JPH11126560A - Manufacture of plasma display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing plasma displays by which a phosphor layer is not formed on the upper faces of barrier ribs and phosphor layers are formed without mixing colors. SOLUTION: This method for manufacturing plasma displays comprises the process of forming at least an electrode layer and barrier rib layers on a glass substrate and then the process of forming phosphor layers by application process of applying photosensitive phosphor pastes, drying process, exposure process, developing process, and baking process. A photomask having groove width [S] of the barrier ribs and pattern width [L] satisfying 5<=S-L<=50 μm is employed in the exposure process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel plasma display manufacturing method.

[0002]

2. Description of the Related Art Plasma displays (hereinafter referred to as PDPs) are capable of displaying images at a higher speed and larger in size than liquid crystal panels. I have. Further, progress in the field of high-definition television is highly expected.

With the expansion of such applications, attention has been paid to color PDPs having a large number of fine display cells. P
DP generally causes plasma discharge between an anode and a cathode facing each other in a discharge space provided between a front glass substrate and a rear glass substrate, and emits light from a gas sealed in the discharge space. In the case of a color PDP, a phosphor layer is formed between cells in order to perform red, green, and blue color display. This phosphor layer is usually formed by applying a red, green, and blue photosensitive phosphor paste by a screen printing method, followed by drying and baking steps.

Also, a method of performing screen printing as disclosed in JP-A-6-5205 and then using sandblasting, and a method of applying a cross-linking agent and screen-printing as disclosed in JP-A-5-144375 However, all use screen printing.

However, in the ordinary screen printing method, especially when the panel size is increased or when the pitch of the partition walls is narrowed due to the high definition, the positions of the partition walls formed on the back plate in advance and the printing location of the phosphor paste are changed. Since the alignment is very difficult and the positional accuracy cannot be obtained, a phosphor layer is often formed up to the upper surface of the partition wall, or the phosphor layer is mixed with the adjacent phosphor in many cases. In addition, since this operation is performed for each color, there is a problem that the yield is low.

[0006] With the increase in the area of the PDP and the increase in the resolution, the method of forming the phosphor layer by the screen printing technique makes the production of a high-definition phosphor layer technically more difficult and disadvantageous in cost. It is becoming.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the above-mentioned problems of the prior art, and to provide a PDP in which no phosphor layer is formed on the upper surface of the partition wall and a phosphor layer without color mixture can be formed. It is to provide a manufacturing method of.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to form at least an electrode layer and a partition layer on a glass substrate,
A method for producing a PDP in which a phosphor layer is formed through a step of applying a photosensitive phosphor paste, a drying step, an exposure step, a development step, and a baking step, wherein the groove width [S] of the partition wall and the pattern in the exposure step This can be achieved by a PDP manufacturing method characterized by using a photomask whose width [L] satisfies the following expression.

5 ≦ SL ≦ 50 [μm]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The method of manufacturing a PDP of the present invention comprises a step of forming an electrode layer and a partition layer on a glass substrate, and then applying a photosensitive phosphor paste to an arbitrary place or the whole surface (coating step). It comprises a drying step (drying step), an exposure step (exposure step), a development step (development step), and a baking step (sintering step). In the exposure step, the groove width [S] of the partition wall and the pattern width [L] Is 5 to 5
It is necessary to use a 0 μm photomask.

Here, the PDP of the present invention will be described with reference to FIGS.
The photomask used in the method for manufacturing the device will be described in detail. FIG. 1 is a diagram showing a relationship between a groove width [S] of a partition wall and a pattern width [L] of a photomask preferred in the present invention, and FIG. 2 is a diagram showing a groove width [S] of a partition wall used in conventional photolithography. FIG. 11 is a diagram showing a relationship between “′” and a pattern width [L ′].

In FIG. 1, an electrode 1e, a dielectric layer 1c and a partition 1b are provided on a glass substrate 1f.
A photomask 1a is disposed above the photomask 1a. Similarly, in FIG. 2, an electrode 2e, a dielectric layer 2c, and a partition 2b are provided on a glass substrate 2f, and a photomask 2a is disposed above the electrode 2e, the dielectric layer 2c, and the partition 2b.

