JP2000251701A - Display manufacturing method - Google Patents

Abstract

(57) [Summary] [Problem] To provide a display with high color purity and vivid color specification, high luminance, and small luminance variation. Kind Code: A1 The emission color C of a phosphor powder for a display is disclosed.
The IE chromaticity coordinates of the red light-emitting phosphor are (0.60-0.
72, 0.22 to 0.33), for the green light emitting phosphor (0.08 to 0.12, 0.75 to 0.82), and for the blue light emitting phosphor (0.13 to 0.24, 0. 01-0.
08).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a display, and more particularly to an image display apparatus using a plasma display panel (PDP) or an electron-emitting device having excellent display performance.

[0002]

2. Description of the Related Art As an alternative to a liquid crystal display, an image display apparatus using a PDP or an electron-emitting device which is a self-luminous discharge type display can obtain a brighter image than a liquid crystal display and has a wide viewing angle. In addition, since the demand for larger screens and higher definition can be met, the needs are increasing.

The electron-emitting devices include a thermionic electron-emitting device and a cold cathode electron-emitting device. The cold cathode electron-emitting devices include a field emission type (FE type), a metal / insulating layer / metal type (MIM type), and a surface conduction type. An image forming apparatus using such a cold cathode electron source displays an image by irradiating a phosphor with an electron beam emitted from each type of electron-emitting device to generate fluorescent light. An image display device using an electron-emitting device has advantages such as being flat, bright and easy to see.

[0004] PDPs can permeate at higher speeds than liquid crystal displays and can be easily made larger, and thus have penetrated into fields such as OA equipment and public information display devices. Further, progress in the field of high-definition television is highly expected.

[0005] With the expansion of such applications, attention has been paid to a color PDP having a fine and large number of display cells.
The PDP generates a plasma discharge between an anode and a cathode facing each other in a discharge space provided between a front glass substrate and a rear glass substrate, and emits ultraviolet light generated from a gas sealed in the discharge space. The display is performed by hitting the phosphor layer provided in the discharge space. In this case, a partition (also referred to as a barrier or a rib) is provided to keep the spread of the discharge in a certain area and to perform display in a specified cell and to secure a uniform discharge space.

These partition walls are often formed in a stripe shape, and their size (line width, height, pitch) is PD
It depends on the performance of P. In order to increase the number of pixels in a fixed screen size in order to increase the definition of PDP, 1
It is necessary to reduce the size of the pixel. In this case, it is necessary to reduce the pitch between the partition walls. However, when the pitch is reduced, the discharge space is reduced, and the luminance is reduced because the phosphor application area is reduced.

The partition is usually formed on the rear glass substrate,
Phosphor layers for performing red (R), green (G), and blue (B) color display are formed between cells formed by the partition walls, respectively. This phosphor layer forming technology is an elemental technology that affects the quality of PDP, and the phosphor paste is used not only at the bottom of the cell but also for higher brightness.
It has been devised to be applied also to the side surfaces of the partition walls. Further, in order to eliminate the unevenness of the screen, it is necessary to apply a stable and uniform film thickness.

[0008] JP-A-10-77469 and JP-A-1
Japanese Patent Publication No. 0-154466 describes the size, shape, and particle size distribution of the particles of the phosphor powder. For displays capable of high-quality display such as improvement in luminance and color purity of the phosphor and improvement in afterglow. It was not enough as a phosphor.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a display having a high color purity and capable of providing a vivid color specification. A second object of the present invention is to provide a display having a high luminance and a small luminance variation.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a display in which phosphor layers containing phosphors emitting red, green and blue light are formed on a substrate, respectively. The CIE chromaticity coordinates of the emission colors of the red, green, and blue phosphors are (Rx, Ry), (Gx, Gy),
(Bx, By), the following relational expressions (1) and (2)
And (3) are achieved by a method of manufacturing a display characterized by satisfying (3).

(1) 0.60 ≦ Rx ≦ 0.72 and 0.22 ≦ Ry ≦ 0.33 (2) 0.08 ≦ Gx ≦ 0.14 and 0.70 ≦ Gy
≦ 0.82 (3) 0.13 ≦ Bx ≦ 0.24 and 0.01 ≦ By
≦ 0.08

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a color PDP, a phosphor layer made of phosphors emitting light of three colors, R, G and B, is formed in a discharge space partitioned by partition walls, and the phosphors are excited by vacuum ultraviolet radiation. Then, light emission is performed, and each light emission color is additively mixed to obtain a color image. Since the color reproduction range of the color PDP is determined by the emission color of the phosphor, it is important to use a phosphor with good color purity for each color.

