigment made of an inorganic material having the same color as the emitted color of the phosphor 201 (in other words, the light absorber 202 is surrounded (surrounded) by a plurality of granular phosphors 201 around its periphery. ),
Provided substantially at the center of the outer shape S of the phosphor 201).

FIG. 6A shows a case where the light absorber 202 has a plurality of fine particles gathered.
(B) shows a case where the light absorber 202 is constituted by a single particle. 6A and 6B, the configuration of the light absorber 202 is different, but since the functions and effects of each are the same, the following description will be made.
The description will be made without particularly distinguishing between FIGS. 6A and 6B.

The phosphor material 200 is composed of a phosphor 201 and a light absorber 202. The light absorber 202 has a light emission efficiency of 70 compared to a case where the light absorber 202 is not contained.
It is contained in the phosphor material 200 to such an extent that it does not become less than the percent, that is, it does not become too dark. Since the light absorber 202 is made of an inorganic material, it can be manufactured at a high temperature.

The pigment used in the light absorber 202 described here is, for example, a red light absorber is iron oxide,
Cobalt green is used for the green light absorber, and cobalt aluminate is used for the blue light absorber.

The phosphor material 100 shown in FIG. 6 is defined by its outer shape S (for example, a virtual sphere including the light absorber 11 and the plurality of phosphors 102 in a single phosphor material 100). The resulting particle size is about 3 μm. The light absorber 202 has a particle size of about 3 μm.
m are provided (contained) intensively at substantially the center of the phosphor material 200.

As described above, the ultraviolet fluorescent material 201 is used.
When light enters, absorption, excitation, and emission are performed up to about several hundred angstroms from the surface of each phosphor 201, so that the light absorber 202 as shown in FIG. Never.

For this reason, the pigment as the light absorber does not reflect or absorb energy rays such as ultraviolet rays and electron beams, and it is possible to prevent the luminous efficiency of the phosphor material from being impaired as in the prior art. . Therefore, the conversion efficiency of energy rays such as ultraviolet rays and electron beams into visible light is improved,
In particular, when the absorption length of each of the phosphors 201 is short, such as ultraviolet light used in a PDP, a tremendous effect can be exhibited in improving the luminous efficiency.

On the other hand, external light which enters the inside of the discharge cell 9 from the outside, such as through the front substrate 5, reaches the light absorber 202 at the center of the plurality of granular phosphor 201 outer shapes S. The light other than the emission wavelength of the phosphor 201 is absorbed and captured by the light absorber 202. Therefore, it reaches the inside of the discharge cell 9 and the outside of the folded discharge cell 9,
In particular, since the amount of light reflected to the outside via the front substrate 5 is reduced (reflection is suppressed), an image is formed by suppressing reflection from the discharge cells 9 due to external light in a state where display discharge is not performed. The display contrast can be increased.

In this case, the content of the light absorber 202 with respect to the entire phosphor material 200 can be set arbitrarily. However, as the content of the light absorber 202 increases, the conversion efficiency of ultraviolet light into visible light becomes relatively low. , And conversely, the light absorber 2
When the content of 02 decreases, the ratio of reflection of external light from the discharge cells 9 relatively increases. As a result of repeated studies by the inventors, the luminance obtained by including the light absorber 202 in the phosphor material 200 is 70% or less of the luminance obtained by the phosphor material 200 not including the light absorber 202. Light absorber 202 so that
It has been found that by adjusting the content ratio, the effect of improving the contrast can be maximized while suppressing the decrease in luminance.

The method of manufacturing the phosphor material according to the second embodiment is basically the same as the method of manufacturing the phosphor material described in the first embodiment. By baking with a shorter baking time, the light absorber is formed in a state surrounded by a plurality of granular phosphors as shown in FIG.