In the present invention, as shown in FIG. 1, a phosphor layer can be formed only in a cell by using a photomask having a pattern width [L] smaller than a groove width [S] of a partition wall. At this time, it is necessary that the pattern width [L] is smaller than the groove width [S] of the partition wall by 5 to 50 μm. 5μ
If it is less than m, a phosphor layer is formed in an adjacent cell due to alignment accuracy or partition accuracy. On the other hand, if it exceeds 50 μm, the pattern width is too narrow to form a phosphor layer on the side wall of the partition. It is preferable that the pattern width [L] is smaller than the groove width [S] of the partition wall by 10 to 30 μm.

On the other hand, as shown in FIG. 2, when the groove width [S '] of the partition and the pattern width [L'] are the same,
When the alignment accuracy or the partition wall width accuracy is poor, the phosphor layer is formed on the upper surface of the partition or in the adjacent cell.

In the present invention, it is preferable to use non-parallel light in the exposing step from the viewpoint of improving the side coatability. In particular, when the pattern width is reduced, there is a case where the side wall of the partition is peeled off by development and cannot be formed because the side wall of the partition is not exposed. However, when an exposure method using non-parallel light is used, the side wall of the partition is also exposed and the pattern formation is easy.

Here, the non-parallel light is defined in comparison with the parallel light. In the present invention, light emitted from a light source is applied to a substrate surface via a cold mirror, a fly-eye lens, a concave mirror, or the like. In this case, the angle between the parallel light beam from the concave mirror and the optical axis is preferably ± 1 ° or more, more preferably ± 0.5 ° or more.

The shape of the phosphor layer to be formed has a top thickness [Lt], a half width width [Lh] and a bottom thickness [Lh].
b] is preferably as follows.

Lt = 10 to 50 [μm] Lh = 10 to 50 [μm] Lb = 10 to 50 [μm] 0.2 ≦ Lt / Lb ≦ 5 0.2 ≦ Lh / Lb ≦ 5 Refers to the thickness of the phosphor layer at 2 to 10 μm from the top of the partition. Lt, Lh and Lb are 10 μm
Above is preferable in that the ultraviolet rays generated by the discharge are not absorbed before reaching the phosphor layer, and the luminance is particularly excellent.

On the other hand, when the thickness is 50 μm or less, the discharge space is appropriately maintained, and the plasma region and the phosphor layer have a constant interval, so that the phosphor is not sputtered and the life is prolonged.

When Lt / Lb and Lh / Lb are in the range of 0.1.
It is particularly preferable that it is in the range of 2 to 5.0 from the viewpoint of securing the aperture ratio and the coating property of the phosphor.

Next, a method of forming a phosphor layer in the method of manufacturing a PDP of the present invention will be further described.

(1) Application Step A photosensitive phosphor paste is applied to an arbitrary place on a glass substrate on which an electrode layer and a partition layer are formed. When a photosensitive phosphor paste is used, it may be applied to an arbitrary place or the whole surface. As a coating method, a known method such as screen printing, a bar coater, a roll coater, a die coater, and an ink jet can be used. The coating thickness can be adjusted by selecting the number of coatings, the gap of the coater, the mesh of the screen, and the viscosity of the paste. As described above, the phosphor layer of the PDP is formed on the bottom and side surfaces of the partition wall.
It preferably has a thickness of 0 to 50 μm, and preferably has a thickness of about 20 to 80 μm in consideration of shrinkage due to drying and baking.

In particular, it is preferable to form the phosphor layer in a red, green, and blue stripe shape in that color display is possible.

(2) Drying Step In the drying step, drying the glass substrate by inclining it by 150 to 210 degrees forms a phosphor layer uniformly on the side and bottom of the partition, and a phosphor having a thickness of 10 to 50 μm. This is preferable in that the layer can be easily formed. More preferably 170
~ 190 degrees. In the conventional drying method, since the drying is performed at an inclination of 0 degrees, the phosphor paste is accumulated on the bottom after application, and it is difficult to form the phosphor layer on the side wall of the partition.

