JP2000260310A - Manufacture of plasma display and paste applying device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a paste applied layer on a whole surface with a uniform height without raising an end of the paste applied layer, by outwardly expanding a paste-delivering groove toward the tip of the delivering groove. SOLUTION: When a paste is applied from a delivering groove, by outwardly expanding the delivering groove toward the tip of the delivering groove, a paste applied layer can be stably formed with a uniform height without raising an end of the applied paste-applied-layer. Since the delivering groove is constituted so that spacer width at each tip of it is L longer than spacer width (c) in a manifold region, the paste having traveled in an upper part of a land region with a uniform height further expands outward by the width L at the tips of the delivering groove. Therefore, thickness of the both ends of the paste delivered from the tip of the base is reduced. As a result, the paste applied layer with a uniform height without raising both ends of the paste applied layer after the application can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plasma display manufacturing method and a paste coating apparatus.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Can display at a higher speed than a liquid crystal panel.
Because it is easy to increase the size, it has permeated the fields of OA equipment and public information display devices. Further, progress in the field of high-definition television is highly expected. With such expanded use, color PDPs having delicate and many display cells have attracted attention. This color PD
P generates plasma discharge between opposing anode and cathode electrodes in a discharge space provided between the front glass substrate and the rear glass substrate, and discharges ultraviolet light generated from gas sealed in the discharge space. The display is performed by hitting a phosphor provided in the space. In this case, a partition (referred to as a barrier or a rib) is provided in order to suppress the spread of the discharge to a certain area, to perform display in a specified cell, and to secure a uniform discharge space. The shape of this partition is approximately 20 to 80 μm in width and 100 to
200 μm. Examples of the method for forming the partition include a screen printing method, a dry film method, a sand blast method, and a photosensitive paste method. Among them, the screen printing method has a height of 100 to 20 because a single coating thickness is several tens of μm.
In order to form a 0 μm partition layer, printing / drying needs to be repeated many times, generally 10 times or more, and there is a problem that productivity is extremely poor. Further, there is a disadvantage that the surface flatness of the top of the partition wall is deteriorated because mesh marks of the screen pattern remain.

As a method of forming a partition layer by one application, there are, for example, a spin coating method, a dip method, a slit die coating method and the like. Among them, the spin coating method and the dipping method have a disadvantage that when the substrate size is increased, not only the uniformity of the coating film is deteriorated, but also the economic efficiency is deteriorated.

[0004] On the other hand, coating discharged from a die having a discharge groove, for example, slit die coating, can apply only a necessary amount of paste to a substrate, and therefore has the feature of being extremely excellent in economy and productivity. . However, when the paste is discharged from the die having the discharge grooves and applied, the end of the paste applied layer rises immediately after the application. Furthermore, since the drying speed of the solvent from the end of the paste coating layer during the paste drying is faster than near the center,
Fluidization of the paste to the application end occurs, and the end becomes thicker. For example, when the paste film thickness at the center is 200 μm, the applied end portion is about 250 μm and rises by about 50 μm, so that there is a problem that a paste applied layer having a uniform height cannot be formed on the entire surface.

[0005]

SUMMARY OF THE INVENTION According to the present invention, in a step of applying a paste from a die having a discharge groove and forming a paste applied layer, the end of the paste applied layer is not raised and the coated layer having a uniform height is formed. It is an object of the present invention to provide a method of manufacturing a plasma display and a paste coating apparatus, which can form a paste on the entire surface.

[0006]

In order to solve the above-mentioned problems, the present invention is characterized in that, when a paste is applied from a die having a discharge groove, the discharge groove extends outward toward the tip of the discharge groove. A paste application layer having a uniform height can be formed on the entire surface without the edges of the paste application layer rising.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a method of applying a paste containing an inorganic powder and an organic binder from a die having a discharge groove, for example, there is a slit die coat application.
This application is a method in which the paste is discharged from a die having a so-called slit-shaped discharge groove using a pressure feed, a syringe pump, a diaphragm pump, a gear pump, or the like, and applied. Since this slit die coat application can apply only a necessary amount of paste, there is a feature that no waste liquid is theoretically generated. Therefore, it is very economical as compared with other coating methods.