Next, an example of a method for manufacturing a phosphor material having a structure as shown in FIG. 6 will be described for each color. (Method of Manufacturing Red Phosphor Material) FIG. 12 is a flowchart showing a method of manufacturing a red phosphor material.
This will be described with reference to FIG. First, a red pigment (light absorber for red light) having a particle size of 10 to 100 nmφ made of iron oxide Fe ₂ O ₃ is dispersed in water, and either yttrium nitrate or yttrium chloride is used as a salt containing yttrium. (Yttrium nitrate in FIG. 12) and either europium nitrate or europium chloride (Europium nitrate in FIG. 12) as a salt containing europium are dissolved (first step: SR21).

To form a red phosphor material, iron oxide Fe ₂ O ₃ is used as a red pigment, and water is used as a dispersion medium for dispersing the same. Such as a dispersant when using water as the dispersion medium, includes a polycarboxylic acid,
For example, if Poise 532A (manufactured by Kao Corporation; main component: ammonium polycarboxylate) is used, a more uniform dispersion state of the red pigment in the dispersion medium can be realized, and the uniformity of the particle size of the phosphor material can be maintained.

Next, the pH was adjusted to pH 9 by dropwise addition of ammonia.
Raise to In the process of raising the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the red pigment as a nucleus (second step: SR2
2). Thereafter, the precipitate of the composite hydroxide is filtered and dried (third step: SR23).

Further, this is fired in the air (in an oxygen atmosphere) at 1200 degrees Celsius, for example, for 2 hours to form a composite oxide. At this time, a phosphor material having a structure as shown in FIG. 6 is obtained by grain growth of the phosphor during firing, and a red phosphor Y ₂ O ₃ : Eu containing a red pigment (Fe ₂ O ₃ ) at a central portion is formed. (Fourth step: SR24). Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The first step SR21 is the first step described above, the second step SR22 is the second step, the third step SR23, and the fourth step S23.
R24 corresponds to the third step, respectively.

By using the manufacturing method described above, a phosphor material having the same function and effect as that described in the first embodiment can be manufactured in a shorter time.

(Method of Manufacturing Green Phosphor Material) FIG. 13 is a flowchart showing a method of manufacturing a green phosphor material, which will be described below with reference to FIG. First, a green pigment (light absorber of green light) composed of cobalt green TiO ₂ —Cr ₂ O ₃ —CoO—Al ₂ O ₃ is dispersed in water, and then an alkoxide containing zinc and silicic acid are contained therein. Dissolve each alkoxide of alkoxide and alkoxide containing manganese (first step: SG2
1).

The above-mentioned alkoxide is an alcohol group (C
_n H _m ) to which a metal ion (M having a valence a) is added to a general chemical formula (C _n H _m ) _a -M, which is a material (salt);
For example, methoxide when n = 1, m = 3, n = 2, m =
In the first step, alkoxide having any chemical formula may be used.

Further, to form a green phosphor material,
Cobalt green TiO ₂ —Cr ₂ O ₃ — as a green pigment
Using CoO-Al ₂ O _3, using water containing alcohol as a dispersion medium for dispersing them. Such a dispersant when water containing an alcohol is used as a dispersion medium includes, for example, homogenol L-1 containing a polycarboxylic acid.
When 8 (manufactured by Kao Corporation; main component: polycarboxylate) is used, a more uniform dispersion state of the green pigment in the dispersion medium can be realized, and the particle size of the phosphor material can be kept uniform.

Next, the pH was adjusted to pH 9 by dropwise addition of ammonia.
Raise to In the step of raising the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the green pigment as a nucleus (second step: SG2
2). Thereafter, the precipitate of the composite hydroxide is filtered and dried (third step: SG23).

Further, the composite oxide is formed by firing at 800 ° C. in the air (in an oxidizing atmosphere) for, eg, 2 hours, and further in a reducing atmosphere at 1200 ° C., eg, for 6 hours. At this time, the phosphor material having the structure shown in FIG. 5 is obtained by grain growth of the phosphor during firing, and a green pigment (TiO ₂ —Cr ₂ O ₃₎ is obtained.
-CoO-Al ₂ O ₃ ) in the center of the green phosphor Z
Form n ₂ SiO ₄ : Mn (Fourth Step: SG2
4). Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The first step SG21 is the first step described above, the second step SG22 is the second step, the third step SG23, and the fourth step SG23.
G24 corresponds to the third step, respectively.

