JP3252829B2 - Plasma display substrate, plasma display, and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma display used for a large television or a computer monitor.

[0002]

2. Description of the Related Art Plasma displays (PDPs) are widely used in fields such as OA equipment and public information display devices because they can display at higher speeds and can be made larger than liquid crystal panels. I have. It is also expected to be used in the field of high-definition television. With the expansion of such uses, color PDPs having fine and large numbers of display cells have attracted particular attention as PDPs.

A PDP generates a plasma discharge between an anode and a cathode located opposite to each other in a discharge space formed between a front glass substrate and a rear glass substrate, and a gas sealed in the space. Display is performed by light emission from

A PDP is formed by laminating a front glass substrate and a rear glass substrate provided with electrodes, a dielectric layer, and the like, respectively. Usually, a plurality of stripe-shaped partitions are formed on the rear glass substrate. A phosphor layer for performing RGB color display is formed in each of the cells formed between the adjacent partition walls. These phosphor layers are usually coated with R (red) light-emitting phosphor, G (green) light-emitting phosphor, and B (blue) light-emitting phosphor in each cell by a screen printing method, and dried, It is formed through a firing step. For higher brightness,
A phosphor screen is also provided by providing a phosphor layer not only on the bottom surface but also on the side surfaces of the cell.

As described above, the cells for displaying RGB are formed between the stripe-shaped partitions, and the partitions are formed at a constant pitch. Therefore, each size of the RGB phosphor layers is the same.

[0006] Currently, red light-emitting phosphors that have been developed include Y ₂ O ₃ : Eu, YVO ₄ : Eu, and (Y, Gd) B.
O ₃ : Eu, Y ₂ O ₃ S: Eu, γ-Zn ₃ (PO ₄ ) ₂ : M
n, (ZnCd) S: Ag + In ₂ O ₃ and the like.

The green light emitting phosphor is Zn_TwoG
eO_Two: Mn, BaAl₁₂O₁₉: Mn, Zn_TwoSiO_Four,
LaPO_Four: Tb, ZnS: Cu, Al, ZnS: A
u, Cu, Al, (ZnCd) S: Cu, Al, Zn_Two
SiO_Four: Mn, As, Y_ThreeA1_FiveO ₁₂: Ce, CeMg
Al₁₁O₁₉: Tb, Gd_TwoO_TwoS: Tb, Y_ThreeA1_FiveO₁₂:
Tb, ZnO: Zn and the like.

Further, as the blue light emitting phosphor, S
r ₅ (PO ₄ ) ₃ Cl: Eu, BaMgAl ₁₄ O ₂₃ : E
u, BaMgAl ₁₆ O ₂₇ : Eu, BaMg ₂ Al
₁₄ O ₂₄ : Eu, ZnS: Ag + red pigment, Y ₂ SiO ₃ :
Ce and the like.

Luminance, emission color, and afterglow are important as emission characteristics of these light emitting phosphors, but few are perfect. In particular, the luminance of the blue light-emitting phosphor is lower than the luminance of the red and green light-emitting phosphors, and there is a problem that a color image with good balance cannot be obtained when displaying in color. The design is done according to the level.

[0010]

SUMMARY OF THE INVENTION The present invention provides a plasma display substrate capable of displaying a well-balanced and brighter color image, a plasma display, and a method of manufacturing the same.

In the conventional plasma display, since the partition having the same constant pitch and width is used, R
The cells of the respective colors of GB have the same size, and in order to improve the balance of color display, the luminance is adjusted to the blue light emitting phosphor at the lowest level. Therefore, the abilities of the red and green light emitting phosphors are not sufficiently exhibited. In order to obtain a brighter screen, improvement of a blue light-emitting phosphor having high luminance is being studied, but a material having the same level of luminance as that of the red and green light-emitting phosphors has not yet been developed.

In addition, when the light is emitted from the entire surface, the luminance of blue becomes low, and the entire screen becomes yellowish. For this reason, there is a problem that a beautiful white color shown by a cathode ray tube or the like cannot be reproduced.

The present invention improves the brightness of a blue light-emitting phosphor on a color screen, makes the red and green light-emitting phosphors exhibit more brightness, and makes the entire color image brighter. The purpose is to realize beautiful white color on the screen.

[0014]

To achieve the above object, a plasma display according to the present invention has the following arrangement.

[0015] In a plasma display substrate, a phosphor layer for emitting each color of RGB is formed in a stripe shape on a glass substrate, and a partition wall for partitioning the RGB phosphor layer is formed. When the distance between the formed partition walls is Pr and the distance between the partition walls where the B phosphor layer is formed is Pb, the relationship of Pb> Pr is satisfied, and Sr ₅ (PO ₄ )
₃ Cl: Eu, BaMgAl ₁₄ O ₂₃ : Eu, BaMgA
l ₁₆ O ₂₇ : Eu, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Zn
S: Ag + red pigment, Y ₂ SiO ₃ : Ce, (Ba, E
u) A substrate for a plasma display, wherein at least one kind of phosphor selected from MgAl ₁₀ O ₁₇ is used.