Here, the angle of inclination will be described with reference to FIGS. FIG. 3 shows an example in which the glass substrate is inclined at a preferable inclination angle in the drying step of the present invention, and FIG. 4 shows a case where the inclination angle of the glass substrate conventionally performed is 0 degree. .

As shown in FIG. 4, the partition 4b and the phosphor layer 4
d, the angle B 'of the glass substrate 4f in a state where the dielectric layer 4c and the electrode 4e are formed is set to 0 degree. Based on this, as shown in FIG. 3, when the glass substrate 3f on which the partition walls 3b, the phosphor layers 3d, the dielectric layers 3c, and the electrodes 3e are formed is tilted clockwise or counterclockwise, The angle B of the glass substrate 3f is an angle of inclination.

(3) Exposure Step Exposure can be performed by a mask exposure method using a photomask as in ordinary photolithography. Particularly, at this time, it is preferable that the phosphor layer can be formed up to the upper portion of the side wall of the partition wall by performing the mask exposure with the non-parallel light as described above.

In the case of performing exposure over a large area, the photosensitive phosphor paste is applied, and then the exposure is carried out while being conveyed.
A large area can be exposed.

The active light source used at this time is, for example,
Visible light, near-ultraviolet light, ultraviolet light, electron beam, X-ray, laser light and the like are preferable, and among them, ultraviolet light is preferable. Etc. can be used. Among these, an ultra-high pressure mercury lamp is preferred.

For a photomask, the design of the pattern width is important. Usually, the same width (space) as the partition wall width minus the partition wall width is used, but in the present invention, it is necessary to use a photomask having a pattern width 5 to 50 μm narrower than the groove width of the partition walls.

(4) Development Step After exposure, development is performed using a developer.
An immersion method, a spray method, or a brush method is used.

As the developing solution, an organic solvent in which the organic components in the photosensitive phosphor paste can be dissolved can be used. In addition, water may be added to the organic solvent as long as the dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive phosphor paste, development can be performed with an aqueous alkali solution. As the alkali aqueous solution, a metal alkali aqueous solution such as a sodium hydroxide or calcium hydroxide aqueous solution 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, known amine compounds can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by weight, and 0.1 to 5% by weight.
Is more preferred. If the alkali concentration is too low, the unexposed portions are not removed, and if the alkali concentration is too high, the pattern portions may be peeled off and the exposed portions may be corroded, which is not preferable. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

(5) Firing Step Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of the photosensitive phosphor paste and the glass substrate, but it is preferable to fire in air, an atmosphere of nitrogen, hydrogen, or the like. The firing temperature is usually 400 to 610 ° C. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

In the above steps, a heating step at 50 to 300 ° C. may be introduced for the purpose of drying and preliminary reaction.

The glass substrate having the phosphor layer obtained by the above steps can be used on the back side of the PDP panel.

The glass substrate thus formed is
By sealing together with the glass substrate on the front and back, and filling a rare gas such as helium, neon and xenon,
Panel parts of PDP can be manufactured.

Further, a PDP can be manufactured by mounting a driver IC for driving.

Hereinafter, the glass substrate and the photosensitive phosphor paste which are preferably used in the method of manufacturing the PDP of the present invention will be described.

The glass substrate used in the present invention is:
Although not particularly limited, general soda lime glass or glass obtained by annealing soda lime glass, or
High strain point glass or the like can be used. The size of the glass substrate is not particularly limited, and glass having a thickness of 1 to 5 mm can be used.

On the glass substrate described above, silver, aluminum,
An electrode made of copper, gold, nickel, tin oxide, ITO, or the like is formed by screen printing, a photolithography method using a photosensitive conductive paste, or the like, and a partition is further provided.

For stabilizing the discharge, a glass substrate having a dielectric layer on the electrode layer may be used.

As a material for the partition walls, a glass material containing an oxide of silicon and boron as an essential component is preferably used. Further, it is particularly preferable that the partition wall is formed by a photolithography method to contain 70% by weight or more of a glass material having a refractive index of 1.5 to 1.68.

The photosensitive phosphor paste used in the present invention preferably includes a phosphor powder, an organic solvent and other organic components.