The display color of each phosphor can be displayed on a CIE chromaticity diagram. In the chromaticity diagram, the three primary colors R, G, B
The color inside the triangle connecting the three points indicating the chromaticity coordinates can be expressed.

According to the present invention, the CI of the phosphor of each of R, G and B
The coordinate values (Rx, Ry), (Gx, G
y) and (Bx, By) are the following relational expressions (1),
It is characterized in that phosphors satisfying (2) and (3) are selected respectively.

(1) 0.60 ≦ Rx ≦ 0.72 and 0.22 ≦ Ry ≦ 0.33 (2) 0.08 ≦ Gx ≦ 0.14 and 0.70 ≦ Gy
≦ 0.82 (3) 0.13 ≦ Bx ≦ 0.24 and 0.01 ≦ By
≦ 0.08 A more preferable range is as follows.

(4) 0.65 ≦ Rx ≦ 0.72 and 0.24 ≦ Ry ≦ 0.33 (5) 0.08 ≦ Gx ≦ 0.12 and 0.75 ≦ Gy
≦ 0.82 (6) 0.16 ≦ Bx ≦ 0.20 and 0.01 ≦ By
≦ 0.06 The chromaticity of the R phosphor having coordinate values (0.60 to 0.72, 0.22 to 0.33) satisfying the range of the relational expression (1) means that the phosphor is biased toward orange or purple. This is a preferable range in order to maintain the color purity as red without performing. More preferable coordinate values are (0.65 to 0.72, 0.24 to 0.33).

The coordinate values (0.08 to 0.14, 0.70 to 0.8) satisfying the range of the relational expression (2) for the chromaticity of the G phosphor.
That 2) is a preferable range in order to maintain the color purity of green without biasing to yellow or blue. More preferable coordinate values are (0.08 to 0.12, 0.75 to
0.82).

The coordinate values (0.13 to 0.24, 0.01 to 0.0) that the chromaticity of the B phosphor satisfies the range of the relational expression (3).
8) is a preferable range in order to maintain the color purity as blue without being biased to green or purple. More preferable coordinate values are (0.16 to 0.20, 0.01 to
0.06).

By setting the chromaticity coordinate values within the range of the present invention as described above, red, green, and blue with high color purity can be obtained.
As a result, beautiful and vivid color expression is possible, and the white balance is improved. The balance between luminance and chromaticity is also improved.

The phosphors emitting red light include (Y _{1 -x} E
u _x ) ₂ O ₃ (0.040 ≦ x ≦ 0.070), (Y _1-x Eu _x ) BO
₃ (0.025 ≦ x ≦ 0.060), Y ₂ SiO ₅ : Eu, (Y, G
d, Eu) BO ₃ , Y (P, V) O ₄ : Eu, GdB
O ₃ : Eu, ScBO ₃ : Eu, general formula Lm ₂ O ₃ : R (L
m is at least one of Gd, Y, La, and Lu; and R is at least one selected from the group consisting of Eu, Tb, Pr, Dy, Tm, Ce, and Yb).
Preferably, a seed is used. Two or more kinds may be used as a mixture.

The phosphor emitting green light is Zn ₂ SiO ₄ : Mn.
_x (0.5 ≦ x ≦ 3), BaMgAl ₁₂ O ₁₉ : Mn, B
aAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, (Ba, Sr,
Mg) O.5Al ₂ O ₃ : Mn, BaMgAl ₁₆ O ₂₆ : E
u, Mn, formula (1-a) (bMO · 6Al 2 O 3) ·
a is _{(MMg 1-c Mn c Al} 10 O 17) (M is Ba, at least one of Sr, a, b, c respectively 0.05 ≦
a ≦ 1.0, 0.64 ≦ b ≦ 0.86, 0.05 ≦ c ≦ 1.0 and 0.05 ≦
manganese-activated aluminate a × c ≦ 0.3 satisfies number made), the general formula _{(M x Ce y Tb z)} PO 4 (M is La,
X, y, and z are each at least 0.50. ≦ x ≦ 90, 0 ≦ y ≦ 0.3, and 0.04 ≦ z ≦ 0.16.
At least one member selected from the group is used. Two or more kinds may be used as a mixture.

The blue-emitting phosphor is Ba_1-xEu_xMgA
l₁₄O_{twenty three}(0.03 ≦ x ≦ 0.15), Ba_{1- x}Eu_xMgAl_TenO
₁₇(0.045 ≦ x ≦ 0.25), Ba_1-xySr_xEu_yMgAl
_TenO ₁₇(0.1 ≦ x + y ≦ 0.6), 3 (Ba, Mg) O · 8
Al_TwoO_Three: Eu, CaWO_Four: Pb, Y_TwoSiO_Five: C
e, YPVO_FourUsing at least one selected from the group
You. Two or more kinds may be used as a mixture.