Further, the plasma display according to the present invention has a front substrate in which electrodes, a dielectric and a protective film are formed on a glass substrate, and a rear substrate in which electrodes, dielectrics, partitions, and a phosphor are formed on a glass substrate. A phosphor layer that emits each color of RGB is formed in a stripe shape on a glass substrate;
In a plasma display substrate on which partition walls for partitioning the phosphor layer are formed, the distance between the partition walls on which the R phosphor layer is formed is Pr, and the distance between the partition walls on which the B phosphor layer is formed is Pb. At this time, the relationship of Pb> Pr is satisfied, and Sr ₅ (PO ₄ ) is added to the B phosphor layer.
₃ Cl: Eu, BaMgAl ₁₄ O ₂₃ : Eu, BaMgA
l ₁₆ O ₂₇ : Eu, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Zn
S: Ag + red pigment, Y ₂ SiO ₃ : Ce, (Ba, E
u) A plasma display substrate using at least one or more phosphors selected from MgAl ₁₀ O ₁₇ is used as a back substrate.

Further, the method for manufacturing a plasma display substrate according to the present invention for manufacturing the plasma display substrate according to the present invention includes the steps of:
After a step of applying a photosensitive paste, a step of performing pattern exposure, and a step of removing a portion dissolved in a developer by development, baking is performed at 450 ° C. to 620 ° C.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The height of a partition wall of a plasma display is suitably from 80 μm to 200 μm. The pitch (P) of the partition walls is often 100 μm ≦ P ≦ 500 μm. For a high-definition plasma display, the pitch (P) of partition walls is 100 μm ≦ P ≦ 250 μm.
m, and the line width (L) is preferably 10 μm ≦ L ≦ 50 μm. Such a high-definition partition wall can be formed by a sand blast method or a photosensitive paste method, but the latter photosensitive paste method is more preferable.

As a material for forming the partition wall, a glass material containing an oxide of silicon and / or boron as an essential component is preferably used.

Conventionally, the partition walls are formed in a stripe shape at a constant pitch, and phosphors emitting light of each of RGB colors are applied to cells formed between adjacent stripe-shaped partition walls for color display. Color pixels are formed. In other words, pixels having one set of three colors of RGB are arranged in a stripe pattern at a constant pitch. For example, if the pitch of the partition walls is 150 μm, all the light emitting regions of RGB are formed with the same size at the pitch of this value.

At present, KX-504A is used for red light emission and P is used for green light emission.
For 1-G1S and blue light emission, there is KX-501A (both manufactured by Kasei Optonics Co., Ltd.). Among these phosphors, blue light emitting phosphor KX-501A (composition: (B
a, Eu) MgAl ₁₀ O ₁₇ ) has a light emission luminance of red light-emitting phosphor KX-504A (composition: (Y, Gd, Eu) B
O ₃ ) or green light-emitting phosphor P1-G1S (composition: (Z
n, Mn) ₂ SiO ₄ ), which is １ ／ to レ ベ ル the level.

Conventionally, since there is a difference in luminance between the phosphors of the respective colors as described above, the difference in luminance is matched in cells of the same size. In this case, the emission luminance of red and green is adjusted. The problem was that they were not fully utilized.

In the substrate for a plasma display of the present invention, the difference in emission luminance between the red phosphor layer and the blue phosphor layer is particularly problematic, and the distance between the partition walls of the cell in which the blue phosphor layer is formed is problematic. It has been found that by making Pb larger than the distance Pr between the partitions of the cell where the red phosphor layer is formed, the overall luminance level can be increased and the color image can be made brighter. Furthermore, by making Pb larger than the distance Pg between the partitions of the cell where the green phosphor layer is formed, the overall luminance level can be further increased.

Further, by having the relationship of 1 <Pb / Pr ≦ 2, the problem that the emission luminance of blue is low and the problem that the luminance of red is high and the color temperature is easily lowered can be simultaneously solved. Further, by having a relationship of 1 <Pb / Pg ≦ 2, the luminance of blue can be further improved. In addition, by having a relationship of 1 <Pg / Pr ≦ 2, it is possible to manufacture a plasma display in which the luminance of green with high luminosity of the eyes is increased and the emission luminance perceived by the eyes is further increased.

By setting the difference between Pb and Pr to 5 μm to 200 μm, and more preferably 5 μm to 100 μm, the characteristics of the red phosphor which emits light strongly and the characteristics of the blue phosphor which emits light are balanced, and the luminance and the color balance are improved. It is preferable because an excellent plasma display can be obtained. Also,
Similarly, the difference between Pb and Pg is preferably 5 μm to 200 μm, more preferably 5 μm to 100 μm.

When the difference is too small, a sufficient effect of improving the brightness cannot be obtained as compared with the conventional case. On the other hand, if the difference is too large, the difference between the discharge spaces in which the respective RGB light is emitted becomes too large, so that driving becomes difficult.