The phosphor powder is not particularly limited. For example, for red, Y ₂ O ₃ : Eu, YVO ₄ : Eu, (Y,
Gd) BO ₃ : Eu, Y ₂ O ₃ S: Eu, γ-Zn ₃ (PO
₄ ) ₂ : Mn, (ZnCd) S: Ag + In ₂ O ₃ and the like. In green, Zn ₂ GeO ₂ : M, BaAl ₁₂ O ₁₉ : M
n, Zn ₂ SiO ₄ : Mn, LaPO ₄ : Tb, ZnS:
Cu, Al, ZnS: Au, Cu, Al, (ZnCd)
S: Cu, Al, Zn ₂ SiO ₄ : Mn, As, Y ₃ Al ₅
O ₁₂ : Ce, CeMgAl ₁₁ O ₁₉ : Tb, Gd ₂ O ₂ S:
There are Tb, Y ₃ Al ₅ O ₁₂ : Tb, ZnO: Zn and the like.
In blue, Sr ₅ (PO ₄ ) ₃ Cl: Eu, BaMgAl
₁₄ O ₂₃ : Eu, BaMgAl ₁₆ O ₂₇ : Eu, BaMg ₂
Al ₁₄ O ₂₄ : Eu, ZnS: Ag + red pigment, Y ₂ Si
O ₃ : Ce or the like.

Thulium (Tm), terbium (T
b) tantalum substituted with at least one element selected from the group consisting of europium (Eu) and at least one host element rare earth element selected from yttrium (Y), gadolinium (Gd) and lutetium (Lu) Acid rare earth phosphors are also included. Preferably, the rare earth tantalate phosphor has a composition formula of Y _1-x Eu _x TaO ₄ , wherein
X is approximately 0.005 to 0.1), which is a europium-activated yttrium tantalate phosphor.

For the red phosphor, europium-activated yttrium tantalate is preferable, and for the green phosphor, a rare earth tantalate phosphor is represented by a composition formula Y _1-x Tb _x TaO ₄ (wherein:
X is approximately 0.001 to 0.2), and terbium-activated yttrium tantalate is preferable. As the blue phosphor, rare earth tantalate phosphor is Y _1-x Tb _x TaO.
4 (where X is approximately 0.001 to 0.2) is preferred. Thulium-activated yttrium tantalate is preferred. In the green phosphor, Mn is zinc silicate (Zn ₂
(SiO ₄ ) 0.2% by weight or more and less than 0.1% by weight based on the amount of the matrix.
m or less manganese-activated zinc phosphor (Zn ₂ SiO ₄ : M
n) and the general formula is (Zn _1-x M n _x ) O · αSiO
₂ (where X and α are 0.01 ≦ X ≦ 0.2, 0.
The manganese-activated zinc silicate phosphor represented by the formula (5 <α ≦ 1.5) is preferable.

The amount of the phosphor powder is preferably 40 to 75% by weight based on the entire photosensitive phosphor paste. If it is less than 40% by weight, peeling or cracking may occur due to a large shrinkage rate, and if it exceeds 75% by weight, the shrinkage rate is so small that the phosphor layer becomes 50 μm or more.

The particle diameter of the phosphor powder is selected in consideration of the line width, width interval (space) and thickness of the phosphor layer pattern to be produced.
It is preferable that the specific surface area is 0.1 to 2.0 m ² / g. Within this range, light is sufficiently transmitted during exposure to ultraviolet light, and a highly accurate pattern shape can be obtained. Further, it is preferable because the luminous efficiency of the phosphor is good and the life is long. If the powder particle size is less than 1.0 μm and the specific surface area exceeds 2.0 m ² / g, the powder becomes fine and light is scattered at the time of exposure, and the unexposed portion may be photocured.

As the shape of the phosphor powder, a polyhedral (granular) shape can be used, but a powder having no aggregation is preferable. Among them, a spherical powder is particularly preferable because the influence of scattering at the time of exposure can be reduced. Further, the spherical powder has a sphericity of 80.
It is preferable that the particles have a particle shape of several percent or more, since scattering by the phosphor powder does not occur at the time of exposure to ultraviolet light, and a high-definition pattern can be obtained. The sphericity was measured by measuring the phosphor powder with an optical microscope for 30 minutes.
Photographing is performed at a magnification of 0, and counting is performed by counting the number of particles that can be counted. The ratio of spherical particles is defined as the sphericity.

