JP2003292946A - Fluorescent paste, plasma display part and plasma display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorescent paste exhibiting little change of panel luminescent characteristic by the lighting of the panel for a long period, and provide a plasma display part and a plasma display. <P>SOLUTION: The fluorescent paste contains particles of a fluoride in a fluorescent paste. The plasma display part and the plasma display contain the fluorinate particles in the fluorescent layer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma display (hereinafter abbreviated as PDP) having a phosphor layer, a plasma display member, and a phosphor paste as a raw material thereof.

[0002]

2. Description of the Related Art PDPs are drawing attention as displays that can be used in thin and large-sized televisions. FIG. 1 shows an exploded perspective view of a structural example of a PDP. The PDP is provided with a phosphor layer. The phosphor layer is made of phosphor powder that is excited by ultraviolet rays to emit light. A paste made of phosphor powder and a resin component, or a sheet-shaped paste is placed on a panel substrate. Then, it is baked at around 500 ° C., and is formed through a process of burning away the resin component in the paste. Examples of the phosphor layer forming method include a screen printing method, a method of discharging a paste from a nozzle hole, and a photosensitive paste method.

Further, in order to improve the display quality of the PDP, it is desired to improve the luminous intensity and luminous efficiency of the phosphor layer. In particular, when the panel is turned on for a long period of time, the emission intensity is lowered and the color shift is likely to occur. In particular, a blue phosphor using an aluminate phosphor in which divalent europium is activated has a problem in that the emission intensity and the chromaticity shift are large, the panel emission brightness is reduced, and the white color temperature is reduced. . Also, W.Lehmann: J.Electrochem.S
oc., 130 (2), 426 (1983). Zn ₂ SiO ₄ : Mn, which is often used for green phosphors, is weak against the impact of charged particles such as electrons and ions, and has emission characteristics. Has been shown to be variable.

On the other hand, as an improvement of the phosphor powder itself, by adjusting the activation amount of divalent europium with respect to the barium to be replaced in the aluminate phosphor, the emission intensity is lowered by firing or long-time discharge. Techniques for suppressing are also disclosed. Japanese Unexamined Patent Publication (Kokai) No. 11-246856 discloses that the activation amount of divalent europium is limited to 8 at% with respect to the barium element to be replaced, whereby the decrease in emission intensity due to firing can be suppressed. Further, in JP-A-8-60147, the substitution amount of Ba having a large ionic radius is reduced as compared with divalent europium,
That is, it is disclosed that the activation amount of divalent europium is increased and the change over time due to long-time lighting discharge is suppressed.

Further, in JP-A-7-320645, for the purpose of protecting the fluorescent substance from ions during discharge light emission, a thin film of a translucent substance having a smaller refractive index than the fluorescent substance has a desired uniform thickness. The technique of coating with is disclosed.

However, even by these means, the effect of suppressing the decrease in emission intensity during long-time lighting after paneling is still insufficient. Further, the technique of coating the powder with a constant thickness has a problem that it is difficult to control the thickness, particles are likely to aggregate with each other through the coating material, and the cost is easily increased.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention has been made in view of the above-mentioned problems in the prior art.
It is an object of the invention to provide a highly reliable and long-life plasma display by suppressing a decrease in emission intensity during long-time lighting after being made into a panel.

[0008]

In order to solve the above problems, the present invention has the following constitution. That is, it is a phosphor paste containing phosphor powder and a resin component, wherein the paste contains fluoride particles. In addition, the fluoride is LiF, MgF ₂ ,
CaF ₂ , BaF ₂ , CeF ₄ , ThF ₄ , SrF ₂ , Al
F ₃ · 3NaF, a phosphor paste containing at least one selected from the group of LiSrAlF _6, LiCaAlF _6.

Further, it is a plasma display in which at least an electrode, a dielectric layer, a partition wall and a phosphor layer are formed, wherein the phosphor layer contains a fluoride.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below. First, the phosphor paste of the present invention will be described. When the phosphor layer is formed on the PDP, the phosphor paste itself may be applied in a sheet form instead of applying the phosphor paste itself.