For example, assuming that partition walls having a pitch of 150 μm are formed at equal intervals, to implement the present invention, Pb = 200 μm and Pr = Pg = 125 μm
Is possible. The difference in the distance between the partitions in this case is 75 μm. Higher luminance can be obtained compared to a phosphor layer formed at a pitch of 150 μm at equal intervals, so that it is possible to design a drive circuit that increases the luminance of other phosphors in accordance with the higher luminance, and a brighter color image can be obtained. It becomes possible to obtain a plasma display.

The substrate for a plasma display of the present invention comprises:
It can be manufactured by forming an electrode formed of silver, copper, or chromium, and forming a partition wall and a phosphor layer emitting light of each color of RGB on a dielectric made of a glass component.

The formation of such partition walls is performed using a photosensitive paste containing an organic component containing inorganic fine particles and a photoreactive compound as an essential component, thereby simplifying the manufacturing process and achieving high-precision pattern processing. It is preferable because it can be used.

As the inorganic fine particles, glass, ceramic (alumina, cordierite, etc.) and the like are preferable because of their excellent transparency. In particular, glass and ceramics containing silicon oxide, boron oxide, or aluminum oxide as an essential component are preferable.

The particle size of the inorganic fine particles is selected in consideration of the shape of the pattern to be produced. The volume average particle size (D50) is preferably 1.5 μm or more from the viewpoint of pattern formation, preferably 2 μm. More preferably, it is the above. However, when D50 is 10 μm or more, the surface becomes uneven during pattern formation, so that D50 is 1.5 to 1.5 μm.
It is preferably 10 μm, more preferably 2 to
8 μm. It is particularly preferable to use glass fine particles having a specific surface area of 0.2 to ³ m ² / g in pattern formation.

By using inorganic fine particles having a spherical shape as the inorganic fine particles, patterning with a high aspect ratio becomes possible. Specifically, the sphericity is preferably 80% by number or more. More preferably, the average particle size is 1.5 μm to 4 μm, the specific surface area is 0.5 to 1.5 m
² / g and sphericity of 90% by number or more. Here, the sphericity is a ratio of particles having a spherical or elliptical shape in a microscope observation, and is observed as a circle or an ellipse in an optical microscope.

Since the partition walls are patterned on a glass substrate having a low thermal softening point, it is preferable to use inorganic fine particles containing at least 60% by weight of glass fine particles having a thermal softening temperature of 350 ° C. to 600 ° C. as the inorganic fine particles. . By adding glass fine particles or ceramic fine particles having a heat softening temperature of 600 ° C. or more, the shrinkage rate during firing can be suppressed, but the amount is preferably 40% by weight or less.

By using glass particles having a high light transmittance, a pattern with a more accurate shape can be obtained. As the glass fine particles having a high light transmittance used in this case, the glass fine particles are melted to produce a glass plate having a thickness of 40 μm, and then the wavelength of the light to be exposed, particularly 365
nm, 405 nm, 429 nm, 436 nm, 488 n
The light transmittance at any wavelength of m is measured, and the total light transmittance is preferably 70% or more, more preferably 80% or more.

In order to prevent the glass substrate from warping during firing, the linear expansion coefficient should be 50 to 90 × 10 ⁻⁷ ,
Further, it is preferable to use glass fine particles of 60 to 90 × 10 ⁻⁷ .

As the composition in the glass fine particles, silicon oxide is preferably blended in the range of 3 to 60% by weight, and when less than 3% by weight, the denseness, strength and stability of the glass layer are reduced. In addition, the thermal expansion coefficient deviates from a desired value, and a mismatch with a glass substrate is likely to occur. Further, by setting the content to 60% by weight or less, there is an advantage that the heat softening point is lowered and baking on a glass substrate becomes possible.

By mixing boron oxide in the range of 5 to 50% by weight, electrical insulation, strength, coefficient of thermal expansion,
Electrical, mechanical, and thermal properties such as the denseness of the insulating layer can be improved. If it exceeds 50% by weight, the stability of the glass will decrease.

By using glass fine particles containing at least one of bismuth oxide, lead oxide and zinc oxide in an amount of 5 to 50% by weight, such glass fine particles have a temperature characteristic that enables pattern processing on a glass substrate. A glass paste can be obtained. In particular, when glass particles containing 5 to 50% by weight of bismuth oxide are used, advantages such as long pot life of the paste can be obtained.

As the bismuth-based glass fine particles, it is preferable to use a glass powder having the following composition. Bismuth oxide: 10 to 40 parts by weight Silicon oxide: 3 to 50 parts by weight Boron oxide: 10 to 40 parts by weight Barium oxide: 8 to 20 parts by weight Aluminum oxide: 10 to 30 parts by weight Lithium oxide, sodium oxide, potassium oxide Among them, glass fine particles containing at least one kind in an amount of 3 to 20% by weight may be used, but in this case, the addition amount of an oxide of an alkali metal such as lithium, sodium, and potassium is 2%.
When the content is 0% by weight or less, preferably 15% by weight or less, the stability of the paste can be improved.