[0008] However, when the paste is applied from the die having the discharge groove, the thickness of the end portion of the paste application layer becomes large as shown in FIG. For example, when the film thickness is 200 μm, the edge of the paste application layer is about 2 cm wide and about 50 cm from the center.
μm thicker. In such a state, when pattern processing and baking are performed to form a partition, and the PDP panel is bonded to the front plate, the cross-talk (crosstalk) occurs because the thickness of the partition at the end is thicker than that at the center. Or sealing cannot be performed.

Therefore, in the present invention, when the paste is applied from the discharge groove, the discharge groove extends outward toward the tip of the discharge groove, so that the end of the applied paste coating layer does not bulge and is uniform. A paste application layer having a height can be stably formed.

FIGS. 4 to 6 show a conventional die structure of a slit die coat. The shape of the spacer 10 was linear from the manifold to the land.

On the other hand, an example of the die structure of the present invention is shown in FIGS. The front lip 6 and the rear lip 7
Thus, the spacer 10 is interposed therebetween, and the gap between the front lip 6 and the rear lip 7 becomes a discharge groove. The spacer 10 has a shape as shown in FIG. 2 and has a role of forming a wall in the width direction of the discharge groove and defining the thickness of the discharge groove. The paste flows into the base through the manifold 9 and flows through the space (land 11) formed by the front lip 6, the rear lip 7, and the spacer 10. Then, the ink is discharged from the end of the discharge groove (the lower end in the figure).

In the present invention, the expression that the ejection groove extends outward toward the tip of the ejection groove means that the spacer width at the tip of the ejection groove is larger than the spacer width c in the manifold region as shown in FIG. This means that the structure is longer at both ends by L. With such a structure, the paste that has passed through the upper part of the land area with a uniform thickness spreads further outward by the width L at the tip of the discharge groove. Becomes thinner. Therefore, it is possible to form a paste application layer having a uniform height without raising both end portions of the paste application layer after application.

Here, the cross section in the width direction of the discharge groove is made to spread outward toward the tip, but the cross section in the thickness direction or both of them may be made to spread outward toward the tip. However, it is preferable that the shape of the spacer is processed as described above so that the cross section in the width direction of the discharge groove expands outward toward the front end, because it is accurate and simple.

Next, FIG. 7 shows a structural diagram of a typical example (for example, a slit die coat) of a coating apparatus for applying a paste using a die having a discharge groove described in the present invention. The base moves in the application direction 2 with a certain clearance 3 above the substrate 5. Alternatively, the base 5 may be moved with the base fixed. The paste to be applied flows from the manifold 9 into the base, passes through the discharge groove, and is discharged from the discharge groove tip 8 (lip tip).

In the present invention, it is preferable that the size of L is larger than the bulging width L 'of the coating end portion when the coating is performed using a conventional die with L = 0. Here, FIG. 8 shows a cross-sectional view of the paste application layer in which the edge is raised.
When the average height of the paste applied layer is extended in the end direction, the edge ridge height g is defined by extending the edge point g where the paste is applied in the vertical direction, and the intersection f with the average height of the paste applied layer. The height of the swell is the distance d 'between the height of the most swelled portion and the average height of the paste application layer at the end of the coating layer.

The height d of the divergent portion of the spacer is preferably larger than the height d 'of the swelling of the paste coating layer.

That is, L'≤L (1) d'≤d (2) is preferred.

In the present invention, the corner portion of the spacer at the tip of the land lip is cut straight, but may be tapered, corrugated, saw-toothed, or the like. Further, the angle d / L of the portion that has been cut off is not particularly limited as long as the angle satisfies the above formulas (1) and (2). Further, the angles and shapes of both end portions may be different between left and right.

Further, the shape of the spacer 10 in the thickness direction is not particularly limited. It may be on a straight line as shown in FIG. 3 or, for example, a pyramid shape as shown in FIG.
Alternatively, it may have a tapered shape as shown in FIGS.

In the present invention, the method of discharging the paste from the discharge groove includes a pressure feeding method, a syringe pump method, a diaphragm pump method, a gear pump method, and the like, and any of these methods may be used. These may be used in combination.

The substrate on which the paste is applied is a glass substrate or a glass substrate on which electrodes, dielectrics, etc. are formed.