The phosphor paste of the present invention comprises phosphor powder and
Includes a resin component as an essential component, and fluoride in the paste
It is necessary to include particles. And these are organic solvents
Etc. dispersed and dissolved in a suitable solvent such as. Hugh
Made with this paste by including the oxide particles
Fluoride particles are placed on the phosphor layer of the plasma display.
Therefore, the light emission is
The change in light emission characteristics such as
To make a reliable and long-life plasma display
it can. Here, the fluoride particles are fluorine and other elements.
(For example, alkali metal, alkaline earth metal, transition gold
Compounds of genus, rare earth, etc., crystal and glass
Anything is fine. For example, as the fluoride, LiF, Mg
F₂, CaF₂, BaF₂, CeF_Four, ThF_Four, SrF₂,
AlF₃・ 3NaF, LiSrAlF₆, LiCaAlF
₆It is preferable that at least one selected from the group
Good From the ease and cost of producing fluoride particles
Is MgF₂, CaF₂, BaF ₂Is preferred. Fluoride
The average particle size of is preferably 1 to 30,000 nm.
Good More preferably 1 to 800 nm, even more preferably
Is 1 to 200 nm, more preferably 1 to 30 nm
It The average particle size of fluoride is crystalline structure, crystalline, impure
The smaller the thing, the better.

Since the purpose of the present invention is to protect the particles from charged particles while ensuring the transparency of ultraviolet rays, it is effective that the average particle diameter of the fluoride is as small as possible, that is, the distance to the phosphor surface is short. Even if fluoride is added at the same ratio, the smaller the average particle size, the higher the coverage of the phosphor surface.

Fluoride reacts with oxides or carbonates and hydrofluoric acid (for example, by reacting calcium carbonate with hydrofluoric acid, CaF
2) can be created. For example, Morita Chemical Co., Ltd. "fluorine compound for optical glass" can be used. Furthermore, if necessary, dry / wet pulverization and classification can be performed to adjust the particle size distribution. Further, when the fluoride is water-soluble, it can be prepared by using a spray dry method.

In the plasma display, ultraviolet rays are generated by applying a high voltage to the electrodes and discharging the discharge gas, and the ultraviolet rays cause the phosphors to emit light. Xe-Ne as discharge gas
When a mixed gas is used, the wavelength of the generated ultraviolet rays is 1
47 nm (resonance line) and 172 nm (molecular beam). The intensity ratio of resonance line and molecular beam depends on the Xe ratio, but Xe is 5%.
In -Ne gas, the resonance line is several times higher in intensity. During the discharge, not only ultraviolet rays but also charged particles such as ions and electrons and high-speed neutral atoms and molecules are present, and the phosphor surface is exposed to these particles. Therefore, it is considered that the crystal structure and the chemical state of the surface of the phosphor are changed and the emission characteristics are changed. When the phosphor layer contains fluoride, the fluoride is distributed on the surface of the phosphor, so that the phosphor layer acts as a protective film against charged particles. That is, it is considered that the change in the crystal structure or the chemical state is reduced, and thus the change in the light emission characteristics due to long-time lighting is suppressed. Furthermore, since there are fluorides on the surface of the phosphor powder, it is possible to expect an effect of suppressing thermal deterioration during paste firing.

It is conceivable to use a phosphor coated with MgF ₂ or the like in a wet or dry manner for the same effect. However, since the phosphor powders tend to aggregate with each other depending on the coating material, the present invention is more preferable. Simple and effective. It is also superior from the cost point of view when using a coated phosphor. Generally, a fluoride has a wide bandgap and is transparent with little absorption in the excitation wavelength range of a plasma display. Therefore, the fluoride can function as a protection for charged particles without reducing the intensity of ultraviolet light that excites the phosphor.

On the other hand, particles other than fluoride (for example, oxide glass, oxides such as silica, titania and alumina,
Metals such as gold, silver, and chrome) absorb a large amount of ultraviolet rays, effectively reducing the amount of ultraviolet rays that reach the phosphor, resulting in low emission intensity. However, particles other than fluoride may be included for the purpose of improving paste properties such as dispersibility and thixotropy of the phosphor paste. Since the present invention relates to suppression of deterioration of light emission characteristics due to long-time lighting,
Particles other than fluoride (excluding phosphor powder) are preferably 0.1 to 40% by weight with respect to fluoride. More preferably 1 to 15% by weight, still more preferably 2-1
It is 0% by weight.