In this case, as specific glass fine particles, it is preferable to use glass powder having the following composition. Lithium oxide: 2 to 15 parts by weight Silicon oxide: 15 to 50 parts by weight Boron oxide: 15 to 40 parts by weight Barium oxide: 2 to 15 parts by weight Aluminum oxide: 6 to 25 parts by weight In the above composition, instead of lithium oxide Alternatively, sodium oxide or potassium oxide may be used, but lithium oxide is preferred from the viewpoint of paste stability.

Further, when glass fine particles containing both a metal oxide such as lead oxide, bismuth oxide and zinc oxide and an alkali metal oxide such as lithium oxide, sodium oxide and potassium oxide are used, a lower alkali content is obtained. The amount can easily control the thermal softening temperature and the coefficient of linear expansion.

Further, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide and the like, especially aluminum oxide, barium oxide and zinc oxide to the glass fine particles, the workability is improved. From the viewpoint of controlling the thermal softening point, the thermal expansion coefficient and the refractive index, the content is preferably 40% by weight or less, more preferably 2% by weight or less.
5% by weight or less.

Generally, glass used as an insulator has a refractive index of about 1.5 to 1.9. When the average refractive index of the organic component is significantly different from the average refractive index of the inorganic fine particles, reflection and scattering at the interface between the inorganic particles and the photosensitive organic component are increased, and the total light transmittance and the straight transmittance are improved. And it is difficult to obtain a pattern with a high aspect ratio and high accuracy.

The refractive index of a general organic component is 1.45 to
Since it is 1.7, in order to match the refractive index of the inorganic fine particles and the organic component, the average refractive index of the inorganic particles should be 1.5 to 1.5.
It is preferably 1.75. More preferably, by setting the refractive index to 1.5 to 1.65, there is an advantage that the range of selection of the organic component is widened.

When glass or ceramic containing a large amount of boron oxide or silicon oxide is used as the inorganic fine particles,
Since the refractive index is relatively small, as an organic component, 1.5 to
The use of 1.6 allows the refractive index to be more easily matched.

However, glass fine particles containing lead oxide, bismuth oxide, and zinc oxide are often used as the fine glass particles used for forming the pattern of the partition walls of the plasma display, since firing on a glass substrate is required. However, glass containing these metals has a refractive index of 1.
Often it is 65 or more.

Therefore, there is a method of adjusting the contents of lead oxide, bismuth oxide and zinc oxide to 5 to 16% by weight.
By using glass microparticles containing a total of 5 to 20% by weight of alkali metal oxides such as lithium oxide, sodium oxide and potassium oxide, the average refractive index can be easily controlled, and thermal softening that can be printed on a glass substrate It has a temperature and an average refractive index of 1.5 to 1.65, which makes it easy to reduce the difference in the refractive index from the organic component.

The organic component used in the photosensitive paste is an organic component in the paste containing a photosensitive organic substance (a part obtained by removing the inorganic component from the paste).

The organic component also preferably has a high light transmittance. Wavelength of light to be exposed, in particular, 365 nm,
The total light transmittance at a thickness of 40 μm measured at any one of the wavelengths of 405 nm, 420 nm, 436 nm, and 488 nm is preferably 70% or more.

The organic component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and, if necessary, a binder, a photopolymerization initiator, and a photopolymerization initiator. Add additives such as absorbers, sensitizers, sensitization aids, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, organic or inorganic precipitation inhibitors and leveling agents. Is also performed.

As the photosensitive component, there are a photo-insolubilizing type and a photo-solubilizing type, and the following (A) to (E) are typical.

The photo-insolubilized type includes (A) a functional monomer, an oligomer, and a polymer having at least one unsaturated group in the molecule, (B) an aromatic diazo compound, an aromatic azide There is a so-called diazo resin such as a compound containing a photosensitive compound such as a compound or an organic halogen compound, or a condensate of (C) a diazo-based amine and formaldehyde.

As the photo-solubilizing type, (D) a complex of a diazo compound with an inorganic salt or an organic acid, a compound containing a quinone diazo compound, or (E) a quinone diazo compound combined with an appropriate polymer binder. For example, there is a naphthoquinone-1,2-diazide-5-sulfonic acid ester of a phenol novolak resin.

As the photosensitive component used in the present invention, all of the above can be used. As the photosensitive component that can be easily used as a photosensitive paste by mixing it with inorganic fine particles, those described in (A) above are preferable.

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond. Specific examples thereof include monofunctional and polyfunctional (meth) acrylates, vinyl compounds, allyl compounds. Etc. can be used. These can be used alone or in combination of two or more.

In addition to these, the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

Also, an oligomer or polymer obtained by polymerizing at least one kind of a compound having a carbon-carbon double bond can be used. At the time of polymerization, these monomers can be copolymerized with other photosensitive monomers such that the content of these monomers is at least 10% by weight, more preferably at least 35% by weight.

By copolymerizing an unsaturated acid such as an unsaturated carboxylic acid, the developability after exposure can be improved. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. The acid value (AV) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably in the range of 50 to 180.
The range of 0 to 140 is more preferable.

