JPH09312135A - Plasma display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diaphragm layer with high precision and a high aspect ratio by using glass having a specified composition for the diaphragm layer of a plasma discharge part. SOLUTION: In a patterning process of a diaphragm layer, a photosensitive paste consisting of glass fine particles, an ultraviolet ray absorbent, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a solvent, etc., is applied to a glass substrate. Then, a desired pattern is formed by development after the exposure process is carried out with ultraviolet rays from a high pressure mercury lamp using a photomask. After that, the resultant glass substrate is kept at, for example, 520-610 deg.C for 10-60 minutes in a firing furnace to fire the patterned paste and form a diaphragm layer. As the composition of glass to be used as the glass fine particles, the respective component and contents are set to be as following; 15-50wt.% of silicon oxide, 15-40wt.% of boron oxide, 2-10wt.% of barium oxide, 6-25wt.% of aluminum oxide, 1-15wt.% of lithium oxide. Consequently, the refractive index of the glass is made similar to that of the organic components and light scattering in the paste inside at the time of exposure can be suppressed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma discharge part of a plasma display or a plasma addressed liquid crystal display.

[0002]

2. Description of the Related Art In recent years, the definition of a display has been improved, and accordingly, the pattern processing technology has been required to be improved. In a display involving plasma discharge such as a plasma display and a plasma liquid crystal display, a partition layer is formed as a partition of each pixel in order to suppress color crosstalk and the like. As the definition of a display becomes higher, there is an increasing demand for forming a partition layer with high accuracy and a high aspect ratio using an inorganic material such as glass.

Conventionally, when patterning an inorganic material, screen printing using a paste composed of an inorganic powder and an organic binder is often used. However, screen printing has a drawback that a pattern with high accuracy cannot be formed.

As a method for solving this problem, Japanese Patent Laid-Open No.
Japanese Patent Application Laid-Open Nos. 296534/1990, 165538/1993 and 5342929/1993 propose a method of forming a photosensitive paste using a photolithography technique. However, since the sensitivity and resolution of the photosensitive paste are low, a high aspect ratio and high definition partition cannot be obtained. For example, when patterning a material having a thickness exceeding 80 μm, a plurality of processing steps (coating , Exposure and development steps), which has the disadvantage of lengthening the steps.

In Japanese Patent Application Laid-Open No. 2-165538, after a photosensitive paste is coated on transfer paper,
Japanese Patent Application Laid-Open No. 3-57138 proposes a method of transferring a transfer film onto a glass substrate to form partitions, in which grooves of a photoresist layer are filled with a dielectric paste to form partitions. . In addition, JP-A-4-109
Japanese Patent No. 536 proposes a method of forming partition walls using a photosensitive organic film. However, these methods have a problem that the number of processes is increased because a transfer film, a photoresist, or an organic film is required. Further, a partition having a high definition and a high aspect ratio has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present inventors have thought that the formation of a partition layer using a photosensitive paste is easier and more accurate than that of other methods, and that the formation of a pattern is possible.
We worked diligently. However, conventionally, it has been difficult to make a photosensitive paste containing inorganic fine particles and an organic component into a thick-film photosensitive material. Therefore, in order to pattern a photosensitive paste having a thickness of 100 μm or more, a plurality of coating steps are required. And the exposure step had to be repeated.

An object of the present invention is to provide a plasma display having a partition wall layer having a high definition and a high aspect ratio, which can be manufactured by a small number of steps.

[0008]

The object of the present invention is achieved by a plasma display characterized in that a glass component having an average refractive index of 1.5 to 1.7 is used as a material of the partition wall layer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION
It is formed by performing pattern processing on a glass substrate using a paste containing glass fine particles and an organic component as essential components, followed by firing. The formation of the partition walls using a photosensitive paste containing a photosensitive organic compound in an organic component is simple and can realize high-precision pattern processing.