It is preferable that the crystallinity of the fluoride is good and the amount of impurities is small in view of the transparency of ultraviolet rays.

In the phosphor paste of the present invention, the amount of fluoride is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the phosphor powder. It is more preferably 1 to 10 parts by weight. It is more preferably 2 to 7 parts by weight.
If the amount is less than 0.1 parts by weight, the effect of suppressing the change in light emission characteristics due to long-time lighting tends to be difficult to be exhibited. If the amount is more than 30 parts by weight, the emission brightness may be too low.

Generally, the powder tends to aggregate more easily as the average particle size becomes smaller, but as protection from charged particles,
It is desirable for the fluoride to be as nearly monodisperse as possible in the phosphor paste. Fluoride may be added directly at the time of preparing the paste, but it is better to prepare a slurry or sol of fluoride in advance and use this in order to improve the dispersibility. For example, as the solvent for the slurry, alcohol solvents such as methanol, ethanol, isopropyl alcohol, etc., esters, ethers, etc. can be used.

The phosphor powder is not particularly limited, but the following phosphors are preferable from the viewpoint of emission intensity, chromaticity, color balance, life and the like. Blue is an aluminate phosphor activated with divalent europium. Further, from the viewpoint of suppressing deterioration during paste firing, it is preferable that the aluminum element is in excess of the stoichiometric composition. Further, the excess amount of aluminum element is preferably 10% or less with respect to the stoichiometric composition. If the excess amount is more than 10%, a by-product is not generated during the phosphor powder synthesis to form a single phase, the emission intensity is reduced and the y value of chromaticity is increased, and the blue color purity is reduced, resulting in a panel failure. The color reproducibility range of is likely to be narrowed. Preferably from 0.1 to 9 relative to stoichiometric composition.
It is within the range of 5%. It is more preferably within the range of 1 to 9%, and even more preferably within the range of 2 to 8%.

Here, an aluminate having a stoichiometric composition is used.
For example, MMgAl₁₄O_{twenty three}, MMgAl_TenO₁₇,
MMg₂Al₁₆O₂₇, MMg₂Al₁₄O_{twenty four} , M₂Mg₂A
l₁₂O_{twenty two} , M₃Mg_FourA_l8O₁₈ , M₃Mg_FiveAl₁₈O_{twenty five} 
And so on. Element M is low in Ba, Sr and Ca.
It is preferable to include at least one kind. Above all, the panel
The point that emission intensity decreases when lit and chromaticity shift is small
From MMgAl_TenO ₁₇More atomic formula aluminate
It is preferably used.

Further, in the case of the atomic formula aluminate phosphor of MMgAl ₁₀ O ₁₇ , the amount of magnesium element is 90 to 100 relative to the stoichiometric composition in order to suppress the brightness decrease and the chromaticity shift due to the paste firing. % Is preferable. This is because when the amount of elemental magnesium is less than 90% or more than 100% with respect to the stoichiometric composition, there is a tendency that the luminance decreases and the chromaticity shift increases after the paste is fired.

Further, the substitution amount of divalent europium in the aluminate phosphor is preferably within the range of 5 to 20 at% with respect to the element M. If the substitution amount is less than 5 at%, an electron trap having a deep energy level may be formed in the vicinity of the divalent europium due to long-time lighting after the panel is formed, and the emission intensity may decrease and the chromaticity shift may increase. . When the substitution amount is larger than 20 at%, the emission intensity may be decreased and the chromaticity shift may be large due to the firing of the paste, and when the substitution amount is 50 at% or more, the emission intensity tends to be decreased to the unfired phosphor powder due to concentration quenching. .

In the case of green, Zn ₂ Si is used in terms of panel brightness.
_{O 4: Mn, YBO 3:} Tb, BaMg 2 Al 14 O 24: E
u, Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl
₁₄ O ₂₃ : Mn is preferred. More preferably Zn ₂ S
iO _4: is Mn.

For red, similarly (Y, Gd) BO ₃ : E
u, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are preferable. More preferably (Y, Gd) BO ₃ : Eu
Is.