By adding a photoreactive group to a side chain or a molecular terminal to the above-mentioned polymer or oligomer, it can be used as a photosensitive polymer or a photosensitive oligomer having photosensitivity. Preferred photoreactive groups are
It has an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

The addition of such a side chain to an oligomer or a polymer may be carried out by adding an ethylenically unsaturated compound having a glycidyl group or an isocyanate group to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer, or acrylic acid chloride. , Methacrylic acid chloride or allyl chloride.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl ether crotonic acid and glycidyl ether isocrotonic acid. .

Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate. The ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is used in an amount of 0.05 to 1 mol based on the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add an equal amount.

As the binder, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate ester
Examples include methacrylate copolymers, α-methylstyrene polymers, and butyl methacrylate resins.

Specific examples of the photopolymerization initiator include benzophenone, methyl O-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, and 4,4-dichlorobenzophenone. , 4-benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone , Pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketal, benzylmethoxyethylacetal, benzoy Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-
t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone, 4
-Azidobenzalacetophenone, 2,6-bis (p-
(Azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-
Methoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime,
1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenyl Thioacridone, 4,
4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide, and eosin, a photoreducing dye such as methylene blue Examples include a combination of reducing agents such as ascorbic acid and triethanolamine.

In the present invention, one or more of these can be used. The photopolymerization initiator is preferably added in the range of 0.05 to 10% by weight, more preferably in the range of 0.1 to 5% by weight, based on the photosensitive component. If the amount of the polymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

It is also effective to add a light absorbing agent. By adding a compound having a high effect of absorbing ultraviolet light or visible light, a high aspect ratio, high definition, and high resolution can be obtained.

As the light absorber, those comprising an organic dye are preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, diphenyl dyes A cyanoacrylate dye, a triazine dye, a p-aminobenzoic acid dye, or the like can be used. The organic dye is preferable because it does not remain in the insulating film after firing even when added as a light absorber, so that the deterioration of the insulating film characteristics due to the light absorber can be reduced. Among these,
Azo and benzophenone dyes are preferred.

The addition amount of the organic dye is 0.05 to 5% by weight.
Is preferred. When the content is less than 0.05% by weight, the effect of adding the light absorber is reduced, and when it exceeds 5% by weight, the properties of the insulating film after firing are deteriorated. More preferably, 0.
0.5 to 1% by weight.

As an example of the method of adding the light absorbing agent comprising an organic dye, a method in which a solution in which an organic dye is dissolved in an organic solvent in advance is prepared and kneaded at the time of preparing a paste, There is a method of drying after mixing the inorganic fine particles. By this method, a so-called capsule-like powder in which the surface of each of the inorganic fine particles is coated with an organic film can be produced.

A sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone,
2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone,
4,4-bis (diethylamino) benzophenone, 4,
4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole,
1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethyl Ethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-
5-ethoxycarbonylthiotetrazole and the like. One or more of these can be used.

Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

To adjust the viscosity of the solution, an organic solvent may be added to the photosensitive paste. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ
-Butyl lactone, bromobenzene, chlorobenzene,
Dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing at least one of them are used.

The refractive index of the organic component is the refractive index of the organic component in the paste at the time when the photosensitive component is exposed to light. In other words, when the paste is applied and the exposure is performed after the drying step, it refers to the refractive index of the organic component in the paste after the drying step. For example, there is a method of applying a paste on a glass substrate, drying the paste at 50 to 100 ° C. for 1 to 30 minutes, and measuring the refractive index.

The refractive index of the organic component is 1.5 to 1.
It is preferably in the range of 65, more preferably
1.5 to 1.6. In particular, when the average refractive index of the glass fine particles is in the range of 1.55 to 1.65 and the average refractive index of the organic component is 1.5 to 1.6, the range of selection of the glass fine particles and the organic component is widened, There is an advantage that the straight transmittance can be easily improved.

However, glass powder containing 10% by weight or more of bismuth oxide or lead oxide, which can be baked on a glass substrate, may have a refractive index of 1.6 or more. Needs to have a high refractive index. In this case, it is necessary to introduce a high refractive index component into the organic component, and a compound having a sulfur atom, a bromine atom, an iodine atom, a naphthalene ring, a biphenyl ring, an anthracene ring, and a carbazole ring in the organic component is 10% by weight or more. It is effective to increase the refractive index. However, depending on the type of these compounds, the transmittance may decrease due to light absorption, so that the content is preferably 20% by weight or less. Further, by containing a benzene ring in an amount of 20% by weight or more, a high refractive index can be obtained. In particular, by including a sulfur atom or a naphthalene ring in an amount of 10% by weight or more, the refractive index of the organic component can be more easily increased. However, if the content is 60% by weight or more, a problem occurs in that the photosensitivity is reduced. Therefore, the total content of the sulfur atom and the naphthalene ring is preferably in the range of 10 to 60% by weight.

As a method for increasing the refractive index of the organic component, it is effective to use a compound having a sulfur atom and a naphthalene ring in a photosensitive monomer or a binder.