The paste used in the present invention contains an inorganic powder such as a glass powder and an organic binder. Hereinafter, an example of the photosensitive glass paste used in the photolithography method will be specifically described, but the present invention is not limited thereto. For example, a paste for a partition used in a sandblast method, a dry film method, or the like may be used.

The photosensitive paste contains at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and further includes an organic solvent, a photopolymerization initiator, a sensitizer, and a sensitization aid. , Polymerization inhibitors, binders,
Additional components such as a plasticizer, a leveling agent, and an ultraviolet absorber may be contained.

The glass powder used in the present invention is 50 to 4
The coefficient of thermal expansion at 00 ° C (α ₅₀ to ₄₀₀ ) is 50 to 90 × 10
It is preferably ^-7 . In addition, 3 pieces of silicon oxide
６０60% by weight and boron oxide in the range of 5 重量 50% by weight provide electrical insulation, strength, coefficient of thermal expansion,
Electrical, mechanical, and thermal properties such as the denseness of the insulating layer can be improved. Glass transition temperature is 430-500
° C and a softening point are preferably 470-580 ° C.
If the glass transition temperature is 500 ° C. and the softening point is higher than 580 ° C., it must be fired at a high temperature, and the substrate is distorted during firing. Further, the glass transition temperature is 430
In the case of glass having a softening point of lower than 470 ° C., a dense partition wall layer cannot be obtained, which causes peeling, disconnection and meandering of the partition walls. The particle diameter of the glass powder is selected in consideration of the line width and height of the partition wall to be produced, but the 50% by volume particle diameter (average particle diameter D50) is 1 to 6 μm, and the maximum particle size is 30 μm.
Hereinafter, the specific surface area is preferably 1.5 to ⁴ cm ² / g.

The photosensitive monomer is a compound having a carbon-carbon unsaturated bond, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
sec-butyl acrylate, isobutyl acrylate, t-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, isobonyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene Glycol acrylate, Carboxy glycol acrylate, octa fluorosilicone pentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated hexane Siji acrylate, 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, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acryle DOO, benzyl acrylate, 1-
Examples include naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, thiophenol acrylate, and acrylate such as benzyl mercaptan acrylate.

In addition, by adding 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 content of these monomers is preferably 5 to 30% by weight based on the sum of the glass powder and the photosensitive component. A range outside these ranges is not preferred because the pattern formability deteriorates and insufficient curing after curing occurs. As the photosensitive oligomer and the photosensitive polymer, those obtained by synthesizing one or more of the above-described photosensitive monomers can be used. The content of the photosensitive oligomer and the photosensitive polymer is 5 to 3 with respect to the sum of the glass powder and the photosensitive monomer.
0% by weight is preferred. Outside of these ranges, it is not preferable because the pattern cannot be formed, the pattern becomes thick, or the meandering becomes large.

The organic solvent used in the present invention refers to a liquid having a boiling point at normal pressure of 20 to 250 ° C. Points to consider when selecting an organic solvent to be added are the boiling point at normal pressure, volatility, solubility in photosensitive compounds, miscibility,
Dispersion characteristics, rheological characteristics, etc. Specifically, γ-
Cellosolves such as butyrolactone (hereinafter abbreviated as γ-BL), methyl cellosolve, ethyl cellosolve, butyl cellosolve, isopropyl alcohol, methyl alcohol;
Alcohols such as ethyl alcohol, butyl alcohol and normal propyl alcohol, methyl ethyl ketone, ketones such as dioxane, acetone, cyclopentanone, diethyl ketone, methyl isobutyl ketone and diisobutyl ketone, ethyl lactate and methyl acetate, ethyl acetate and isopropyl acetate; Normal propyl acetate, isobutyl acetate, normal pentyl acetate, isopentyl acetate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3
-Methyl-butyl acetate, propylene glycol 1
Esters such as monomethyl ether-2-acetate, hydrocarbons such as hexane, cyclohexane, benzene, toluene and xylene, methylene chloride,
Chlorinated hydrocarbons such as chloroform and dichloromethane are exemplified, and one or more of them can be added.