In the phosphor paste, the above phosphor powder or
Although it may contain other phosphors or other inorganic particles,
The content of the phosphor powder is preferably 70% by weight or more. Than
It is preferably 85% by weight or more. More preferably 9
It is 5% by weight or more. Specifically, 3Ca₃(PO_Four)₂
・ Ca (F, Cl)₂: Sb, Sr_Ten(PO4)₆C
l₂: Eu, (Sr, Ca)_Ten(PO_Four)₆Cl₂: Eu,
(Sr, Ca)_Ten(PO_Four) ₆Cl₂・ NB₂O₃: Eu,
(Ba, Ca, Mg)_Ten(PO_Four)₆Cl₂: Eu, Sr₂
PO₇: Sn, Ba₂P₂O₇: Ti, Ca₃(PO_Four)₂:
Tl, (Ca, Zn) ₃(PO_Four)₂: Tl, Sr₂P
₂O₇: Eu, SrMgP₂O₇: Eu, Sr₃(P
O_Four)₂: Eu, (Ba, Sr, Mg)₃Si₂O₇: P
b, (Ba, Mg, Zn)₃Si₂O₇: Pb, BaSi₂
O_Five: Pb, Ba₃MgSi₂O₈: Eu, Y₂SiO_Five: C
e, CaWO_Four: A phosphor such as Pb may be included. firefly
Other than light bodies, carbon black, titanium black, etc.
Including pigments and binders such as water glass and low melting point glass
But it's okay.

The particle size of the phosphor powder has a cumulative average particle size D50 of 0.5 measured by a laser diffraction scattering method (for example, wet measurement using an HRA particle size distribution meter manufactured by Microtrac).
It is preferably within the range of 10 to 10 μm, and more preferably within the range of 1 to 5 μm. More preferably, it is 1 to 4 μm.
When the average particle size is 0.5 μm or more, the cohesiveness of the powder is suppressed, the paste applicability is improved, and the denseness and homogeneity of the coating film and the phosphor layer after firing are further improved. can do. By setting the thickness to 10 μm or less, it is possible to suppress unevenness on the surface of the phosphor layer after firing, and further prevent a decrease in brightness and a variation in brightness due to diffuse reflection of light emission.

The maximum particle size of the phosphor powder is 40 μm.
It is preferable that the thickness is 20 μm or less. By setting the maximum particle size to 40 μm or less, the unevenness of the phosphor layer after firing can be further suppressed. Furthermore, it is preferable that the particle size be 20 μm or less in terms of powder filling property. Also, the maximum particle size is related to the method of applying the phosphor paste, and in the case of the screen printing method, it is related to the aperture ratio of the mesh, and is related to the inner diameter of the nozzle such as the dispenser method, so consider these points. Is essential.

The resin component of the phosphor paste of the present invention is usually 400 to 550, which causes less deterioration of the emission intensity of the phosphor powder.
A thermoplastic resin that is calcined at a relatively low temperature of about 0 ° C. is preferable, and as a resin component that can be calcined at such a low temperature, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxymethyl cellulose, hydroxyl ethyl cellulose, hydroxyl propyl cellulose, hydroxyl ethyl propyl cellulose, etc. Cellulose resins and polymethylmethacrylate, poly-i-propylmethacrylate, poly-i-butylmethacrylate and, if necessary, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acryl DOO, dimethylaminoethyl (meth) acrylate, hydroxyl ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyl butyl (meth) acrylate, phenoxy -
An acrylic resin or the like obtained by copolymerizing an acrylic monomer such as 2-hydroxypropyl (meth) acrylate or glycidyl (meth) acrylate can be used.

The content of the phosphor powder and the resin component is 70 to 95 based on the phosphor paste in the dry state.
It is preferable that the content is 5% by weight and the resin component is 5 to 30% by weight. More preferably, the phosphor powder is 80 to 90% by weight, and the resin component is 10 to 20% by weight. Here, the resin component refers to the solid content before the resin is dissolved in the solvent.

When the amount of the resin component is too small, it becomes difficult to obtain the dispersion stability of the phosphor powder in the paste, the viscosity and fluidity of the paste, and the film thickness retention of the coating film. Further, if the resin component is too much, the removal of the resin component by firing tends to be incomplete, and the emission intensity tends to remain as a residue, and it also takes time to remove the organic component by firing, resulting in a phosphor powder. The firing deterioration of itself tends to increase.