The photosensitive paste is usually composed of inorganic fine particles, a light absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator,
After blending various components such as a glass frit and a solvent so as to have a predetermined composition, the mixture is uniformly mixed and dispersed with a three-roller or a kneader to produce.

The viscosity of the paste is determined by using inorganic fine particles, a thickener,
It is appropriately adjusted by the addition ratio of the organic solvent, the plasticizer, the precipitation inhibitor and the like, and the range is from 2000 to 200,000 cps (centipoise). For example, when the coating on the glass substrate is performed by a spin coating method other than the screen printing method, 200 to 5000 cps is preferable. In order to obtain a film thickness of 10 to 20 μm by applying once by a screen printing method, 50,000 to 200,000 cps is preferable. When a blade coater method, a die coater method, or the like is used, 2000 to 2
0000 cps is preferred.

The formation of the partition walls using the photosensitive paste is performed as follows. A photosensitive paste is applied to a glass substrate. As a coating method, a general method such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste.

Here, when the paste is applied on a glass substrate, a surface treatment of the glass substrate can be performed in advance in order to enhance the adhesion between the glass substrate and the coating film.
As the surface treatment liquid, a silane coupling agent, for example,
Vinyltrichlorosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ -Chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or the like, or an organic metal such as organic titanium, organic aluminum,
Organic zirconium and the like. A silane coupling agent or an organic metal is used as an organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and the like.
It is preferable to use those diluted to a concentration of ５5%.
Next, the surface treatment liquid is uniformly applied on a glass substrate with a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to complete the surface treatment.

After the application of the photosensitive paste, exposure is performed using an exposure device. The exposure is generally performed by a mask exposure using a photomask, as is performed by ordinary photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Alternatively, a method of directly drawing with a laser beam or the like without using a photomask may be used.

When exposing using a photomask, a photomask having openings corresponding to the pitch of the partition walls is used. In this case, a predetermined value difference is produced between the partition walls for applying phosphors of RGB colors. By exposing to light, a partition wall satisfying the requirements of the present invention can be formed.

As an exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. Also,
In the case of performing exposure in a large area, a large area can be exposed by an exposure machine having a small exposure area by applying a photosensitive paste on a glass substrate and performing exposure while transporting the photosensitive paste.

The active light source used at this time includes, for example, visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, laser light and the like. Of these, ultraviolet rays are most preferred,
As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a germicidal lamp, and the like can be used. Among these, an ultra-high pressure mercury lamp is preferred. Exposure conditions vary depending on the coating thickness, but 1 to 100 mW /
Exposure is performed for 0.5 to 30 minutes using an ultra-high pressure mercury lamp having an output of cm ² .

By providing an oxygen blocking film on the surface of the applied photosensitive paste, the pattern shape can be improved. As an example of the oxygen barrier film, a film such as polyvinyl alcohol or cellulose, or a film such as polyester can be given.

The polyvinyl alcohol film is formed by uniformly applying an aqueous solution having a concentration of 0.5 to 5% by weight on a substrate by a method such as a spinner, and then applying the aqueous solution at 70 to 90 ° C. for 10 minutes.
This is done by evaporating the water by drying for ~ 60 minutes. At this time, it is preferable to add a small amount of alcohol to the aqueous solution because the wettability is improved and the evaporation is facilitated.
More preferred solution concentration of polyvinyl alcohol is 1
３3% by weight. Within this range, the sensitivity is further improved. The reason why the sensitivity is improved by applying polyvinyl alcohol is presumed to be as follows. That is, when the photosensitive component undergoes a photoreaction, it is estimated that oxygen in the air interferes with the reaction. For this reason, the presence of a polyvinyl alcohol film can block excess oxygen, thereby improving sensitivity during exposure. It is considered that the presence of the polyvinyl alcohol film is preferable.

When a transparent film of polyester, polypropylene, polyethylene, or the like is used, there is a method in which these films are attached to the photosensitive paste after application.

After exposure, development is carried out by utilizing the difference in solubility between the exposed part and the non-exposed part in the developing solution.
It is performed by a dipping method, a spray method, or a brush method.

As the developer, an organic solvent in which the organic components in the photosensitive paste can be dissolved is used. In addition, water may be added to the organic solvent as long as its solvent power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkali aqueous solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkali aqueous solution since the alkali component can be easily removed at the time of firing.

As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not good. The development temperature during development is 20 to 50 ° C.
Is preferably performed in terms of process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The firing temperature is 400-1000 ° C
Do with. When processing a pattern on a glass substrate, 45
The sintering is performed at a temperature of 0 to 620 ° C. for 10 to 60 minutes.

After the formation of the partition walls, a phosphor layer which emits light of each color of RGB is formed. A phosphor layer can be formed by forming a phosphor paste containing a phosphor powder, an organic binder, and an organic solvent as main components between predetermined partition walls. As a method of forming the phosphor paste between predetermined partitions, a method of pattern printing by a screen printing method or a method of forming the phosphor paste by discharging the phosphor paste between predetermined partitions from a die having discharge holes of a predetermined pitch is used. Can be used. In addition, by using the above-described organic component having photosensitivity as the organic binder, a photosensitive phosphor paste can be prepared, and a phosphor layer of each color can be formed at a predetermined position by a photolithography method.