The organic components constituting the photosensitive phosphor paste used in the present invention include an organic component containing a photosensitive compound, a plasticizer and, if necessary, additives such as a dispersant and a leveling agent.

The organic component containing a photosensitive compound includes a photosensitive component selected from at least one of a photosensitive polymer, a photosensitive monomer, and a photosensitive oligomer, and further includes a photopolymerization initiator, if necessary, Additives such as sensitizers and ultraviolet absorbers are added.

The amount of the organic component containing the photosensitive compound used in the present invention is preferably 25 to 60% by weight in the photosensitive phosphor paste. When the content is 25% by weight or more, the photosensitivity is excellent and the pattern property becomes good.
It is preferable in that the binder removal property during firing becomes good and the firing is sufficiently performed.

The photosensitive component includes a photo-insolubilizing type and a photo-solubilizing type. The photo-insolubilizing type includes: (A) a functional monomer having at least one unsaturated group in the molecule. (B) those containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds. (C) So-called diazo resins such as condensates of diazo amines and formaldehyde. And others.

Examples of the photo-soluble type include (D) a complex of a diazo compound with an inorganic salt or an organic acid, and a compound containing quinone diazos. (E) a quinone diazo combined with an appropriate polymer binder. For example, there are naphthoquinone 1,2-diazido-5-sulfonic acid ester of phenol and novolak resin.

In the present invention, any of the above-mentioned photosensitive components may be used, but (A) is preferred because it can be easily mixed with inorganic fine particles (phosphor powder).

Examples of the photosensitive monomer include compounds containing a carbon-carbon unsaturated bond. Specific examples thereof include methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
-Butyl acrylate, sec-butyl acrylate,
Iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, Glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate ,
Methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate,
1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate Acrylate, polypropylene glycol diacrylate,
Triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, bisphenol A-ethylene oxide adduct Diacrylate, bisphenol A-
Diacrylate of propylene oxide adduct, thiophenol acrylate, benzyl mercaptan acrylate, and 1 to 5 hydrogen atoms of these aromatic rings
Monomer substituted with chlorine or bromine atom, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, Brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, and those in which some or all of the acrylates in the molecule of the above compound have been changed to methacrylates, γ-methacryloxypropyltrimethoxysilane,
1-vinyl-2-pyrrolidone and the like.

In the present invention, one or more of these can be used.

By using an unsaturated acid such as an unsaturated carboxylic acid in addition to the above-mentioned photosensitive components, the developability after exposure can be improved. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid,
Or an acid anhydride of these.

At this time, as the binder, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate copolymer, α-methylstyrene polymer, butyl methacrylate resin and the like are used. be able to.

Further, at least one of the compounds containing a carbon-carbon unsaturated bond described above as the photosensitive monomer is used.
Oligomers and polymers obtained by polymerizing the types can be used. Upon polymerization, it can be copolymerized with other photosensitive monomers so that the content of these monomers is 10% by weight or more, more preferably 35% by weight or more.

Examples of the monomer to be copolymerized at this time include unsaturated acids such as the above-mentioned unsaturated carboxylic acids, and the copolymerization can improve the developability after exposure.

The acid value (AV) of the thus obtained polymer or oligomer having an acidic group such as a carboxyl group in the side chain is preferably from 50 to 180, more preferably from 70 to 140. . When the acid value is less than 50, the allowable development width becomes narrow. In addition, the acid value is 18
If it exceeds 0, the solubility of the unexposed portion in the developer decreases, and if the concentration of the developer is high, the exposed portion may be peeled off, making it difficult to obtain a high-definition pattern.

By adding a photoreactive group to a side chain or a molecular end of the polymer or oligomer described above, it can be used as a photosensitive polymer or a photosensitive oligomer having photosensitivity.