By using the manufacturing method described above, a phosphor material having the same function and effect as that described in the first embodiment can be manufactured in a shorter time.

(Method of Manufacturing Blue Phosphor Material) FIG. 14 is a flowchart showing a method of manufacturing a blue phosphor material, which will be described below with reference to FIG. First, an aqueous solution in which urea is dissolved is formed, and cobalt aluminate CoO—Al ₂ O ₃ as a blue pigment is dispersed therein (first step: SB21).

When forming a blue phosphor material, cobalt aluminate CoO—Al ₂ O ₃ is used as a blue pigment in the same manner as when forming a red phosphor material, and a dispersion for dispersing the same is used. Water in which urea is dissolved is used as a medium.
Such a urea is dissolved, but as a dispersing agent when water is basically used as a dispersion medium, the polydispersing agent containing, for example, the above-mentioned Pois 532A is used. A more uniform dispersion state can be realized, and uniformity of the particle size of the phosphor material can be maintained.

Next, any of barium acetate, barium chloride or barium nitrate (barium acetate in FIG. 14) as a salt containing barium, and any of magnesium nitrate or magnesium chloride as a salt containing magnesium (FIG. 14) Magnesium salt), either aluminum nitrate or aluminum chloride as a salt containing aluminum (aluminum nitrate in FIG. 14), and either europium nitrate or europium chloride as a salt containing europium (europium chloride in FIG. 14) The solution is constantly stirred during this dispersing and dissolving, and the temperature of the solution is adjusted to 40 ° C. or lower (second step: SB22).

Further, the liquid temperature is raised to 80 degrees Celsius while stirring. At this time, the pH in the liquid increases due to the ammonia formed by the decomposition of urea. In the step of increasing the pH, a composite hydroxide serving as a phosphor is generated. At this time, the composite hydroxide grows with the blue pigment as a nucleus (third step: SB23). Thereafter, the precipitate of the composite hydroxide is filtered and dried (fourth step: SB24).

Further, for example, in the atmosphere (oxygen atmosphere) at 800 degrees Celsius for 6 hours, and then at 1200 degrees Celsius for 10 hours, for example, in a reducing atmosphere, for example, in a mixed gas atmosphere of 96% nitrogen and 4% hydrogen. Calcination to form a composite oxide. At this time, a phosphor material having a structure shown in FIG. 5 is obtained by grain growth of the phosphor during firing, and is finally washed with water, and a blue phosphor BaMgAl ₁₀ O containing a blue pigment (CoO—Al ₂ O ₃ ) at its center. ₁₇ : Eu is obtained (fifth step: SB25). Here, the firing time is appropriately set according to the decomposition rate of the raw material of the phosphor to be used or the reaction rate or amount in the solid phase reaction or the temperature rising rate.

The first step SB21 and the second step SB22 are the first step described above, the third step SB23 is the second step, and the fourth step SB23 is the fourth step SB21.
B24 and the fifth step SB25 correspond to the third step, respectively.

By using the manufacturing method described above, a phosphor material having the same function and effect as described in the first embodiment can be manufactured in a shorter time.

Note that, depending on the setting of the temperature condition and the firing time, the light absorbing member is partially surrounded by the phosphor while being surrounded by the phosphor, as shown in FIG. 5 and FIG. 5 or 6 as long as it has a structure in which ultraviolet rays are absorbed by the phosphor without being blocked by the light absorber before reaching the light absorber. It has the same effect as the body material.

In the above description, a phosphor material used for a PDP utilizing ultraviolet rays has been described as an energy ray for emitting a phosphor. However, the present invention is not limited to this. It is needless to say again that the same effect as described above can be obtained even when used in a CRT to be used.
In this case, a suitable phosphor capable of converting the energy beam used into light in the visible light region and a suitable light absorber for light having a wavelength to be absorbed are selected.

[0121]

Since the present invention is configured as described above, it has the following effects. According to the first aspect of the present invention, the light absorbing member is constituted by the phosphor that emits light in the visible light range when the energy ray is incident thereon and the light absorber that is provided intensively inside the phosphor. A phosphor material having high luminous efficiency in the phosphor can be obtained without the body hindering the entry of energy rays into the phosphor.