The solvent of the phosphor paste of the present invention may be any organic solvent that does not separate from the resin component, such as alcohols,
Ethers, esters and the like and mixed systems thereof are preferred. In particular, it is preferable to use terpineol (terpineol) because it dissolves the binder resin well, sufficiently disperses the phosphor powder, and has excellent coatability. Commercially available terpineol is a mixture of three isomers and is a liquid with a boiling point of 217-219 ° C. Further, in order to adjust the viscosity of the phosphor paste, it is preferable to mix terpineol with an aromatic alcohol having a similar boiling point, for example, benzyl alcohol. The ratio of the resin component and the solvent can be appropriately adjusted from the viewpoint of the viscosity of the paste, the coatability of the phosphor paste, and the like.

When the phosphor paste of the present invention is formed by a photolithography method, in order to impart photosensitivity, a compound containing a carbon-carbon unsaturated bond as a photosensitive monomer, a photopolymerization initiator such as benzophenone, and a photopolymerization initiator. An organic dye such as Sudan 4 which suppresses light scattering may be contained.

The phosphor paste of the present invention further comprises an organic compound dispersant such as an anionic or nonionic surfactant, a higher aliphatic alcohol, a plasticizer (eg, dibutyl phthalate, dioctyl phthalate), if necessary. , Polyethylene glycol, glycer, etc.) and the like. In addition, a thixotropy-imparting agent may be added, if necessary, from the viewpoint of the stringing of the paste and the shape of the phosphor layer coating. For example, silica fine particles (for example, "380" and "R974" manufactured by Nippon Aerosil).

The phosphor paste of the present invention is not particularly limited, but a phosphor solution is prepared by dissolving a binder resin in a solvent with a stirrer under heating (usually about 80 ° C.). Is kneaded using, for example, a disperser such as a three-roll, ball mill, bead mill,
It can be manufactured. For example, not only mixing the organic binder and the phosphor that have been adjusted to a predetermined amount in advance, but also mixing the organic binder and the phosphor in which the solvent or resin component is less than the predetermined amount, and then the remaining solvent or resin. Ingredients can be added and mixed. Above all, it is possible to mix the organic binder and the phosphor by making the resin component less than the predetermined amount and prepare a slurry in advance, and finally add and mix the remaining resin component and solvent so that the predetermined amount is obtained. preferable.

In the firing process for removing the resin component of the phosphor paste, 430-5 in an atmosphere containing oxygen such as air.
It can be baked at 50 ° C. When an acrylic resin is used as the resin, it is preferable to bake in an atmosphere of an inert gas such as nitrogen. This is because it is easy to suppress the generation of fluorine deficiency due to firing.

Next, the structure and manufacturing procedure of a plasma display member and a plasma display using the phosphor paste of the present invention will be described. The basic structure and the like of the plasma display, which is the most common plasma display, will be described with reference to FIG. 1, but the structure is not limited to this. As shown in FIG. 1, in the plasma display, the phosphor layers 13 to 15 formed on the front plate and / or the back plate (in the case of FIG. 1, the phosphor layer is formed only on the back plate 8) are inside the inner space. In the member formed by sealing the front plate 1 and the rear plate 8 so as to face the discharge gas, the discharge gas is sealed in the internal space. That is, the front plate 1 is provided with transparent electrodes (sustain electrodes 4, scan electrodes 3) for display discharge, which are substrates on the display surface side. In the case of an AC type plasma display, the MgO protective film 7 is often formed as a protective film for the electrodes and the transparent dielectric layer 6. On the back plate 8, electrodes (address electrodes 10) for address-selecting cells to be displayed are formed. A partition layer 12 and a phosphor layer 13 for partitioning cells
Although the components 15 to 15 may be formed on either or both of the front plate 1 and the rear plate 8, they are often formed only on the rear plate 8 as shown in FIG. The plasma display has the front plate 1
And the back plate 8 are sealed, and the inner space between them is
A discharge gas such as Xe-Ne or Xe-Ne-He is enclosed.

(Back Plate) As the substrate used for the back plate as the PDP member of the present invention, in addition to soda glass, PD
As a heat-resistant glass for P, "PD200" manufactured by Asahi Glass Co., Ltd. or "PP8" manufactured by Nippon Electric Glass Co., Ltd. can be used.