In this case, when the organic component and the glass fine particles have different average refractive indexes, light scattering occurs inside the paste, which makes it difficult to perform highly accurate pattern processing. Thus, it has been found that light scattering can be suppressed by controlling the refractive index of the glass fine particles and the organic component. The difference between the average refractive index of the glass fine particles and the average refractive index of the organic component is 0.1.
It is preferable that the average refractive index N1 of the glass microparticles and the average refractive index N2 of the organic component have the relationship of the formula (A), so that high aspect ratio and high precision pattern processing can be performed. Will be possible.

−0.03 ≦ N1−N2 ≦ 0.07 (A) However, the glass generally used as the insulator is 1.
While it has a refractive index of about 5 to 1.9, the refractive index of a general organic component is about 1.45 to 1.7. The average refractive index needs to be 1.5 to 1.7. Preferably, by setting the refractive index to 1.55 to 1.65, there is an advantage that the range of selection of the organic component is widened.

On the other hand, since the partition wall is formed by firing on a glass substrate, the thermal softening temperature of the glass component is 350 to 600.
It is preferable that the temperature is about ° C. If the temperature is lower than 350 ° C,
There is a problem that the partition layer is deformed in a later sealing step,
If it exceeds, there is a problem that the partition wall layer having low strength is not melted during firing.

As a glass having such temperature characteristics, a glass containing 20% by weight or more of lead oxide or bismuth oxide has been conventionally used. However, the glass fine particles containing 30 wt% or more of lead oxide and bismuth oxide often have an average refractive index of 1.7 or more.

Glass having a refractive index of 1.5 to 1.7 and a thermal softening temperature of 600 ° C. or less has a content of lead oxide or bismuth oxide in the inorganic fine particles of 30% by weight or less, and
It is obtained by containing 1 to 20% by weight of an alkali metal oxide. In addition, the alkali metal oxide is 3 to 2 times.
By containing 0% by weight, the control of the coefficient of thermal expansion, the temperature characteristics, and the refractive index becomes easy. If it exceeds 20% by weight, the water absorption of the glass increases, which is not preferable for use in displays.

Further, bismuth oxide or lead oxide is added in an amount of 30% by weight.
Below, more preferably 20% by weight or less makes it easy to control various properties by adding a small amount of alkali metal oxide.

As the alkali metal oxide, at least one selected from potassium oxide, sodium oxide and lithium oxide can be used. In particular, from the viewpoint of the pot life of the paste, it is preferable to contain lithium oxide.

As for the composition in the glass fine particles, it is preferable to add silicon oxide in the range of 3 to 60% by weight, and more preferably 20 to 60% by weight. If it is less than 3% by weight, the denseness, strength and stability of the glass layer will be lowered, and the coefficient of thermal expansion will deviate from the desired value, and a mismatch with the glass substrate is likely to occur. Further, when the content is set 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.

Boron oxide is preferably blended in the range of 5 to 50% by weight, more preferably 10 to 40% by weight.
It is. By blending in this range, electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion, and denseness of the insulating layer can be improved. 50% by weight
If it exceeds, the stability of the glass will be reduced.

The inclusion of bismuth oxide or lead oxide has the effect of controlling the baking temperature, but it also has the effect of making it higher than the target refractive index, and is preferably 30% by weight or less.

Further, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide, etc., especially aluminum oxide, barium oxide, zinc oxide to the glass, the hardness and workability can be improved. However, the content is preferably 40% by weight or less, more preferably 30% by weight or less from the viewpoint of controlling the thermal softening point, thermal expansion coefficient, and refractive index. The total content is 50% by weight or less.

As an example of the glass composition preferably used, silicon oxide is 15 to 50% by weight, and boron oxide is 15% by weight.
-40 wt%, barium oxide 2-10 wt%, aluminum oxide 6-25 wt%, lithium oxide 1-15
It is a glass composition containing by weight.

The glass particle size used in the above is
The particle size is selected in consideration of the shape of the pattern to be formed, but the particle size of 50% by weight is preferably 0.1 to 10 μm.

By using 50% by weight or more of glass particles having a sphericity of 80% by number or more as the glass particles, it is possible to reduce the glass surface area and suppress light scattering in the paste.

Further, as fine glass particles, 436 nm
It is preferable to use glass fine particles characterized by using glass fine particles having a total light transmittance of 50% or more at the above wavelength. By suppressing the scattering and absorption inside the glass fine particles, the pattern characteristics are improved.