According to the second aspect, since the light absorber is provided at substantially the center of the outer shape of the phosphor surrounding the light absorber, it is ensured that energy rays enter the phosphor. Thus, a phosphor material can be obtained.

According to the third aspect of the present invention, since the light absorber is surrounded by the plurality of phosphor particles, the light absorber does not hinder the entry of the energy ray into the phosphor. Can be obtained in a shorter time.

According to the fourth aspect, since the light absorber is a pigment made of an inorganic material, a phosphor material that can be manufactured at a high temperature can be obtained.

According to the fifth aspect of the present invention, the light absorber is made to have the same color as the emission color of the phosphor, so that the luminous efficiency is high, unnecessary external light can be absorbed, and the contrast is excellent. Phosphor material can be obtained.

According to the sixth aspect, the light absorber is contained so that the luminous efficiency does not become 70% or less as compared with the case where the light absorber is not contained.
A phosphor material having high luminous efficiency can be obtained while preventing a decrease in luminance.

According to the seventh aspect, the pair of display electrodes extending in the line direction for each display line is formed on the inner surface of the front or rear substrate in the pair of substrates sandwiching the discharge space, and the discharge between the pair of substrates is performed. A fluorescent gas including a light absorbing material that is provided intensively inside a fluorescent material that emits light in the visible light region by the incidence of ultraviolet light generated from the discharge gas based on the discharge between the display electrode pair and the discharge gas sealed in the space. Since a phosphor layer made of a body material is provided, a plasma display panel with high luminous efficiency in the phosphor can be obtained without the light absorber interfering with the entry of energy rays into the phosphor.

According to the eighth aspect, since the light absorber in the phosphor material is located substantially at the center of the outer shape of the phosphor surrounding the periphery thereof, it is ensured that the energy ray enters the phosphor. Can be obtained.

In the plasma display panel according to the ninth aspect, the light absorber in the phosphor material is surrounded by the plurality of phosphor particles, so that the light absorber prevents energy rays from entering the phosphor. A phosphor material having high luminous efficiency in the phosphor without any hindrance can be obtained in a shorter time.

In the plasma display panel according to the tenth aspect, since the light absorber in the phosphor material is a pigment made of an inorganic material, a phosphor material that can be manufactured at a high temperature can be obtained. .

In the plasma display panel according to the eleventh aspect, the light absorber of the phosphor material has the same color as the emission color of the phosphor, so that the luminous efficiency is high and unnecessary external light is absorbed. And a phosphor material having excellent contrast can be obtained.

In the plasma display panel according to the twelfth aspect, the phosphor material contains the light absorber so that the luminous efficiency does not become 70% or less as compared with the case where the light absorber is not contained. So
A phosphor material having high luminous efficiency can be obtained while preventing a decrease in luminance.

According to the thirteenth aspect, the phosphor that emits light in the visible light range when the energy ray is incident is grown around the light absorber, and the light absorber is formed so as to be surrounded by the phosphor. Since the step of forming the phosphor is included, a phosphor material having high luminous efficiency in the phosphor can be obtained without the light absorber interfering with the entry of energy rays into the phosphor.

According to the fourteenth aspect, since the phosphor forming step is performed in a liquid containing a predetermined component, it is possible to obtain a phosphor material having stable performance of the obtained phosphor material. it can.

According to the fifteenth aspect, since the phosphor forming step includes the step of increasing the hydrogen ion exponent in the solution, a manufacturing method in which the reaction can be easily controlled can be realized.

According to the method for producing a phosphor material of the sixteenth aspect, after dispersing the inorganic pigment in a predetermined dispersion medium in accordance with the type of the inorganic pigment, the dispersion may contain a metal component constituting the phosphor. A first step of obtaining a solution in which a salt soluble in the dispersion medium is dissolved, a second step of obtaining a precipitate by increasing the hydrogen ion index in the solution obtained by the first step, After filtering and drying the precipitate obtained in the step, the third step of firing under predetermined conditions is included, so that the light absorber emits energy rays to the phosphor by a simple method. It is possible to obtain a phosphor material having a high luminous efficiency in the phosphor without obstructing the invasion, to obtain a phosphor material having a stable performance of the obtained phosphor material, and to manufacture the phosphor with a simple reaction control. The law can be realized.