In phosphor synthesis and powder production,
Since many factors such as the selection and purity of the raw material compounds, the accuracy of blending, the temperature in mixing and melting, and the reaction conditions such as atmosphere affect the setting, the condition setting is an important requirement. In addition, heat treatment conditions that determine characteristics such as the powder shape are also important because they affect the phosphor paste formability and the characteristics of the phosphor layer.

As the shape of the phosphor powder, a polyhedral (granular) shape is preferable, and a powder having a shape close to a sphere can be more preferably used, but a powder having no aggregation is particularly preferable.

Voids inside the formed phosphor layer and irregularities on the surface of the phosphor layer are not preferable because they cause a reduction in luminance. Irregularities on the surface of the phosphor layer irregularly reflect light emission, so that the loss of light increases and the luminance is reduced, and the luminance varies.

The thickness of the phosphor layer is 5 to 25 μm, preferably 8 to 20 μm, and more preferably 8 to 1 μm.
5 μm. If it exceeds 25 μm, particularly, the pitch of the high-definition partition walls becomes narrow, so that a sufficient discharge space cannot be obtained. On the other hand, when the thickness is less than 5 μm, the amount of transmitted light increases and the luminance decreases.

Therefore, in order to obtain a PDP having a high luminance, the particle size of the phosphor powder to be mixed with the paste used for forming the phosphor layer is controlled to prevent the particles from agglomerating, to generate internal voids and to reduce surface irregularities. Care must be taken that there are no associated coarse particles and that a dense phosphor layer can be formed.

In the present invention, it is preferable to use a phosphor powder having an average particle size of 1 to 5 μm and a maximum particle size of 30 μm or less.
A more preferable range of the average particle size is 2 to 5 μm. Further, the maximum particle size is more preferably 20 μm or less, and 10 μm or less.
m or less is more preferable.

The cohesiveness of a particle depends on its surface area, and the larger the surface area, the easier it is to aggregate. Therefore, particles having a smaller average particle size are more likely to aggregate. By setting the average particle size to 1 μm or more, it is possible to avoid formation of coarse particles due to aggregation of particles in the paste, and by setting the average particle size to 5 μm or less, it is possible to maintain the denseness of the paste coating film. it can. In addition, particles having an average particle size of less than 1 μm have an excessively large specific surface area, which increases the number of crystal defects, which may lower the luminance.

By controlling the maximum particle size to 30 μm or less, it is possible to suppress generation of voids and surface irregularities in the paste coating film. Since making the maximum particle size as small as possible and simultaneously setting the average particle size in an appropriate range is related to the yield at the time of manufacturing the phosphor powder, the smaller the yield is, the better the economical range is preferable.

Further, since increasing the thickness of the phosphor layer causes a decrease in luminance, the thickness of the phosphor layer is set to 5 as described above.
When it is in the range of from 25 to 25 μm, the preferred maximum particle size of the phosphor powder used is 30 μm or less, more preferably 20 μm or less, and further preferably 10 μm or less.

The phosphor paste is obtained by dispersing and dissolving a phosphor powder and an organic component to be a binder in a solvent. Usually, the phosphor powder is mixed and dispersed in a solution in which an organic component to be a binder is dissolved in a solvent. Formed. It is necessary to adjust the viscosity to an appropriate value according to the coating method, and the viscosity is controlled by controlling the amount of the solvent.

The phosphor paste of the present invention comprises phosphor powder 6
It preferably contains 0 to 95% by weight and 40 to 5% by weight of an organic component. The step of thermally decomposing and removing an organic component as a binder by heat treatment of the phosphor paste coating film to form a phosphor layer is preferably performed at a temperature as low as possible and in a short time, from the viewpoint of maintaining the characteristics of the phosphor itself. From this viewpoint, it is preferable to use an organic component which is thermally decomposed at a low temperature and is easily removed, as little as possible.However, the stability as a paste, the provision of an appropriate viscosity for application, the wettability between the applied partition walls, and the flowability In some cases, the amount of the necessary organic component is increased in order to impart properties such as the properties and the ability to form a dense coating film, and the blending ratio of the phosphor powder and the organic component is preferably controlled within the above range.

When the organic component is less than 5% by weight,
Problems tend to occur in the dispersion stability of the phosphor powder in the paste, the provision of a viscosity suitable for application, the fluidity at the application position and the film thickness retention. On the other hand, when the organic component is more than 40% by weight, it takes time to remove the organic component in the heat treatment step, which causes deterioration of the phosphor itself, or the removal of the organic component is incompletely completed, and the emission performance of the phosphor is reduced. May have adverse effects. Further, since the amount of the organic component removed is large, the formed phosphor layer is not sufficiently dense and internal voids are easily generated, which may cause a problem such as a decrease in luminance.