Address electrodes are formed in stripes on the glass substrate with a metal such as silver, aluminum, chromium or nickel at the pitch of the discharge cells. As a method of forming, a method of pattern-printing a metal paste containing these metal powders and an organic binder as a main component by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a developing step, and further, heating and firing are usually performed at 400 to 600 ° C. to form an electrode pattern. Also, use an etching method in which a metal such as chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, the resist is subjected to pattern exposure / development using a photomask, and then the unnecessary portion of the metal is removed by etching. You can

Further, a dielectric layer may be provided on the address electrode layer in order to stabilize the discharge. On the glass substrate on which the address electrode layer is formed, barrier ribs located in parallel with the electrode layer are formed by a sandblast method, a mold transfer method, a photolithography method or the like. The material of the partition used in the present invention is not particularly limited, and a glass material containing oxides of silicon and boron is applied. Also, the refractive index is 1.5
It is advantageous to include 70% by weight or more of the glass material of 1.68 in the case of forming by the photolithography method. The shape of the partition wall is not particularly limited, but a stripe shape, a cross shape, a hexagonal shape, or the like is preferable.

A phosphor layer is formed using the phosphor paste of the present invention on a glass substrate on which an electrode layer and a partition layer are formed. It can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. Although the thickness of the phosphor layer is not particularly limited, it is 10 to 30 μm, and more preferably 15 to 25 μm in the reflection type plasma display of the three-electrode surface discharge system.
m. The firing for removing the resin component is preferably performed at a temperature at which the resin used is sufficiently debindered. When ethyl cellulose is used as the resin, it is 470 to 550 ° C.
Is. In the case of using polymethylmethacrylate,
430 to 490 ° C. If the firing temperature is too low, the resin component is likely to remain, and if it is too high, distortion is introduced into the glass substrate or the phosphor powder is deteriorated.

In this way, the back plate can be manufactured.

(Front Plate) The glass substrate used for the front plate is the same as that described for the back plate. A transparent electrode such as tin oxide or ITO is lifted off on a glass substrate,
It is formed by a photo etching method or the like.

Next, a bus electrode layer is patterned on the glass substrate on which the transparent electrodes are formed by screen printing silver, aluminum, copper, gold, nickel or the like or by a photolithography method using a photosensitive conductive paste.

A transparent dielectric layer is formed by a screen printing method or the like on the glass substrate on which the transparent electrodes and the bus electrodes are formed. The transparent dielectric material used in the present invention is not particularly limited, but a lead-based glass containing PbO, B ₂ O ₃ , or SiO ₂ or a ZnO-based dielectric material is applied.

Further, for the purpose of protecting the transparent dielectric layer and lowering the discharge voltage, a protective film may be formed so as to cover the transparent dielectric layer. Generally, an oxide of an alkaline earth metal can be used for the protective film. In particular, MgO is excellent in sputter resistance and has a high secondary electron emission coefficient, and thus is preferably used. The MgO protective film is formed by an electron beam evaporation method, a Mg target reactive sputtering method, or an ion plating method. In this way, the front plate can be manufactured.

(Plasma display) After using the back and front plates of these plasma display members to seal the back and front plates, helium, neon, and xenon are placed in the space formed between the front and back substrates. After enclosing a discharge gas composed of, for example, a drive circuit can be attached to produce a plasma display.

[0048]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this.

(Measurement method) (1) Luminance characteristics and maintenance ratio of panel The brightness and chromaticity of the panel were white lighted on the entire surface under a discharge condition of a discharge sustaining voltage of 180 V, a frequency of 30 kHz and a pulse width of 3 μm. Luminance B and chromaticity y were measured using a radiance meter CS-1000, and B / y was calculated. Immediately after manufacturing the plasma display, B ₀
/ Y ₀ (initial light emission characteristic), B ₂₀₀ / y ₂₀₀ after 200 hours of continuous lighting, and the maintenance factor was calculated by the following equation.

Maintenance rate (%) = 100 × (B ₂₀₀ / y ₂₀₀ ).
/ (B ₀ / y ₀ ) (Example 1) First, a back plate was prepared. "PD200"
Use a photosensitive silver paste on a 3-inch glass substrate to make a width of 2
Address electrodes having a thickness of 00 μm, a thickness of 3 μm and a pitch of 360 μm were formed.