According to the method for producing a phosphor material of the seventeenth invention, in the first step of the sixteenth invention, iron oxide is used as the inorganic pigment, water is used as the dispersion medium, and yttrium soluble in this dispersion medium is used. And a salt containing europium, and ammonia in the second step, respectively, and calcination in the third step is performed by: (A) an oxygen atmosphere in the range of 1250-1300 degrees Celsius;
Or (B) in an oxygen atmosphere under either of the following conditions: 1200 ° C. to form a red phosphor material, so that the light absorber is applied to the phosphor by a simple method. It is possible to obtain a red phosphor material with high luminous efficiency in the phosphor without hindering the entry of energy rays, and to obtain a red phosphor material in which the performance of the obtained phosphor material is stable. In addition, it is possible to realize a production method in which reaction control is simple.

According to the method for producing a phosphor material of the eighteenth invention, in the first step of the sixteenth invention, in the first step, cobalt green is used as the inorganic pigment, water is used as the dispersion medium, and zinc which is soluble in this dispersion medium is used. , An alkoxide containing silicic acid, a salt of an alkoxide containing manganese, and ammonia in the second step are used, and the calcination in the third step is as follows: (A1) In an oxygen atmosphere, 850-900 degrees (A2) Further, in a reducing atmosphere, 1250 degrees Celsius
1300 ° C. or (B1) 800 ° C. in an oxygen atmosphere and (B2) further in a reducing atmosphere under 1200 ° C. to form a green phosphor material. By using a simple method, it is possible to obtain a green phosphor material with high luminous efficiency in the phosphor without the light absorber hindering the entry of energy rays into the phosphor, and the performance of the phosphor material obtained is stable , And a production method with simple reaction control can be realized.

According to the method for producing a phosphor material of the nineteenth aspect, in the first step of the sixteenth aspect, in the first step, cobalt aluminate is used as an inorganic pigment, urea is dissolved in water as a dispersion medium, Soluble barium-containing salt, magnesium-containing salt, aluminum-containing salt and europium-containing salt are used, respectively.In the second step, the solution obtained in the first step is stirred. By raising the liquid temperature while increasing the hydrogen ion index, the baking in the third step is performed by: (A1) 850 to 900 degrees Celsius in an oxygen atmosphere; (A2) 1250 to 900 degrees Celsius in a reducing atmosphere
1300 ° C. or (B1) 800 ° C. in an oxygen atmosphere and (B2) further in a reducing atmosphere under 1200 ° C. to form a blue phosphor material. It is possible to obtain a blue phosphor material with high luminous efficiency in the phosphor without the light absorber hindering the entry of energy rays into the phosphor by a simple method, and the performance of the phosphor material obtained is stable Can be obtained, and a production method with simple reaction control can be realized.

In the method for producing a phosphor material according to the twentieth aspect, in the second step of the sixteenth to nineteenth aspects, the value of the attained hydrogen ion exponent is in the range of pH 9 to 12. The material constituting the phosphor is not wasted, and the precipitate can be prevented from being dissolved again.

According to a twenty-first aspect of the present invention, there is provided a plasma display device, comprising: a pair of display electrodes extending in the line direction for each display line on the inner surface of a front or back substrate in a pair of substrates sandwiching a discharge space; Discharge gas sealed in the discharge space, fluorescent light including a light absorber intensively provided inside a fluorescent material that emits light in the visible light region due to the incidence of ultraviolet light generated from the discharge gas based on the discharge between the display electrode pairs Since a plasma display panel including each of the phosphor layers made of a body material and a drive control unit for driving the plasma display panel are provided, a plasma display device having high luminous efficiency and contrast in the phosphor material is provided. Obtainable.