As the glass fine particles used in this case,
Glass fine particles having a 50% by weight particle size of 1 to 7 μm, a 10% by weight particle size of 0.4 to ² μm, a 90% by weight particle size of 4 to 10 μm, and a specific surface area of 0.2 to ³ m ² / g are suitable.

The refractive index of the glass particles in the present invention can be measured by the Becke method. It is accurate to measure the refractive index at the exposure wavelength to confirm the effect. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Further, it is preferable to measure the refractive index at the i-line (365 nm) or the g-line (436 nm).

In the paste used in the present invention,
By adding glass particles or ceramic particles having a heat softening temperature of 600 ° C. or more in a range of 40% by weight or less,
The shrinkage rate during firing can be suppressed. However, it is important that the difference in the refractive index between the fine particles used in this case is 0.1 or less, or even 0.05 or less, in order to form a pattern with high accuracy.

When the partition layer is blackened for the purpose of improving the contrast of the plasma display, the photosensitive partition to be used contains black metal oxide in an amount of 1 to 10% by weight, so that the black partition is formed. Can be formed.

As the black metal oxide used at this time,
A black partition wall layer can be formed by including at least one, and preferably three or more, of oxides of Cr, Fe, Co, Mn, and Cu. In particular, when the oxides of Fe and Mn are each contained in an amount of 0.5% by weight or more, a black partition wall layer can be formed.

A photosensitive paste can be prepared by dispersing the above-mentioned inorganic fine particles containing a glass component in an organic component containing a photosensitive compound. The organic component used in the present invention is an organic component (a part obtained by removing an inorganic component from the paste) in a paste containing a photosensitive organic substance.

With respect to the photosensitive paste used in the present invention, the content of the photosensitive component is preferably 10% by weight or more, more preferably 30% by weight or more in the organic component from the viewpoint of sensitivity to light.

The organic component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer, and further contains a binder, a photopolymerization initiator, an ultraviolet light absorber, if necessary. Additives such as sensitizers, sensitization aids, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, organic or inorganic precipitation inhibitors and leveling agents can also be added. Be seen.

The photosensitive component includes a photoinsolubilizing type and a photosolubilizing type. As the photoinsolubilizing type, (A) a functional monomer having at least one unsaturated group in the molecule. , Containing oligomers and polymers (B) containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds and organic halogen compounds (C) Condensates of diazo amines and formaldehyde, so-called diazo resins There are things that are called.

As the photo-soluble type, (D) a complex containing an inorganic salt of a diazo compound or an organic acid, and a quinone diazo compound (E) a quinone diazo compound bound to a suitable polymer binder, Examples thereof include naphthoquinone 1,2-diazide-5-sulfonic acid ester of phenol and novolac resin.

As the photosensitive component used in the present invention, all of the above can be used. The photosensitive component that can be easily used as a photosensitive paste by mixing with inorganic fine particles is preferably (A).

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and sec-butyl. Acrylate, sec-
Butyl acrylate, iso-butyl acrylate, te
rt-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, 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, methoxide Shi of cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, 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, diacrylate of bisphenol A-ethylene oxide adduct,
Bisphenol A-propylene oxide adduct diacrylate, thiophenol acrylate, benzyl mercaptan acrylate, and monomers in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p -Methylstyrene,
o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α
-Methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and part or all of the acrylate in the molecule of the above compound to methacrylate Modified ones include γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. In the present invention, these may 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.

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

Further, an oligomer or polymer obtained by polymerizing at least one of the compounds having a carbon-carbon double bond can be used.

During the polymerization, the content of these monomers may be 10% by weight or more, and more preferably 35% by weight or more, so that they can be copolymerized with other monomers.

As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing 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.

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 50 to 180, more preferably 70 to 140. When the acid value is less than 50, the allowable development width becomes narrow. On the other hand, if the acid value exceeds 180, the solubility of the unexposed portion in the developing solution decreases, so that if the developing solution concentration is increased, peeling occurs up to the exposed portion, making it difficult to obtain a high-definition pattern.