Next, a dielectric layer having a thickness of 10 μm was formed by a screen printing method. The composition of the dielectric paste was as follows. 80 parts by weight of glass powder A, 1 part by weight of filler (silicon oxide: Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.),
7 parts by weight of titanium oxide, 20 parts by weight of ethyl cellulose resin, dispersant (Nopcos Perth 092 (manufactured by San Nopco)
0.3 parts by weight, 1 part by weight of the leveling agent. The composition of the glass powder A is bismuth oxide 38%, silicon oxide 6%, boron oxide 20%, zinc oxide 20%, aluminum oxide 4%.
The characteristics are a glass transition point of 475 ° C., a softening point of 515 ° C., a thermal expansion coefficient of 75 × 10 ⁻⁷ / ° C., and a density of 4.61 g / cm ³ .

The paste was prepared by kneading a mixture of these components with a three-roller kneader.

Then, a partition layer pattern was formed by a photolithography method using a photosensitive partition layer paste. The composition of the partition paste was as follows. 60 parts by weight of glass powder B, binder (copolymer of methyl methacrylate and methacrylic acid (average molecular weight 25,000, acid value 1
02) 10 parts by weight, 10 parts by weight of a photosensitive monomer (tetrapropylene glycol diacrylate), a photopolymerization initiator (Irgacure 369 manufactured by Ciba-Geigy), and 17 parts by weight of γ-butyrolactone.

The glass powder B has a glass transition point of 495 ° C.,
A softening point of 530 ° C., a thermal expansion coefficient of 75 × 10 ⁻⁷ / ° C. and a density of 2.54 g / cm ³ were used.

The paste was prepared by kneading a mixture of these components with a three-roller kneader.

After the photosensitive paste coating film was dried, it was exposed to 50 mJ / m through a photomask having a stripe pattern.
After an exposure dose of cm ² was applied, development was performed with a 0.2% aqueous monoethanolamine solution to form a partition pattern. Then, it baked at a baking temperature of 570 ° C. for 15 minutes to obtain a partition wall layer having a good shape.

Next, a phosphor layer was formed by the following procedure.
The blue phosphor is the above-mentioned Ba _0.9 MgAl ₁₀ O ₁₇ : Eu.
_0.1 , (Y, Gd) BO ₃ : Eu was used for the red phosphor, and Zn ₂ SiO ₄ : Mn was used for the green phosphor. Prepare a resin component solution that was previously heated and dissolved at 80 ° C. at a ratio of terpineol: benzyl alcohol: ethyl cellulose (“Ethocel 20 cP”) = 10:70:18, and phosphor powder 80 wt%, resin component (solid content) 18 wt %, The phosphor powder and the resin component solution are kneaded with three rollers, and LiF having an average particle diameter of 2800 nm is added so as to be 5 parts by weight with respect to 100 parts by weight of the phosphor powder. This roll was kneaded to obtain a phosphor paste. This phosphor paste was applied on the partition wall by a dispenser method using a discharge port nozzle having a hole diameter of 150 μm so that both the bottom and side walls of the partition wall had a thickness of about 30 μm. 80 ° C, 2
After drying for 0 minutes, baking was performed at 500 ° C. for 15 minutes in the atmosphere to remove the resin component in the phosphor paste. Thus, the back plate was produced.

Next, a front plate was prepared. Asahi Glass Co., Ltd. "P
A scan electrode having a pitch of 1080 μm and a line width of 350 μm was formed on a D200 ″ 3-inch glass substrate using ITO. Further, a bus electrode having an electrode width of 100 μm and a thickness of 3 μm was formed on the substrate by a photosensitive silver paste method. Formed.

Next, a transparent dielectric glass paste was screen-printed to form a transparent dielectric with a thickness of 30 μm so as to cover the bus electrodes in the display portion. A 1.0 μm thick magnesium oxide layer was formed as a protective film on the substrate having the dielectric formed thereon by electron beam vapor deposition to prepare a front plate.

The front plate and the back plate were arranged so that the respective electrodes were positioned vertically, and the front plate and the back plate were sealed using a glass frit made of PbO, B ₂ O ₃ , ceramic filler or the like. . After sealing, the inside of the sealed front plate and the inside of the back plate were evacuated while heating to about 350 ° C., cooled to room temperature, and then Xe5% -Ne bal. The gas was filled up to 66.5 kPa. Finally, the driving circuit was mounted to complete the PDP.