[Brief description of the drawings]

FIG. 1 is a block diagram showing an overall configuration of a surface discharge type plasma display device according to the present invention.

FIG. 2 is a plan view schematically showing a wiring configuration of the surface discharge type plasma display panel according to the present invention.

FIG. 3 is a timing chart of each drive signal in the surface discharge type plasma display device according to the present invention.

FIG. 4 is a cross-sectional view showing a main structure of the surface discharge type plasma display panel.

FIG. 5 is a schematic diagram showing a phosphor material according to the first embodiment of the present invention.

FIG. 6 is a schematic view showing a phosphor material according to a second embodiment of the present invention.

FIG. 7 is an enlarged view of a main part (part A shown in FIG. 4) of the phosphor layer in the embodiment of the present invention.

FIG. 8 is a flowchart illustrating a method for manufacturing a phosphor material according to an embodiment of the present invention.

FIG. 9 is a flowchart showing a manufacturing process of the red phosphor material according to the first embodiment of the present invention.

FIG. 10 is a flowchart showing a manufacturing process of the green phosphor material according to the first embodiment of the present invention.

FIG. 11 is a flowchart showing a process of manufacturing a blue phosphor material according to the first embodiment of the present invention.

FIG. 12 is a flowchart showing a manufacturing process of a red phosphor material according to Embodiment 2 of the present invention.

FIG. 13 is a flowchart showing a process for manufacturing a green phosphor material according to the second embodiment of the present invention.

FIG. 14 is a flowchart showing a manufacturing process of a blue phosphor material according to Embodiment 2 of the present invention.

FIG. 15 is a view showing a conventional phosphor material.

FIG. 16 is a view showing another conventional phosphor material.

[Explanation of symbols]

100, 200, 600 phosphor material, 101, 20
1,601 phosphor, 102,202,602 light absorber (pigment), S1 first step, S2 second step, S
3 Third step, SR11, SR21 First step, SR12, SR2 in the manufacturing process of red phosphor material
2 Second step in the manufacturing process of the red phosphor material, SR13, SR23 Third step in the manufacturing process of the red phosphor material, SR14, SR24 Fourth step in the manufacturing process of the red phosphor material, SG11,
SG21 a first step in the process of manufacturing the green phosphor material, SG12, SG22 a second step in the process of manufacturing the green phosphor material, SG13, SG23 a third step in the process of manufacturing the green phosphor material, SG1
4. SG24 Fourth step in the manufacturing process of green phosphor material, SB11, SB21 First step in the manufacturing process of blue phosphor material, SB12, SB22
The second step in the manufacturing process of the blue phosphor material, S
B13, SB23 Third step in manufacturing process of blue phosphor material, SB14, SB24 Fourth step in manufacturing process of blue phosphor material, SB15, SB25
Fifth step in the manufacturing process of the blue phosphor material.

Claims (21)