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

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

A method for adding such a side chain to an oligomer or a polymer is based on an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid, with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer. There is a method in which chloride, methacrylic chloride or allyl chloride is added to make an addition reaction.

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 crotonate, and glycidyl ether isocrotonic acid. .

Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloyl ethyl 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 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is preferable to add one molar equivalent.

As specific examples of the photopolymerization initiator,
Benzophenone, methyl o-benzoylbenzoate, 4,
4-bis (dimethylamine) benzophenone, 4,4-
Bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, 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, benzyl, Benzyl dimethyl ketanol, benzyl methoxy ethyl 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-butadion-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)
Oximes, Michler's ketones, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4, 4
-Azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphorphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin,
Examples thereof include a combination of a photo-reducing dye such as methylene blue and a reducing agent such as ascorbic acid and triethanolamine. In the present invention, these may be used alone or in combination of two or more. The photopolymerization initiator is added in a range of 0.05 to 10% by weight, more preferably 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 an ultraviolet absorber. A high aspect ratio, high definition and high resolution can be obtained by adding an absorbent having a high ultraviolet absorbing effect. UV absorbers composed of organic dyes, especially 35
Organic dyes having a high UV absorption coefficient in the wavelength range of 0 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 an organic dye is added as a light absorbing agent, it is preferable because deterioration of the insulating film characteristics due to the absorbing agent can be reduced without remaining in the insulating film after firing. Among these, azo dyes and benzophenone dyes are preferred. The amount of the organic dye added is preferably 0.05 to 5% by weight. When the content is less than 0.05% by weight, the effect of adding the ultraviolet absorbent is reduced, and the content is reduced to 5% by weight.
Exceeding the range is not preferred because the properties of the insulating film after firing deteriorate. More preferably, it is 0.1 to 1% by weight. As a method of adding an ultraviolet absorber composed of an organic pigment, after dissolving in an organic solvent, other than a method of kneading at the time of making a paste, a solution in which an organic pigment is previously dissolved in an organic solvent is prepared,
Next, there is a method in which glass powder is mixed with the organic solvent and then dried. 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.

In the present invention, P contained in the inorganic fine particles
Metals and oxides such as b, Fe, Cd, Mn, Co, and Mg may react with the photosensitive components contained in the paste, causing the paste to gel in a short time, making application impossible. In order to prevent such a reaction, it is preferable to add a stabilizer to prevent gelation. As the stabilizer used, a triazole compound is preferably used. Among the triazole compounds, benzotriazole works particularly effectively. To give an example of the surface treatment of glass powder with benzotriazole used in the present invention,
After dissolving a predetermined amount of benzotriazole with respect to the inorganic fine particles in an organic solvent such as methyl acetate, ethyl acetate, ethyl alcohol, and methyl alcohol, the solution is left in a solution for 1 to 24 hours so that these fine particles can be sufficiently immersed. Immerse. After immersion, preferably, the powder is naturally dried at 20 to 30 ° C., and the solvent is evaporated to prepare a powder which has been subjected to a triazole treatment. The ratio of the stabilizer used (stabilizer / inorganic fine particles) is preferably 0.05 to 5% by weight.

The 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-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-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. Can be In the present invention, these may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention, 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.

The polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone,
N-nitrosodiphenylamine, phenothiazine, p-
t-butylcatechol, N-phenylnaphthylamine,
2,6-di-t-butyl-p-methylphenol, chloranil, pyrogallol and the like. When adding a polymerization inhibitor, the amount added, in the photosensitive paste,
Usually, it is 0.001 to 1% by weight.

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

An antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-t.
-4-ethylphenol, 2,2-methylene-bis-
(4-methyl-6-t-butylphenol), 2,2-
Methylene-bis- (4-ethyl-6-t-butylphenol), 4,4-bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-6
-T-butylphenol), 1,1,3-tris- (2
-Methyl-4-hydroxy-t-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-t-
[Butylphenyl) butyric acid] glycol ester, dilaurylthiodipropionate, triphenylphosphite and the like. When adding an antioxidant, the amount added is usually 0.001 to 1% by weight in the paste.