The phosphor paste applied between the partition walls is
After being transferred to the side wall of the partition, the paste is lowered on its side by its own weight, and is equalized by its own weight and surface tension, so that a phosphor paste coating film is formed on the side and its bottom of the partition. If the viscosity of the paste is low, the paste concentrates on the bottom and the thickness of the side wall of the partition wall becomes thin, which causes a loss of luminance and a decrease in luminance at a wide viewing angle. When the viscosity is high, it is effective for securing the luminance, but it is difficult to set conditions for applying a uniform film thickness.

As the organic component, an organic polymer which is soluble in a solvent, can impart an appropriate viscosity, and can be easily removed by thermal decomposition is preferably used.

It is preferable to use an acrylic resin as the organic component used in the present invention. Acrylic resin is 40
It can be removed by thermal decomposition at about 0 ° C., and polymers having various physical properties can be easily obtained by polymerization and copolymerization of acrylates and methacrylates. Suitable for. In the present invention, it is preferable to use polymethyl methacrylate (PMMA), which is a typical polymer of an acrylic resin, or a copolymer thereof. The paste containing PMMA as an organic component can be thermally decomposed and removed by baking at a relatively low temperature of 350 to 450 ° C. In addition, although the reason is not clear, the rare earth element added to the phosphor as an activation element Since the oxidation of the elements is suppressed, the emission luminance of the phosphor layer can be kept high. Further, the paste containing PMMA as an organic component has some disadvantages in the viscosity property and spreadability in the case of the screen printing method, but is suitable for the nozzle coating method and enables a smooth coating. There is.

When an acrylic resin is used as an organic component,
Organic solvents include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone,
Isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and the like, and a mixture containing at least one of these are used.

In the present invention, it is preferable to use a phosphor paste in which the organic component is a photosensitive organic component, in addition to the acrylic resin as described above.

Depending on the method of applying the paste, there is a problem that the phosphor paste adheres to an unnecessary portion such as the top of the partition wall to cause a contaminated site, and a simple method for removing such an unnecessary paste is required.

Further, even when the phosphor paste is applied and dried to form a predetermined coating film, the coating film thickness changes due to thermoplastic deformation from the coating state in the temperature rising process in the next heat treatment step, There is a concern that luminance unevenness and luminance decrease may occur.

As a phosphor paste for solving such a problem, a paste in which an organic component is photosensitive is preferable. That is, the unnecessary paste adhering to the tops of the partition walls can be easily dissolved and removed by subjecting the paste applied between the partition walls to photo-curing by pattern exposure and then developing the paste.
In addition, deformation of the coating film due to heating can be prevented because the photocured coating film has a three-dimensional structure.

The organic photosensitive component includes a type in which the exposed portion is insolubilized and a type in which the exposed portion is solubilized, and any type can be used for the purpose of the present invention. In the case of the insolubilizing type, the paste applied between the partition walls can be exposed to light to make it insoluble in the developing solution, and the paste on the top of the partition walls can be dissolved and removed with the developing solution. On the other hand, in the case of the solubilized type, the top of the partition wall is irradiated with light, which can be removed as soluble in the developer.

According to the present invention, there are advantages of both the removal of the unnecessary portion of the paste and the photo-curing of the coating film, and it is possible to select a type of polymer having good thermal decomposability at the time of heat treatment. It is preferable to use a photo-insolubilizing type photosensitive organic component from the viewpoint of being easily mixed and used.

The photosensitive organic component includes, in addition to a photosensitive monomer, a photosensitive or non-photosensitive oligomer or polymer, a photopolymerization initiator, a sensitizer, a sensitizing aid, an ultraviolet absorber,
A polymerization inhibitor, a plasticizer, a thickener, a dispersant, and other additives can be added as needed.

As the photosensitive monomer, a compound having an active carbon-carbon double bond is used.
Monofunctional and polyfunctional compounds having a vinyl group, an allyl group, an acrylate group, a methacrylate group, an acrylamide group and the like are applied. It is preferable to use a polyfunctional acrylate compound and / or a polyfunctional methacrylate compound for the photosensitive organic component of the present invention.

The photosensitive organic component serves as a component for improving the physical properties of the cured product formed by the photoreaction, adjusting the viscosity of the paste, and controlling the solubility of the unexposed paste. Alternatively, a non-photosensitive oligomer or polymer is used. These oligomers or polymers have a carbon chain skeleton obtained by polymerization or copolymerization of components selected from compounds having a carbon-carbon double bond. It is preferable to use an acrylic oligomer or polymer in consideration of the thermal decomposability of the oligomer or polymer. As the monomer to be copolymerized, an unsaturated carboxylic acid such as acrylic acid or methacrylic acid is useful, and it is possible to give a photosensitive phosphor paste capable of developing an unexposed portion after exposure with an aqueous alkali solution.