Preferred photoreactive groups include those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

As a method for adding such a photoreactive group to a side chain or a molecular terminal of an oligomer or polymer,
There is a method in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, an acrylic acid chloride, a methacrylic acid chloride, or an allyl chloride is added to a mercapto group, an amino group, a hydroxyl group, or a carboxyl group in a polymer.

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 from 0.05 to 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is preferable to add one molar equivalent.

Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, and 4,4-dichlorobenzophenone. , 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-
Diethoxyacetophenone, 2,2-dimethoxy-2-
Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzylbenzyldimethylketane Benzyl, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-
t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4
-Azidobenzalacetophenone, 2,6-bis (p-
(Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-
Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime,
1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio ) Phenyl] -2-morpholino-1-propanone,
Naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide,
Combination of photoreducing dyes such as benzothiazole disulfide, triphenylphorphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine Is mentioned.

In the present invention, one or more of these can be used.

The photopolymerization initiator is added to the photosensitive component in an amount of 0.1%.
It is preferably added in the range of 1 to 6% by weight.
2-5% by weight is more preferred. If the amount of the photopolymerization initiator is too small, the sensitivity to light becomes low. If the amount is too large, the residual ratio of the exposed portion may be too small.

It is also effective to contain an ultraviolet light absorber. A high aspect ratio, high definition, and high resolution can be obtained by adding a light absorbing agent having a high ultraviolet absorbing effect.

As the ultraviolet absorbent, those composed of organic dyes, in particular, organic dyes having a high ultraviolet absorption coefficient in the wavelength range of 350 to 450 nm are preferably used.
Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinones, benzophenones, diphenylcyanoacrylates, triazines, p-aminobenzoic acid dyes and the like can be used. . Even when the organic dye is added as an ultraviolet light absorber, the organic dye does not remain in the phosphor layer after firing, so that a decrease in luminance due to the ultraviolet light absorber can be reduced, which is preferable. Among these, azo dyes and benzophenone dyes are preferred.

The addition amount of the organic dye is preferably 0.05 to 5% by weight based on the organic component. If the amount is less than 0.05% by weight, the effect of adding the ultraviolet absorber is reduced. If the amount exceeds 5% by weight, it may remain in the phosphor layer after firing, which is not preferable. More preferably, it is 0.15 to 1% by weight. An example of a method for adding an ultraviolet light absorber composed of an organic dye is as follows. A solution is prepared by dissolving an organic dye in an organic solvent in advance, and then a glass powder is mixed in the organic solvent, followed by drying. By this method, a so-called capsule-like powder in which an organic film is coated on the surface of each glass powder can be produced.

A sensitizer is preferably added to improve 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-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-
Bis (4-dimethylaminobenzal) acetone, 1,3
-Carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N- Examples include phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. In the present invention, these are
Species or two or more can be used. Some sensitizers can also be used as photopolymerization initiators.
When a sensitizer is added to the photosensitive paste of the present invention, the addition amount is preferably 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 small, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

Further, in the present invention, when it is desired to adjust the viscosity of the photosensitive phosphor paste, an organic solvent may be added. 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, butyl carbitol acetate, dimethyl sulfoxide, γ- Butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and an organic solvent mixture containing at least one of these are used.

The photosensitive phosphor paste is usually composed of a phosphor powder, an ultraviolet absorber, a photosensitive polymer, a photosensitive monomer,
After blending various components of the photopolymerization initiator and the organic solvent so as to have a predetermined composition, the mixture is uniformly mixed and dispersed by using three rollers or a kneading machine.

The paste viscosity is appropriately adjusted depending on the ratio of the phosphor powder, the organic solvent, the plasticizer, the precipitation inhibitor and the like, and the range is preferably 1 to 50 ps from the viewpoint of applicability. Further, it is preferable that the yield value is in the range of 0 to 150 mPa in that the side coatability after drying is improved.

The viscosity and the yield value are determined by the following methods. That is, 2 ml of the photosensitive phosphor paste of each color
Was taken in a parallel cone E-type viscometer, and the rotation speed was 0.5.
A constant shear was applied for 3 minutes at 1.0, 2.5, 5.0 and 10.0 rpm, respectively, and the subsequent shear stress was measured. Shear stress S (millipascal) is plotted against shear speed D, which is the reciprocal of various rotation speeds, viscosity ρ (poise) is obtained from the slope by the least square method, and yield value S ₀ (millipascal) is obtained from the y-intercept. ).