When the thickness of the R phosphor layer is Tr, the thickness of the G phosphor layer is Tg, and the thickness of the B phosphor layer is Tb, 10 μm ≦ Tr <Tb ≦ 50 μm 10 μm ≦ Tg <Tb ≦ 50 μm By having the relationship, the effect of the present invention can be more exhibited. In other words, a plasma display having a better color balance (higher color temperature) can be manufactured by not only increasing the application area but also making the thickness thicker than that of green and red for blue light with low emission luminance. If the thickness of the phosphor layer in this case is less than 10 μm, it is difficult to obtain sufficient luminance. The thickness is 50μ.
When the thickness is larger than m, a problem arises that the discharge space is narrowed and the luminance is likely to be reduced. In this case, the thickness of the phosphor layer is measured as a thickness formed at an intermediate point between adjacent partition walls. That is, it is measured as the thickness of the phosphor layer formed at the bottom of the discharge space (in the cell).

The substrate on which the phosphor layer is formed is baked at 400 to 550 ° C., if necessary, to produce the substrate for a plasma display of the present invention.

The plasma display substrate and the front substrate, that is, transparent electrodes, bus electrodes,
After sealing a glass substrate on which a dielectric and a protective film (MgO) are formed, a discharge gas composed of helium, neon, xenon, or the like is filled in a space formed between the substrates, and a drive circuit is mounted. A plasma display can be manufactured.

[0096]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 A solvent (γ-butyl lactone) and a photosensitive polymer were mixed so as to form a 40% solution of the photosensitive polymer, and heated to 60 ° C. with stirring to dissolve all the polymers homogeneously. I let it. The photosensitive polymer has a weight-average molecular weight of 4 in which 0.4 equivalent of glycidyl methacrylate is added to the carboxyl group of a copolymer consisting of 40% methacrylic acid, 30% methyl methacrylate and 30% styrene.
It is a polymer having a 3,000 acid value of 95. Next, the solution was cooled to room temperature, and a photosensitive monomer, a photopolymerization initiator, a sensitizer and the like were added and dissolved. Thereafter, this solution was filtered using a 400-mesh filter to prepare a photosensitive organic component. Photosensitive monomer, photoinitiator used in this example,
The sensitizer is the following compound. Photosensitive monomer: Compound obtained by adding 4 mol of glycidyl methacrylate to 1 mol of xylylenediamine Photoinitiator: 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butanone-1 Sensitizer: 2,4-diethylthioxanthone.

Next, sudan, an azo organic dye, was weighed at a rate of 0.10% with respect to the glass powder. Sudan was dissolved in acetone, a dispersing agent was added thereto, and the mixture was stirred homogeneously with a homogenizer. Glass powder was added to the solution, homogeneously dispersed and mixed, and then mixed with a rotary evaporator.
Dry at a temperature of 200 ° C. and evaporate the acetone. In this way, a powder in which the surface of the glass powder was uniformly coated with a film of an ultraviolet absorber composed of an organic dye (so-called capsule treatment) was produced.

The glass powder used here was Li ₂ O: 9
%, SiO ₂ : 22%, B ₂ O ₃ : 33%, BaO: 4
%, Al ₂ O ₃ : 23%, ZnO: 2%, MgO: 7%. The glass powder is finely divided in advance with an attractor and has an average particle size of 2.6 μm and a refractive index of 1.58.

The above-mentioned organic component and the glass powder to which the ultraviolet absorber was added were mixed in a proportion of 60 parts by weight of the glass powder, 25 parts by weight of the photosensitive organic component (excluding the solvent), and 15 parts by weight of the solvent (γ-butyl lactone). Were added and mixed and dispersed with three rollers to prepare a photosensitive paste.

On a glass substrate having a stripe-shaped data electrode and a dielectric layer formed at intervals corresponding to the difference in the distance between the partitions forming the phosphor layer, a thickness of 180 μm after drying is obtained by a slit die coater using a slit die coater. After applying the photosensitive paste as described above, it was dried at 80 ° C. for 1 hour.

Next, exposure was performed through a photomask. The mask has a pitch between the partition walls on which the B phosphor layers are formed is 260 μm, a pitch between the partition walls on which the R phosphor layer and the G phosphor layer are formed is 200 μm, and the line width of the partition walls is 30 μm.
This is a chrome mask designed to be able to form a striped partition pattern in a plasma display having a thickness of μm. Exposure was performed using an ultra-high pressure mercury lamp having an output of 50 mW / cm ² to perform 15 J / cm ² ultraviolet exposure. Then, it was developed by immersing it in a 1% aqueous solution of monoethanolamine.

The glass substrate obtained by patterning the photosensitive paste was dried at 120 ° C. for 1 hour, and baked at 560 ° C. for 1 hour. The firing caused shrinkage of about 20%.