The thus obtained oligomer or polymer having an acid group such as a carboxyl group in the side chain is controlled to have an acid value of 50 to 180, preferably 70 to 140.

For use as a photosensitive oligomer or polymer, those having a weight average molecular weight of 500 to 100,000 containing a carboxyl group and an unsaturated double bond in the molecule are preferred. To introduce an unsaturated double bond, a method is used in which an oligomer or polymer having a carboxyl group in the side chain is subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, or methacrylic acid chloride. Is done. In addition, a method of introducing an unsaturated double bond by forming a salt bond with a carboxyl group can also be used, for example, by reacting a dialkylaminoacrylate or a dialkylaminomethacrylate to make an acrylate group or a methacrylate group a photosensitive group. Can be.

The number of carboxyl groups for developing with an aqueous alkali solution and the number of ethylenically unsaturated groups that render the oligomer or polymer photosensitive can be freely selected depending on the reaction conditions.

When the photosensitive phosphor paste having a photosensitive organic component as described above is irradiated with light, the exposed portions become insoluble in a developing solution due to radical polymerization and crosslinking reaction. For that purpose, a photopolymerization initiator is required as a component that generates an active radical to initiate a radical polymerization or a crosslinking reaction.

After the photosensitive phosphor paste applied between the partition walls is photo-cured, the whole is treated with an alkaline aqueous solution of a developing solution, whereby unnecessary portions of the paste such as the top portions of the partition walls are dissolved and removed.

[0053]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. The concentration (%) is% by weight unless otherwise specified.

Example 1 Red phosphor powder (Y _1-x Eu _x ) BO ₃ (x = 0.06)
Was manufactured as follows. Oxalate precipitate was formed using yttrium oxide and europium oxide.
A predetermined amount of the oxide obtained by calcining at 0 ° C. for 3 hours and H ₃ BO ₃ was mixed, barium chloride was added as a flux, and the mixture was sufficiently mixed.
Bake for hours. After that, take out the phosphor, disperse, wash with water,
dry. The average particle size of the red phosphor powder is 1.6 μm.
And the maximum particle size was 5.5 μm.

Green phosphor powder Zn ₂ SiO ₄ : Mn (M
n: 0.7% by weight) was produced as follows. A predetermined amount of raw material powders such as zinc oxide, manganese carbonate and silicon oxide are dry-mixed, and magnesium fluoride and ammonium chloride are added as fluxes, and the mixture is sufficiently pulverized and mixed with a ball mill. After the pulverization and mixing, the phosphor material is packed in a quartz crucible and fired at 1250 ° C. for 3 hours. Thereafter, the phosphor is taken out and dispersed in a ball mill in water, and separated and dried.
The average particle size of the green phosphor powder was 3.2 μm, and the maximum particle size was 13.1 μm.

Blue phosphor powder Ba _0.9 Eu _0.1 MgAl ₁₀
O ₁₇ was produced as follows. Ba, Eu, Mg, Al
Barium carbonate, basic magnesium, aluminum oxide, so that the atomic ratio of is 0.9: 0.1: 1: 10.
Weigh each powder of europium oxide. At the same time, B
Aluminum fluoride is weighed such that the atomic ratio of Al to a becomes 0.3. Using a mortar, the above-mentioned predetermined amounts of barium carbonate, basic magnesium, aluminum oxide, europium oxide and aluminum fluoride are mixed. The mixture is charged into an alumina boat, and calcined in a mixed gas of nitrogen and hydrogen at 1600 ° C. (flow ratio: 380 cc / min: 20 cc / min) for 2 hours using a tubular atmosphere furnace, and represented by the above chemical formula. A phosphor was obtained. This blue phosphor powder has an average particle size of 3.6 μm and a maximum particle size of 1 μm.
It was 5.6 μm.

These phosphors were used after being subjected to a spheroidizing treatment for instantaneous high-temperature treatment in argon plasma. The coordinate values in the CIE chromaticity diagram of each color phosphor thus obtained are as follows: red phosphor powder (0.63, 0.32), green phosphor powder (0.14, 0.71), blue phosphor Body powder (0.15, 0.055).

Using these phosphor powders, a phosphor paste was prepared as follows. Mitsubishi Rayon PM
MA "Acripet" VH is dissolved in a solvent of terpineol / benzyl alcohol (1: 7) and the PMM is 18%
A solution was prepared, and the phosphor powder 9
Were mixed and dispersed to prepare phosphor pastes for each color.