The amount of the organic solvent in the photosensitive phosphor paste of the present invention is preferably 10 to 50% by weight. If the addition amount is less than 10% by weight, the viscosity exceeds 50 Ps, and the paste hardly enters the inside of the partition wall at the time of application. If the addition amount exceeds 50% by weight, the powder precipitates during the preparation of the paste and may be separated.

Hereinafter, the present invention will be described specifically with reference to examples. The concentrations (%) in Examples and Comparative Examples mean% by weight unless otherwise specified.

[0084]

【Example】

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 uniformly dissolve all the photosensitive polymers. Was. The photosensitive polymer is composed of glycidyl methacrylate (GMA) in an amount of 0.4 equivalent to a carboxyl group of a copolymer composed of 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St). Was used and a photosensitive polymer having a weight average molecular weight of 43,000 and an acid value of 95 was used. Then, the solution was cooled to room temperature, and a photosensitive monomer, a photopolymerization initiator, a plasticizer (dibutyl phthalate), and a solvent (γ-butyl lactone) were added and dissolved. Thereafter, this solution was filtered using a 400-mesh filter to prepare a photosensitive organic binder.

Here, the photosensitive monomer and the photopolymerization initiator used are the following compounds.

Photosensitive monomer: TPA330 (trimethylolpropane triacrylate modified represented by the following formula)

Embedded image (Where a, b, and m are integers, a + b = 3) Photopolymerization initiator: Irgacure 907 (2-methyl-1)
[4- (Methylthio) phenyl] -2-monophorinopropanone-1).

Next, Sudan-IV was weighed at a ratio of 0.6% to the phosphor powder. Sudan-IV is a compound of the formula C
It is an azo organic dye having ₂₄ H ₂₀ N 4 _O and a molecular weight of 380.45. The Sudan-IV is dissolved in acetone, a dispersing agent is added thereto, and the mixture is uniformly stirred with a homogenizer. The phosphor powder is added to the solution, and the mixture is uniformly dispersed and mixed. Then, the mixture is heated to 150 to 200 ° C. using a rotary evaporator. Dried at temperature,
The acetone was completely evaporated. In this way, three kinds of powders were prepared in which the surface of the phosphor powder was uniformly coated with the film of the ultraviolet absorbent comprising an organic dye.

The phosphor powder used here is as follows: Red: (Y, Gd, Eu) BO ₃ , 50% particle diameter: 2.7
μm green: (Zn, Mn) 2 SiO ₄ , 50% particle size:
3.6 μm Blue: (Ba, Eu) MgAl ₁₀ O ₁₇ ), 50% particle size:
3.7 μm The photosensitive organic binder and the three types of phosphor powders to which the ultraviolet absorber was added were added so as to have the compositions shown in Table 1, and mixed and dispersed with three rollers to obtain three types of photosensitive fluorescent light. The body paste was adjusted.

Next, a photosensitive red phosphor paste is applied on the entire surface of a glass substrate on which partition walls having a height of 150 μm, a width of 30 μm, and a pitch of 150 μm have been formed, and are then inclined at 180 degrees.
Dried at 0 ° C for 60 minutes.

After drying, the pattern is cooled to room temperature and the pattern width is 100
Put a photo mask of μm and super high pressure mercury lamp 100mJ / c
Exposure at m ² and shower development with an aqueous alkali solution. The exposure was performed by irradiating non-parallel light. The same process was performed for the green photosensitive phosphor paste and the blue photosensitive phosphor paste to form red, green, and blue striped patterns. Further, the obtained glass substrate was baked at 500 ° C. for 30 minutes. The formed glass substrate was sealed together with the front and rear glass substrates, and a rare gas was sealed therein to produce a PDP panel portion.

Further, a PDP was manufactured by mounting a driver IC for driving.