As the photopolymerization initiator, benzophenone, O
Methyl benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone,
Dibenzyl ketone, fluorenone, 2,2-dimethoxyacetophenone, 2,2-dimethoxy-2-methyl-2
-Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyl Dimethyl methyl ketanol, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (P-azidobenzylidene) cyclohexanone, 2-phenyl-1,2- Tanjion 2-(O-methoxycarbonyl) oxime, 1,3-diphenyl - propane trione-2-(O-ethoxycarbonyl) oxime and the like. In the present invention, one or more of these can be used. This photopolymerization initiator is preferably added in the range of 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on the photosensitive organic component.
If the amount of the initiator is too small, the photosensitivity is reduced and the curing is insufficient. On the other hand, if it is too large, the partition wall becomes thick.

As the photosensitive oligomer and the photosensitive polymer, those obtained by synthesizing one or more of the above photosensitive monomers can be used. The content of the photosensitive oligomer and the photosensitive polymer is preferably 5 to 30% by weight based on the sum of the glass powder and the photosensitive organic substance.
Outside of these ranges, it is not preferable because the pattern cannot be formed, the pattern becomes thick, or the meandering tends to increase.

Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3
-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-dimethylaminocinnamylideneimidanone, p-dimethylaminobenzyldenindanone, and the like. . In the present invention, one or more of these can be used. The addition amount is 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, based on the photosensitive organic component. When the amount of the sensitizer is small, the light sensitivity cannot be improved. On the other hand, if it is too large, the light sensitivity becomes too sensitive and the partition walls become thick.

The polymerization inhibitor is added to improve the storage stability. Specific examples include hydroquinone, a monoester compound of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-
Phenylnaphthylamine, chloranil and the like. The amount added is 0.001 to 1% by weight. Examples of the binder include polyvinyl alcohol, polyvinyl butyral, a methacrylate polymer, an acrylate polymer, an acrylate-methacrylate polymer, an α-methylstyrene polymer, and a butyl methacrylate resin.

Examples of the binder include polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate polymer, α-methylstyrene polymer, and butyl methacrylate resin.
Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and glycerin.

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

In the present invention, high definition and high resolution can be obtained by adding an ultraviolet absorber to the photosensitive glass paste. As the ultraviolet absorber, those made of an organic dye are often used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinone dyes,
Benzophenone dyes and the like can be used. The addition amount is preferably 0.05 to 5% by weight based on the glass powder. 0.0
If the content is less than 5% by weight, the effect of adding the ultraviolet absorber is reduced,
Exceeding the weight percent is not preferred because the properties of the insulating film after firing deteriorate. More preferably 0.05 to 0.18% by weight
It is.

An example of a method for adding a light absorber comprising an organic dye in the present invention will be described. The organic dye is dissolved in an organic solvent such as acetone, mixed with the inorganic powder, and sufficiently stirred. Next, the organic solvent is evaporated using a rotary evaporator. By this method, a so-called capsule-like powder in which the surface of each powder of the inorganic fine particles is coated with an organic dye film can be produced.

An antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples include 2,6-di-t-p-cresol, butylhydroxyanisole, 2,6-di-t-4-ethylphenol,
2,2-methylenebis- (4-methyl-6-t-butylphenol) and the like. The amount of addition is 0.001 to 1% by weight based on the paste.

In the use of the photosensitive glass paste of the present invention, it is naturally necessary to dry the paste after application of the paste. However, a precaution during this drying is to keep the photosensitive glass paste horizontal. This is because, if the paste is slightly inclined, the paste flows and unevenness in film thickness occurs. Drying methods include hot air oven, hot plate, far infrared, natural drying,
A commonly used method such as drying under reduced pressure can be used, but the important point is that the photosensitive glass paste layer is dried uniformly in the depth direction.

The drying temperature may be any number as long as the temperature is lower than the temperature at which the photosensitive compound does not cause thermal polymerization. Generally, the range of 60 to 150 ° C. is preferable. Here, the drying temperature refers to, for example, the temperature of the substrate surface when dried using a hot plate or far-infrared rays, or the temperature of hot air in the case of a hot air oven.