A front substrate on which transparent electrodes, bus electrodes, a transparent dielectric layer and a protective layer were formed, and a rear substrate on which address electrodes and partition walls were formed were prepared.

The paste was applied at a pitch of 220 μm and a height of 15 μm.
On a glass substrate on which 961 stripe-shaped partitions having a thickness of 0 μm and a width of 60 μm were formed, phosphor pastes for each of red, green, and blue were applied every third.

The coating was performed by a nozzle having one discharge port having a hole diameter of 150 μm. One nozzle was used for each of the red, green, and blue phosphor pastes. A predetermined amount of the phosphor paste was discharged while the nozzle was running at a constant speed in parallel with the partition walls, and the phosphor paste was applied one by one between the partition walls. First, a red phosphor paste was applied one by one between predetermined partition walls. At this time, the nozzle was moved by 660 μm in the direction perpendicular to the partition wall direction at the position where the first coating was completed, and then the coating was performed between the second partition walls while running the nozzle in the direction opposite to the first coating. By repeating this, 32 at the predetermined position of the red phosphor is
0 were applied. After application, 80 ° C with the application side up
For 40 minutes. Next, 320 green phosphor pastes were similarly applied between the adjacent partitions coated with the red phosphor and dried. Further, 320 blue phosphors were similarly applied between the adjacent partitions coated with the green phosphor and dried. afterwards,
The obtained glass substrate was baked at 450 ° C. for 30 minutes in air to produce a rear glass substrate.

When the thickness of the obtained phosphor layer was observed with an electron microscope, the phosphor of each color was found to be 12 ± 3 μm on the side surface of the partition wall.
m, formed on the bottom with a thickness of 15 ± 3 μm. The phosphor layer was dense, no voids were observed, and the layer surface was smooth.

The front glass substrate is placed and sealed on the rear glass substrate thus manufactured, and a mixed gas of xenon, helium, and neon is supplied to the discharge cell at 500 Torr.
To produce a PDP.

The formed PDP has R, which has high color purity,
G and B were displayed, beautiful and clear display became possible, and the white balance was good.

Example 2 Red phosphor powder (Y _0.63 Gd _0.37 ) BO ₃ : Eu (Eu =
0.065) was produced in the same manner as in Example 1 except that oxalate precipitates were formed using gadolinium oxide, yttrium oxide, and europium oxide. The average particle size of the red phosphor powder was 1.7 μm, and the maximum particle size was 6.5 μm.

Green phosphor powder Zn ₂ SiO ₄ : Mn (M
n: 0.7% by weight) was produced by the method described in Example 1 while changing the blending amount. The average particle size of the green phosphor powder was 2.8 μm, and the maximum particle size was 11.0 μm.

Blue phosphor powder Ba _0.95 Eu _0.05 MgAl
₁₄ O ₂₃ was produced by the method described in Example 1 while changing the blending amount. This blue phosphor powder had an average particle size of 3.7 μm and a maximum particle size of 15.6 μm.

These phosphor powders were heat-treated in the same manner as in Example 1 and used. The coordinate values of the obtained phosphors in the CIE chromaticity diagram are indicated by red phosphor powder (0.68, 0.3
1), green phosphor powder (0.13, 0.75) and blue phosphor powder (0.14, 0.045).

A phosphor paste was prepared in the same manner as in Example 1 using these phosphor powders. PD formed
P displays R, G, and B with high color purity, enables beautiful and clear display, and has a good white balance.

Example 3 A red phosphor powder (Y _0.935 Eu _0.065 ) ₂ O ₃ was prepared by heating and decomposing a coprecipitated oxalate compounded in a predetermined amount at 1000 ° C. to obtain a flux comprising barium chloride, boric acid and ammonium chloride. The mixture was thoroughly dry-mixed, boiled down in a crucible, and baked in an oxidation atmosphere at 1425 ° C. for 5 hours in a muffle furnace. The obtained phosphor was dispersed, washed with water and dried as usual, and passed through a sieve to obtain a red phosphor powder. The average particle size of this red phosphor powder was 3.1 μm, and the maximum particle size was 13.1 μm.

Green phosphor powder (Gd _0.87 Ce _0.1 Tb)
_0.03 ) PO ₄ was produced as follows. Gd source, Ce
A source, a coprecipitated oxide of GdCeTb as a Tb source, and diammonium hydrogen phosphate as a phosphoric acid source are stoichiometrically weighed so as to form a predetermined mixture, and mixed sufficiently. Calcination was performed at 700 ° C. for 2 hours. Cool the calcined product to room temperature, add lithium carbonate, boric acid and ammonium sulfate, mix well, pulverize,
Put again in the quartz crucible,
After firing for a time, the fired product was pulverized, washed, and sieved to obtain a green phosphor powder. The average particle size of the green phosphor powder is 3.
At 7 μm, the maximum particle size was 13.1 μm.