In the evaluation, the top thickness, half width and bottom thickness of the phosphor layer were observed with an electron microscope. Regarding the upper thickness, the thickness at 5 μm from the top of the partition was measured. The luminance was measured with a luminance meter. Table 2 shows the thickness and average luminance characteristics of the obtained phosphor layers. A phosphor layer could be formed up to the upper part of the side wall of the partition wall, and as shown in Table 2, a phosphor having excellent luminance was obtained.

(Examples 2 and 3) A pattern was formed in the same manner as in Example 1 except that the width of the photomask was changed. The phosphor layer was formed up to the upper part of the side wall of the partition. Table 2 shows the results.

Comparative Example 1 A photomask having a width of 60 μm
A pattern was formed in the same manner as in Example 1 except that the pattern was changed. The phosphor layer could not be formed on the side wall of the partition. Table 2 shows the results.

[0095]

[Table 1]

[Table 2]

[0096]

According to the present invention, a photomask in which the difference between the groove width [S] of the partition and the pattern width [L] is 5 to 50 is used in the exposure step, so that the photomask is placed on the upper surface of the partition or in an adjacent cell. No phosphor layer is formed, and a PDP having excellent brightness without color mixing can be manufactured.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a relationship between a pattern width of a photomask and a groove width of a partition used in a method of manufacturing a PDP of the present invention.

FIG. 2 is a conceptual diagram showing a relationship between a pattern width of a photomask and a groove width of a partition used in a conventional PDP manufacturing method.

FIG. 3 is a conceptual diagram showing an example in which a glass substrate is inclined at a preferable inclination angle in a drying step of the present invention.

FIG. 4 is a conceptual diagram showing a glass substrate when the inclination angle is 0 ° in a conventional drying step.

[Explanation of symbols]

 1a, 2a: Photomasks 1b, 2b, 3b, 4b: Partition walls 1c, 2c, 3c, 4c: Dielectric layers 3d, 4d: Phosphor layers 1e, 2e, 3e, 4e: Electrodes 1f, 2f, 3f, 4f: Glass substrate

Claims (9)

[Claims] 1. A plasma for forming a phosphor layer through a step of applying a photosensitive phosphor paste, a drying step, an exposure step, a development step and a baking step after forming at least an electrode layer and a partition layer on a glass substrate. A method for manufacturing a display, comprising using a photomask having a groove width [S] and a pattern width [L] of a partition wall satisfying the following expression in the exposing step. 5 ≦ SL ≦ 50 [μm] 2. The method according to claim 1, wherein in the exposing step, exposing is performed by using non-parallel light. 3. The plasma display according to claim 1, wherein a top thickness [Lt], a half width width [Lh] and a bottom thickness [Lb] of the phosphor layer satisfy the following ranges. Production method. Lt = 10 to 50 [μm] Lh = 10 to 50 [μm] Lb = 10 to 50 [μm] 0.2 ≦ Lt / Lb ≦ 5 0.2 ≦ Lh / Lb ≦ 5 4. The photosensitive phosphor paste according to claim 1, wherein the content of each component is as follows.
4. The method for manufacturing a plasma display according to claim 3. Organic component containing photosensitive compound: 25 to 60% by weight Phosphor powder: 40 to 75% by weight Solvent: 10 to 50% by weight Photopolymerization initiator: 0.1 to 6.0% by weight 5. The method according to claim 1, wherein the red, green, and blue phosphor layers are formed in a stripe shape. 6. The method for manufacturing a plasma display according to claim 1, wherein in the drying step, the glass substrate is dried while being inclined at 150 to 210 degrees. 7. The viscosity ρ [p of the photosensitive phosphor paste
The method according to any one of claims 1 to 6, wherein s] and the yield value S [mPa] satisfy the following expression. 1 ≦ ρ ≦ 50 [ps] 0 ≦ S ≦ 150 [mPa] 8. The phosphor powder in the photosensitive phosphor paste has a 50% by weight particle size of 1 to 6 μm and a specific surface area of 0.
1 to 2.0 m ² / g.
8. The method for manufacturing a plasma display according to claim 7. 9. The organic component containing the photosensitive compound in the photosensitive phosphor paste contains 0.01 to 2% by weight of an organic dye having an ultraviolet absorbing property. 8. The method for manufacturing a plasma display according to any one of 8 above.