The photosensitive glass paste is usually prepared by mixing various components such as glass powder, photosensitive monomers, oligomers, polymers, photopolymerization initiators, sensitizers and organic solvents so as to have a predetermined composition, and then using a three-roller. And uniformly mixed and dispersed with a kneader. The viscosity of the paste is glass powder,
It is determined by the addition ratio of photosensitive monomers, oligomers, polymers, solvents, plasticizers, etc., but the range is 0.5 to
The pressure is 200 Pa · s, but in the case of the slit die coating method, it is preferably 2 to 50 Pa · s.

Next, an example of performing pattern processing using a photosensitive glass paste will be described, but the present invention is not limited to this. Apply a photosensitive paste on the entire surface of a glass substrate, ceramic substrate, or polymer film.
Alternatively, it can be partially applied.

Here, when the paste is applied on the substrate, the surface of the substrate can be treated to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and tris-silane.
(2-methoxyethoxy) vinylsilane, γ-glycidoxypropanetrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane , Γ-mercaptanpropyltrimethoxysilane or the like, or an organic metal, for example,
Organic titanium, organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal in an organic solvent such as ethylene glycol monomethyl ether,
A solution diluted to a concentration of 0.5 to 5% with ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol or the like is used. Next, the surface treatment liquid can be uniformly applied to the substrate with a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform the surface treatment.

After applying the photosensitive glass 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 red or blue laser beam or the like without using a photomask may be used.
As the exposure device, a stepper exposure device, a proximity exposure device, or the like can be used. In the case of performing a large-area exposure, a large-area exposure can be performed with a small exposure area by applying a photosensitive paste on a substrate such as a glass substrate and then performing the exposure while transporting the photosensitive paste.
At this time, the active light source used includes, for example, visible light, near-ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, etc. Among them, ultraviolet light is preferable. Mercury lamps, ultra-high pressure mercury lamps, halogen lamps, germicidal lamps and the like can be used. Among these, an ultra-high pressure mercury lamp is preferable. Exposure conditions vary depending on the coating thickness, but it is more preferable to perform exposure using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm ² for 0.2 to 30 minutes.

By providing an oxygen blocking film on the surface of the applied photosensitive glass paste, the pattern shape can be improved. As an example of the oxygen barrier film, a film of PVA or cellulose, or a film of polyester or the like can be given. The method for forming the PVA film has a concentration of 0.5 to
A 5% by weight aqueous solution is uniformly applied to the substrate by a method such as a spinner, and then dried at 70 to 90 ° C. for 10 to 60 minutes to evaporate water. Further, it is preferable to add a small amount of alcohol to the aqueous solution, since the wettability with the insulating film is improved and the evaporation is facilitated. A more preferred concentration of the PVA solution is 1 to 3% by weight. Within this range, the sensitivity is further improved. The reason why the sensitivity is improved by the PVA application is presumed to be as follows. That is, it is considered that the presence of oxygen in the air when the photosensitive component undergoes a photoreaction impairs the photocuring sensitivity, but the presence of a PVA film can block excess oxygen, thus improving the sensitivity during exposure.
When a transparent film such as polyester, polypropylene, or polyethylene is used, there is a method in which these films are attached to a photosensitive glass paste after application.

After the exposure, development is performed by utilizing the difference in solubility between the photosensitive portion and the non-photosensitive portion with respect to the development. In this case, the development is performed by an immersion method, a spray method, or a brush method. As a developer to be used, an organic solvent in which an organic component in the photosensitive glass paste can be dissolved can be 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 glass paste, it can be developed with an alkaline aqueous solution. As the alkali aqueous solution, a metal alkali aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution or the like is used. However, it is preferable to use an organic alkali aqueous solution since the alkali component can be easily removed during firing. An amine compound can be used as the organic alkali. 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 part will not be removed. 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 preferable. Further, it is preferable from the viewpoint of process control that the development is performed at a development temperature of 20 to 50 ° C.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of the paste substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a belt-type continuous firing furnace such as a batch-type firing furnace or a roller hearth type can be used. Firing temperature is 5
The baking is performed at a temperature of 00 to 610 ° C. for 5 to 60 minutes. A particularly preferred temperature is 530-580 ° C. In addition, drying, during each of the above coating and exposure, development, baking steps,
A heating step at 50 to 200 ° C. may be introduced for the purpose of the preliminary reaction. When manufacturing a plasma display, on the glass substrate on which the electrode layer is formed, using the photosensitive glass paste of the present invention, the partition is formed by the above steps, and the phosphor is further subjected to a screen printing method or a photosensitive glass paste method. Thus, a back substrate can be obtained. A plasma display can be manufactured by connecting the driving circuit after sealing the obtained rear substrate and the front substrate together and introducing a rare gas.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited to this. The concentrations in Examples and Comparative Examples are% by weight unless otherwise specified. (Example 1) 25-inch PD200 2.8 mm thick
The electrode paste was printed with a wet film thickness of 5 μm on the glass substrate of Example 2 by a screen printing method, and then dried in a hot air oven at 80 ° C. for 10 minutes. The film thickness after drying was 3 μm. Next, mask exposure was performed at a pitch of 135 μm and a line width of 15 μm, and then shower development was performed at a water temperature of 35 ° C. using a 0.1% 2-aminoethanol aqueous solution to form an electrode pattern. Thereafter, it was fired at 590 ° C.