As the blue phosphor powder, the same Ba _0.9 Eu _0.1 MgAl ₁₀ O ₁₇ as used in Example 1 was used. This blue phosphor powder has an average particle size of 3.8 μm and a maximum particle size of 1 μm.
It was 5.6 μm.

The coordinate values of these three color phosphor powders in the CIE chromaticity diagram are shown in red phosphor powder (0.65, 0.3
3), a green phosphor powder (0.14, 0.72) and a blue phosphor powder (0.15, 0.055).

A phosphor paste was prepared in the same manner as in Example 1 using these phosphor powders. PD formed
P displays R, G, and B with high color purity, enables beautiful and clear display, and has a good white balance.

Example 4 In Example 1, the phosphor powder having the following coordinate values was obtained by increasing the purity of the starting compound used and strictly controlling the firing atmosphere and temperature in producing each color phosphor. I was able to. That is, a red phosphor (0.66, 0.26) and a green phosphor (0.0
8, 0.78) and a blue phosphor (0.18, 0.03). At this time, the average particle size of the red phosphor powder was 1.0 μm.
The average particle size of the green phosphor powder is 3.0 μm and the maximum particle size is 12.0 μm, and the average particle size of the blue phosphor powder is 3.8 μm and the maximum particle size is 3.8 μm. Is 1
4.3 μm.

A phosphor paste was prepared in the same manner as in Example 1 using these phosphor powders. PD formed
P displays R, G, and B with high color purity, enables beautiful and clear display, and has a good white balance.

Example 5 The powder of each color phosphor used in Example 1 had a particle size distribution having at least two peaks. With such a particle size distribution, the luminance of each phosphor can be further improved, and the display quality can be further improved compared to the first embodiment.

Example 6 In Example 1, 25 parts by weight of a photosensitive polymer (X-4007) and a photosensitive monomer (M) were used in place of the PMMA solution.
GP400) 15 parts by weight, photopolymerization initiator (IC369)
A solution in which 3 parts by weight was dissolved in 67.5 parts by weight of γ-butyrolactone was used. A paste was prepared by mixing 60 parts by weight of the phosphor powder with this solution, and the paste was applied by nozzle application between the partition walls of the rear glass substrate and dried. After the photosensitive paste in the partition was exposed to ultraviolet light, unnecessary paste attached to the top of the partition and the like was dissolved and removed with a developing solution, and then baked to form a 20 μm-thick phosphor layer. Obtained PD
The color purity of P was excellent, and a clear and vivid image display was possible.

Example 9 In Example 1, the baking atmosphere after applying each color phosphor paste between the partition walls was performed in a nitrogen atmosphere having an oxygen concentration of 20 ppm. By firing in such an atmosphere, the oxidation of the rare earth elements used can be prevented, so that the emission color purity of the phosphor layer to be formed is close to that of the phosphor powder as a raw material, which is more beautiful than that of Example 1. And vivid image display was possible.

Comparative Example 1 The red phosphor had a coordinate value of (0.64, 0.36),
In the green phosphor, the coordinate values are (0.25, 0.6
9), and the coordinate value of the blue phosphor is (0.15,
A phosphor paste was prepared in the same manner as in Example 1 using the phosphor of 0.09). The color purity of the formed PDP was reduced, and the range of displayable colors was narrow. Description of abbreviations X-4007: Weight-average molecular weight obtained by subjecting a copolymer composed of 40% of methacrylic acid, 30% of methyl methacrylate and 30% of styrene to addition reaction of 0.4 equivalent of glycidyl methacrylate to 4.3. A photosensitive polymer having an acid value of 95.

MGP400: X ₂ N-CH (CH ₃ ) -CH _2- (OCH ₂ CH (CH ₃ )) _n -NX ₂ X: -CH ₂ CH (H) -CH ₂ O-CO-C (CH ₃ ) = CH ₂ n: 2 to 10 IC-369: “Irgacure” 369 (a product of Ciba-Geigy) 2-Phen-2-yl-2-methylamino-1- (4-morpholinophenyl) phthalanone-1

[0082]

By using the phosphor powder of the present invention, three primary colors having excellent color purity can be obtained, and the color reproduction range can be widened.