[Claims] 1. A phosphor material, comprising: a phosphor that emits light in a visible light range when an energy ray is incident thereon; and a light absorber that is provided intensively inside the phosphor. 2. The light absorbing member is provided substantially at the center of the outer shape of a phosphor surrounding the light absorbing member.
The phosphor material as described in the above. 3. The phosphor material according to claim 1, wherein the light absorber is surrounded by a plurality of phosphor particles. 4. The phosphor material according to claim 1, wherein the light absorber is a pigment made of an inorganic material. 5. The phosphor material according to claim 1, wherein the light absorber has the same color as the emission color of the phosphor. 6. The light-absorbing material according to claim 1, wherein the light-absorbing material is contained such that the luminous efficiency does not become 70% or less as compared with a case where no light-absorbing material is contained. Phosphor material. 7. A pair of display electrodes extending in the line direction for each display line on the inner surface of the front or back substrate in the pair of substrates sandwiching the discharge space, and sealed in the discharge space between the pair of substrates. Material comprising a discharge gas and a light absorber intensively provided inside a phosphor that emits light in a visible light region by incidence of ultraviolet light generated from the discharge gas based on discharge between the display electrode pairs. A plasma display panel comprising: a phosphor layer comprising: 8. The plasma display panel according to claim 7, wherein the light absorber in the phosphor material is positioned substantially at the center of the outer shape of the phosphor surrounding the light absorber. 9. The plasma display panel according to claim 7, wherein the light absorber in the phosphor material is surrounded by a plurality of phosphor particles. 10. The plasma display panel according to claim 7, wherein the light absorber in the phosphor material is a pigment made of an inorganic material. 11. The plasma display panel according to claim 7, wherein the light absorber of the phosphor material has the same color as the emission color of the phosphor. 12. The light-absorbing material in the phosphor material is contained so that the luminous efficiency does not become 70% or less as compared with when the light-absorbing material is not contained. A plasma display panel according to any one of the above. 13. A phosphor forming step of growing a phosphor that emits light in the visible light range by the incidence of energy rays around the light absorber, and forming the light absorber so as to be surrounded by the phosphor. A method for producing a phosphor material, comprising: 14. The method for producing a phosphor material according to claim 13, wherein the phosphor forming step is performed in a liquid containing a predetermined component. 15. The method according to claim 1, wherein the step of forming the phosphor includes a step of increasing the hydrogen ion exponent in the liquid.
5. The method for producing a phosphor material according to item 4. 16. After dispersing an inorganic pigment in a predetermined dispersion medium according to the type of the inorganic pigment, a solution in which a salt containing a metal component constituting a phosphor and soluble in the dispersion medium is dissolved is used. A first step of obtaining, a second step of obtaining a precipitate by increasing the hydrogen ion exponent in the solution, and a third step of filtering and drying the precipitate, followed by firing under predetermined conditions. A method for producing a phosphor material, comprising: 17. In the first step, iron oxide is used as an inorganic pigment, water is used as a dispersion medium, a salt containing yttrium and europium soluble in the dispersion medium, and ammonia is used in a second step. Each of them is used and firing in the third step is performed as follows: (A) In an oxygen atmosphere, 1250 to 1300 degrees Celsius
17. The method according to claim 16, wherein the step (B) is performed in an oxygen atmosphere under a condition of 1200 degrees Celsius to form a red phosphor material. 18. In the first step, cobalt green as an inorganic pigment, water as a dispersion medium, zinc-containing alkoxide, silicic acid-containing alkoxide, and manganese-containing alkoxide soluble in the dispersion medium. Ammonia is used in the second step, and the calcination in the third step is as follows: (A1) 850 to 900 degrees Celsius in an oxygen atmosphere;
(B1) 800 ° C. in an oxygen atmosphere, (B2) further performed in a reducing atmosphere under a condition of 1200 ° C. to form a green phosphor material. The method for producing a phosphor material according to claim 16. 19. In the first step, cobalt aluminate is used as an inorganic pigment, and urea is dissolved in water as a dispersion medium.
A salt containing barium soluble in the dispersion medium, a salt containing magnesium, a salt containing aluminum and a salt containing europium, respectively, are used, and the second step is obtained in the first step. The hydrogen ion exponent is increased by increasing the liquid temperature while stirring the solution, and baking in the third step is performed by: (A1) 850 to 900 degrees Celsius in an oxygen atmosphere; (A2) further in a reducing atmosphere 1250 Celsius
1300 ° C. or (B1) 800 ° C. in an oxygen atmosphere, (B2) further performed in a reducing atmosphere under a condition of 1200 ° C. to form a blue phosphor material. The method for producing a phosphor material according to claim 16. 20. The method for producing a phosphor material according to claim 16, wherein in the second step, the value of the attained hydrogen ion exponent is in the range of pH 9 to 12. 21. A pair of display electrodes extending in the line direction for each display line on the inner surface of the front or rear substrate in the pair of substrates sandwiching the discharge space, and sealed in the discharge space between the pair of substrates. A discharge gas, comprising a phosphor material including a light absorber intensively provided inside a phosphor that emits light in a visible light region by incidence of ultraviolet light generated from the discharge gas based on discharge between the display electrode pairs. A plasma display device, comprising: a plasma display panel including each of phosphor layers; and a drive control unit for driving the plasma display panel.