Next, a dielectric paste was screen-printed on the previously formed electrode pattern to a wet film thickness of 6 μm.
And dried in a hot air oven at 80 ° C. for 15 minutes. The film thickness after drying was 4 μm. Then 580
The resultant was fired at a temperature of ° C. to form a dielectric layer.

Next, a photosensitive glass paste for a partition was applied on the dielectric layer. The photosensitive glass paste for partition walls was prepared by dissolving each of the following organic components at 80 ° C. while heating, then adding a glass powder and kneading with a kneading machine. Glass _{powder: Li 2 O: 8.6%,} SiO 2: 20.1
_{%, B 2 O 3: 31} %, BaO: 3.8%, Al 2 O 3: 2
0.6%, ZnO: 2.1%, MgO: 5.9%, Ca
O: 4.2% composition (analytical value).

The average refractive index was 1.586. Also,
This glass powder was used after coating with an ultraviolet absorber. Photosensitive monomer _{(MGP-400): X 2} -N-CH (CH 3) -CH 2
_{- (O-CH 2 -CH (} CH 3)) n -NX 2 X: -CH 2 -CH (OH) -CH 2 O-CO-C = CH
₂ n: 2 to 10 Photosensitive polymer (X-4007): 40% methacrylic acid,
A weight-average molecular weight obtained by addition-polymerizing 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer composed of 30% methyl methacrylate and 30% styrene 4
3,000, a photosensitive polymer having an acid value of 95. Photopolymerization initiator (IC-369): Irgacure-3
69 (Ciba-Geigy) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 sensitizer (DETX-S): 2,4-diethylthioxanthone UV absorber (Sudan): Azo dye C ₂₄ H ₂₀ N ₄ O Organic solvent: γ-butyrolactone (boiling point 200 to 208
The calculated average refractive index of these organic components is about 1.59, which is very close to the refractive index of glass of 1.586.

Paste composition Glass powder: 51.90% Photosensitive monomer: 11.64% Photopolymer: 9.46% Photopolymerization initiator: 2.60% Sensitizer: 2.60% Ultraviolet light absorber: 0 .10% organic solvent: 21.70% As a base, a base having a spacer having the following shape in FIG. 2 was used.

A: 49 mm b: 50 mm c: 460 mm d: 1 mm L: 3 mm Thickness: 400 μm The coating conditions are as follows.

Application speed: 0.5 m / min Discharge pressure (pressure feeding): 2 kg / cm ² Paste viscosity: 200 Pa · s Under such conditions, immediately after applying the above photosensitive glass paste for a partition on a dielectric, a laser was used. -The cross-sectional shape of the paste coating layer was measured using a focus displacement meter. The laser focus displacement meter LT-8120 (KEY
Scan speed 0.25 m / min.
I went in. The horizontal magnification was × 1 and the vertical magnification was × 20.

The thickness of the paste coating layer is 250 at the center.
μm and 249 μm and 250 μm at both ends, respectively, and the coating layer could be formed at a uniform height without swelling at the ends.