Further, the average particle size of the phosphor powder is 1 to 5 μm.
By controlling the m and the maximum particle size to 30 μm or less, a phosphor paste having good dispersibility of the phosphor powder and excellent applicability can be obtained. As a result, a dense and uniform phosphor layer without surface irregularities can be obtained, so that high-luminance display is possible. It is preferable to use an acrylic resin as an organic component of the phosphor paste, and it is more preferable to use these as a photosensitive organic component. Thereby, the emission luminance can be kept high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/78 CPB C09K 11/78 CPB CPK CPK CPV CPV 11/80 CPM 11/80 CPM 11/81 CPW 11 / 81 CWP 11/83 CPV 11/83 CPV H01J 11/02 H01J 11/02 B 29/20 29/20 F term (reference) 4H001 CA05 CA06 XA05 XA08 XA12 XA13 XA14 XA15 XA20 XA23 XA25 XA30 XA38 XA39 XA56 XA63 XA58 XA64 XA65 XA74 YA25 YA58 YA59 YA63 YA65 YA66 YA69 YA70 YA82 5C028 FF16 HH14 5C040 FA01 FA02 GA03 GG08 GG09 JA13 MA02 MA03

Claims (9)

[Claims] 1. A method for manufacturing a display, wherein phosphor layers including phosphors emitting red, green, and blue light are respectively formed on a substrate, wherein the emission colors of the red, green, and blue phosphors are provided. CIE chromaticity coordinates of (Rx, Ry)
A method for manufacturing a display, wherein the following relational expressions (1), (2) and (3) are satisfied when (Gx, Gy) and (Bx, By). (1) 0.60 ≦ Rx ≦ 0.72 and 0.22 ≦ Ry
≦ 0.33 (2) 0.08 ≦ Gx ≦ 0.14 and 0.70 ≦ Gy
≦ 0.82 (3) 0.13 ≦ Bx ≦ 0.24 and 0.01 ≦ By
≦ 0.08 2. The method according to claim 1, wherein the phosphor has an average particle size of 1 to 5 μm and a maximum particle size of 30 μm or less. 3. The method according to claim 1, wherein said red phosphor is (Y ₁ -xE _x ) ₂ O ₃
(0.040 ≦ x ≦ 0.070), (Y _1-x Eu _x ) BO ₃ (0.025 ≦
x ≦ 0.060), Y ₂ SiO ₅ : Eu, (Y, Gd, Eu)
BO ₃ , Y (P, V) O ₄ : Eu, GdBO ₃ : Eu, S
cBO ₃ : Eu and the general formula Lm ₂ O ₃ : R (Lm is G
at least one of d, Y, La and Lu;
R is at least one selected from the group consisting of Eu, Tb, Pr, Dy, Tm, Ce and Yb)
The method for manufacturing a display according to claim 1, wherein the display is a seed. Wherein said green phosphor, Zn ₂ SiO _4: Mn _x
(0.5 ≦ x ≦ 3), BaMgAl ₁₂ O ₁₉ : Mn, Ba
Al ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, (Ba, Sr, M
g) O · 5Al ₂ O ₃ : Mn, BaMgAl ₁₆ O ₂₆ : E
u, Mn, formula (1-a) (bMO · 6Al 2 O 3) ·
a is _{(MMg 1-c Mn c Al} 10 O 17) (M is Ba, at least one of Sr, a, b, c respectively 0.05 ≦
a ≦ 1.0, 0.64 ≦ b ≦ 0.86, 0.05 ≦ c ≦ 1.0 and 0.05 ≦
manganese-activated aluminate a × c ≦ 0.3 satisfies number made), the general formula _{(M x Ce y Tb z)} PO 4 (M is La,
X, y, and z are each at least 0.50. ≦ x ≦ 90, 0 ≦ y ≦ 0.3, and 0.04 ≦ z ≦ 0.16.
3. The method for manufacturing a display according to claim 1, wherein the method is at least one selected from the group consisting of: 5. The method according to claim 1, wherein the blue phosphor is Ba _1-x Eu _x MgAl.
₁₄ O ₂₃ (0.03 ≦ x ≦ 0.15), Ba _1-x Eu _x MgAl ₁₀ O ₁₇
(0.045 ≦ x ≦ 0.25), Ba _1-xy Sr _x Eu _y MgAl ₁₀
O ₁₇ (0.1 ≦ x + y ≦ 0.6), 3 (Ba, Mg) O · 8A
l ₂ O ₃ : Eu, CaWO ₄ : Pb, Y ₂ SiO ₅ : Ce,
The method according to claim 1, wherein the method is at least one selected from the group consisting of YPVO ₄ . 6. An organic component 4 comprising 60 to 95% by weight of a phosphor powder.
6. The method according to claim 1, wherein the phosphor layer is formed by applying a phosphor paste containing 0 to 5% by weight on the substrate. 7. The method according to claim 6, wherein an acrylic resin is used as the organic component. 8. The method according to claim 6, wherein the organic component is a photosensitive organic component. 9. The display manufacturing method according to claim 1, wherein the display is an image forming apparatus using a plasma display panel or an electron-emitting device.