An RGB phosphor was applied by a screen printing method on a substrate on which electrodes, dielectrics, and partition walls were formed, and dried and fired to form a phosphor layer. The phosphor was applied not only on the bottom surface but also on the side surfaces of the partition walls to form phosphor screens on the bottom surface and the side surfaces.

After the rear glass substrate thus formed is combined with a separately prepared front glass substrate, sealing is performed.
Gas filling was performed, a driving circuit was joined, a plasma display was manufactured, and a voltage was applied to perform display.

When the obtained blue light emission luminance was measured,
It was confirmed that the emission luminance of the plasma display of Comparative Example 1 was about 10% higher than that of the plasma display, and that the entire panel display displayed a beautiful white color in blue when the entire display was illuminated.

The color temperature without color correction by the driving circuit was 10,000 degrees, which proved to be excellent in display products.

Example 2 As a photomask, the pitch between the partition walls where the B phosphor layers are formed is 260 μm, the pitch between the partition walls where the G phosphor layers are formed is 240 μm, and the pitch between the partition walls where the R phosphor layers are formed. A plasma display was manufactured in the same manner as in Example 1, except that a chromium mask designed to enable formation of a stripe-shaped partition pattern in a plasma display having a partition width of 30 μm and a line width of 30 μm was used. Display was performed by applying a voltage.

When the obtained blue light emission luminance was measured,
It was confirmed that the emission luminance of the plasma display of Comparative Example 1 was higher than that of the plasma display by about 15%, and that the entire panel display displayed a beautiful white color in blue when the entire panel was illuminated.

Further, the color temperature without color correction by the drive circuit was 12000 ° C., which proved to be excellent in display products.

Comparative Example 1 As a photomask, an R phosphor layer, a G phosphor layer and a B phosphor layer were used.
Except for using a chromium mask designed to be able to form a stripe-shaped partition pattern in a plasma display in which the pitch between partition walls on which the phosphor layers are formed is all 220 μm and the line width of the partition walls is 30 μm. 1
In the same manner as in the above, a plasma display was manufactured, and a voltage was applied to perform display. The color temperature without the color correction by the drive circuit was 4000 degrees.

[0112]

According to the plasma display of the present invention, it is possible to solve the problem of the conventional plasma display that the red and green light-emitting phosphors do not exhibit the full capability compared to the blue light-emitting phosphor. This makes it possible to use the luminance capabilities of the light emitting phosphors almost equally, to display a well-balanced and brighter color image, and to provide a beautiful white image when the entire surface is illuminated, which is the conventional plasma display. The problem that display is difficult is solved, and a beautiful white image can be displayed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01J 9/02 H01J 9/02 F (56) References JP-A-11-54047 (JP, A) JP-A-10-308179 ( JP, A) JP-A-8-190869 (JP, A) JP-A-9-115466 (JP, A) JP-A-10-247458 (JP, A) JP-A-1-181074 (JP, U) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) H01J 11/02 H01J 9/02

Claims (6)

(57) [Claims] 1. A plasma display substrate comprising a glass substrate, on which a phosphor layer emitting each of RGB colors is formed in a stripe shape, and a partition wall for partitioning the RGB phosphor layer is formed. When the distance between the partition walls where the layer is formed is Pr and the distance between the partition walls where the B phosphor layer is formed is Pb, there is a relationship of Pb> Pr, and Sr ₅ ( PO ₄ )
₃ Cl: Eu, BaMgAl ₁₄ O ₂₃ : Eu, BaMgA
l ₁₆ O ₂₇ : Eu, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Zn
S: Ag + red pigment, Y ₂ SiO ₃ : Ce, (Ba, E
u) A substrate for a plasma display, wherein at least one kind of phosphor selected from MgAl ₁₀ O ₁₇ is used. 2. The method according to claim 1, wherein the (B, Eu) MgAl ₁₀
Plasma display substrate of claim 1, wherein the use of O _17. 3. The distance Pr between the partitions on which the R phosphor layers are formed and the distance Pg between the partitions on which the G phosphor layers are formed have a relationship of 1 <Pg / Pr ≦ 2. Item 3. The substrate for a plasma display according to item 1 or 2 . 4. The thickness of the R phosphor layer is Tr, the thickness of the G phosphor layer is Tg, and the thickness of the B phosphor layer is T.
when it is b, a plasma display substrate according to claim 1 or 2 having a 10μm ≦ Tr <Tb ≦ 50μm 10μm ≦ Tg <Tb ≦ 50μm the relationship. 5. A front substrate having an electrode, a dielectric and a protective film formed on a glass substrate, and an electrode, a dielectric, and a
A plasma display comprising a rear substrate on which partitions and phosphors are formed, wherein the plasma display substrate according to any one of claims 1 to 4 is used as a rear substrate. 6. A step of applying a photosensitive paste on a glass substrate, a step of performing pattern exposure, and a step of removing a portion dissolved in a developing solution by development, and then performing the process at 450 ° C.
The method for producing a plasma display substrate according to any one of claims 1 to 4 , wherein the partition walls are formed by firing at a temperature of from 620 to 620C.