Next, the partition wall paste applied at 80 ° C. for 120 minutes using a hot air oven was dried. Thereafter, exposure was performed using an exposure apparatus. The mask used was pitch 1.
This is a chrome mask having a line width of 35 μm and a line width of 25 μm. Next, using a 0.2% 2-aminoethanol aqueous solution, shower development was performed at a water temperature of 35 ° C., and unexposed portions were washed away to form a partition pattern. Next, baking was performed at 570 ° C. to burn off organic components such as a binder. Next, the phosphor paste for R was printed with a thickness of 20 μm by screen printing, and baked at 570 ° C. Subsequently, a phosphor paste for G and a phosphor paste for B were sequentially printed and baked to produce a back plate for a plasma display panel. (Example 2) An experiment was performed in the same manner as in Example 1 except that the shape of the spacer was changed as follows.

A: 47 mm b: 50 mm c: 460 mm d: 3 mm L: 3 mm Thickness: 400 μm The thickness of the paste coating layer is 254 μm at the center, 252 μm and 255 μm at both ends, and the edges are not raised. A coating layer could be formed at a uniform height. (Comparative Example 1) Example using a conventional die in which the shape of the spacer is as follows, that is, a spacer in which the width of the discharge groove of the die is the same length from the manifold to the tip of the discharge groove in the application direction. The experiment was performed in the same manner as in Example 1.
The thickness of the paste coating layer was 252 μm at the center and 298 μm and 300 μm at both ends, respectively. The width was 20 mm from the end, and the width of the paste was raised by 50 μm with respect to the center.

A: 50 mm b: 50 mm c: 460 mm d: 0 mm L: 0 mm Thickness: 400 μm

[0057]

According to the present invention, when the paste is applied from the discharge groove by using a die having the discharge groove, the paste is applied by applying the paste because the discharge groove extends outward toward the tip of the discharge groove. A paste application layer having a uniform height can be formed stably without the edge of the layer being raised.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view in the width direction showing the structure of a die according to the present invention

FIG. 2 is a cross-sectional view in the width direction showing a spacer of a base according to the present invention.

FIG. 3 is a sectional view in the thickness direction of the die according to the present invention.

FIG. 4 is a cross-sectional view in the width direction showing the structure of a conventional die.

FIG. 5 is a cross-sectional view in the width direction showing a conventional base spacer.

FIG. 6 is a sectional view in the thickness direction of a conventional die

FIG. 7 is a diagram showing a paste application device according to the present invention.

FIG. 8 is a cross-sectional view of a paste coating layer with raised edges.

FIG. 9 is a sectional view of a cap having a pyramid-shaped spacer thickness according to the present invention.

FIG. 10 is a sectional view of a die having a tapered spacer thickness according to the present invention.

FIG. 11 is a sectional view of a die having a tapered spacer thickness according to the present invention.

[Explanation of symbols]

 1 ··· Spacer thickness (slit width) 2 ··· Application direction 3 ··· Clearance 4 ··· Paste 5 ··· Substrate 6 ··· Front lip 7 ··· Rear lip 8 ··· Discharge groove tip 9 ··· Manifold 10 ·· Spacer 11 ·· Land

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F041 AA05 CA02 CA15 5C027 AA09 5C040 GF19 JA02 JA15 JA40 KA09 KA16 MA24

Claims (5)

[Claims] 1. A paste containing an inorganic powder and an organic binder is discharged from a die having a discharge groove, and 30 to 30
A method of manufacturing a plasma display, comprising forming a paste layer having a thickness of 500 μm, patterning the paste layer, and baking to form partition walls, wherein the discharge groove extends outward toward the tip of the discharge groove. A method of manufacturing a plasma display. 2. The method of manufacturing a plasma display according to claim 1, wherein the cross section of the discharge groove in the width direction is extended outward toward the tip of the discharge groove. 3. The method according to claim 1, wherein the paste is a photosensitive paste containing a photosensitive compound, and the step of patterning is performed by photolithography. 4. A paste coating apparatus for discharging a paste containing an inorganic powder and an organic binder from a mouthpiece having a discharge groove, wherein the discharge groove extends outward toward a tip of the discharge groove. Paste application equipment. 5. A paste coating device for discharging a paste containing an inorganic powder and an organic binder from a die having a discharge groove, wherein the die is formed of a front lip, a rear lip and a spacer, and A paste coating apparatus characterized in that a cross section in the width direction extends outward toward the tip of the discharge groove.