(Example 2) The average particle diameter of the added particles was 250
A plasma display was produced in the same manner as in Example 1 except that 0 nm of CaF ₂ was used.

Example 3 The average particle diameter of the added particles is 150
A plasma display was manufactured in the same manner as in Example 1 except that BaF _{2 of} 0 nm was used.

(Examples 4 to 11, 16, 17) A plasma display was produced in the same manner as in Example 1 except that the additive particles were MgF ₂ and the average particle diameter and the concentration of the additive particles were as shown in Table 1. did.

(Examples 12 to 14) The additive particles were MgF ₂ having an average particle size of 10 nm, 10 parts by weight with respect to the phosphor powder, and a blue phosphor represented by the chemical formula shown in Table 1 was used. A plasma display was produced in the same manner as in Example 1 except for the above.

(Example 15) Example 15 was carried out except that a slurry in which 5 parts by weight of MgF ₂ having an average particle diameter of 10 nm was dispersed in isopropyl alcohol in advance in preparing phosphor paste was used. A plasma display was produced in the same manner as in Example 1.

Example 18 PMMA was used as the resin for the phosphor paste instead of ethyl cellulose.
A plasma display was produced in the same manner as in Example 15 except that the phosphor layer was baked in a nitrogen atmosphere at 460 ° C. for 15 minutes.

(Comparative Example 1) A plasma display was produced in the same manner as in Example 1 except that the fluoride particles were not added.

(Comparative Examples 2 to 4) Table 1
A plasma display was produced in the same manner as in Example 1 except that the phosphor paste to which the particles as shown in 1 above were added was used.

With respect to Examples 1 to 18 and Comparative Examples 1 to 4, Table 1 shows added particles and their average particle diameters, addition ratios, chemical formulas of blue phosphors, initial light emission characteristics, and retention rates.

[0070]

[Table 1]

Examples 1 to 15 and 17 are Comparative Examples 1 to 3.
On the other hand, the initial light emission characteristics and the retention rate are good. In particular, Example 13 is a display having excellent initial light emission characteristics, high maintenance rate, high reliability, and long life. Comparative Examples 2 and 3 have good retention rates but poor initial light emission characteristics. In Comparative Example 4, the phosphor layer showed conductivity, and it was difficult to display a good result.

[0072]

EFFECTS OF THE INVENTION According to the present invention, since fluoride particles are contained in the phosphor layer, it is possible to provide a highly reliable and long-life plasma display member and a plasma display which can suppress a decrease in emission intensity due to long-time lighting.

[Brief description of drawings]

FIG. 1 is an exploded perspective view of a plasma display.

[Explanation of symbols]

1: Front plate 2: Glass substrate 3: Scan electrode 4: Sustain electrode 5: Bus electrode 6: Transparent dielectric layer 7: MgO protective film 8: Back plate 9: Glass substrate 10: Address electrode 11: Dielectric layer 12: Partition layer 13: Red phosphor layer 14: Green phosphor layer 15: Blue phosphor layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01J 17/04 H01J 17/04

Claims (7)

[Claims] 1. A phosphor paste containing phosphor powder and a resin component, wherein the paste contains fluoride particles. 2. The phosphor paste according to claim 1, wherein 0.1 to 30 parts by weight of the fluoride is included with respect to 100 parts by weight of the phosphor powder. 3. The average particle size of the fluoride is 1 to 30000n.
It is in the range of m, The phosphor paste of Claim 1 characterized by the above-mentioned. 4. Fluoride is LiF, MgF ₂ , CaF ₂ , B
_{aF 2, CeF 4, ThF 4} ,, SrF 2, AlF 3 · 3N
The phosphor paste according to claim 1, containing at least one selected from the group consisting of aF, LiSrAlF ₆ , and LiCaAlF ₆ . 5. The phosphor powder is BaMgAl ₁₀ O ₁₇ : E.
u, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaAl ₁₂
The phosphor paste according to claim 1, which is represented by one of the chemical formulas of O ₁₉ : Mn and (Y, Gd) BO ₃ : Eu. 6. A plasma display member manufactured by using the phosphor paste according to claim 1. 7. A plasma display in which at least an electrode, a dielectric layer, a partition wall, and a phosphor layer are formed, wherein the phosphor layer contains a fluoride.