An organic solvent may be added to the photosensitive paste of the present invention when the viscosity of the solution is desired to be adjusted. 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-butyrolactone, bromobenzene, Chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing one or more of these are used.

The refractive index of the organic component is the refractive index of the organic component in the paste when the photosensitive component is exposed to light by exposure. 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.

The measurement of the refractive index in the present invention is preferably performed by the V-block method which is generally performed, and the wavelength to be measured is measured by the wavelength of light to be exposed after applying the paste in order to confirm the effect. Be accurate. In particular, 350-6
It is preferable to measure with light having a wavelength in the range of 50 nm. Furthermore, i-line (365 nm) or g-line (43
6 nm) is preferred.

In addition, in order to measure the refractive index after the organic component is polymerized by irradiation with light, the same light as in the case of irradiating light into the paste can be measured by irradiating only the organic component.

The glass powder containing bismuth oxide or lead oxide in an amount of 10% by weight or more, which can be baked on a glass substrate, may have a refractive index of 1.6 or more. It needs to be high.

In this case, it is necessary to introduce a high refractive index component into the organic component, and a sulfur atom, a bromine atom,
It is effective to use a compound having an iodine atom, a naphthalene ring, a biphenyl ring, an anthracene ring, and a carbazole ring in an amount of 10% by weight or more to increase the refractive index. Further, by containing 20% by weight or more of the benzene ring, the refractive index can be increased.

Particularly, a sulfur atom or a naphthalene ring is
When the content is 0% by weight or more, the refractive index of the organic component can be more easily increased. However, if the content is 6
If the content is 0% by weight or more, a problem occurs in that the photosensitivity is reduced.

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

Examples of the monomer containing a sulfur atom in the molecule include compounds represented by the following general formula (a), (b) or (c).

[0065]

Embedded image R in the structural formula represents a hydrogen atom or a methyl group. X is S or O, l is an integer of 1 to 3, m, n, p, and q are 0 to 0.
Indicates an integer of 3.

As the sensitizer, one having absorption at the exposure wavelength is used. In this case, since the refractive index becomes extremely high in the vicinity of the absorption wavelength, it is possible to add a large amount of the sensitizer. The refractive index can be improved. In this case, the sensitizer may be added to the paste in an amount of 0.5 to 10% by weight. More preferably, it is 1 to 6% by weight.

The photosensitive paste is usually glass fine particles,
After preparing various components such as an ultraviolet light absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, and a solvent so as to have a predetermined composition, the mixture is uniformly mixed and dispersed with a three-roller or a kneading machine.

The viscosity of the paste is appropriately adjusted by the addition ratio of the inorganic fine particles, the thickener, the organic solvent, the plasticizer and the suspending agent, and the range is 2000 to 200,000 cp.
s (centipoise). For example, when coating on a glass substrate is performed by a spin coating method,
cps is preferred. 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 20000 cps is preferable.

Next, an example of patterning the partition layer of the plasma display according to the present invention will be described. However, the present invention is not limited to this.

On a glass substrate or polymer film,
The photosensitive paste is applied entirely or partially. As a coating method, a general method such as screen printing, a bar coater, and a roll coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the mesh of the screen, and the viscosity of the paste. However, the partition wall of the plasma display needs to have a thickness of 100 to 200 μm, and in consideration of shrinkage due to drying and baking, 120 to 200 μm.
It is preferable to apply with a thickness of about 300 μm.

Here, the surface treatment of the glass substrate can be carried out in order to enhance the adhesion between the paste and the glass substrate. As the surface treatment liquid, a silane coupling agent such as vinyltrichlorosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ -Chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like, or organic metals such as organic titanium, organic aluminum and organic zirconium. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. Next, the surface treatment liquid is uniformly applied on a substrate with a spinner or the like, and then surface-treated by drying at 80 to 140 ° C. for 10 to 60 minutes. By applying a paste sheet (photosensitive green sheet) on a glass substrate, application onto the glass substrate can be easily performed.

The glass substrate used in the present invention is not particularly limited as long as it is a general one, but general soda lime glass, glass obtained by annealing soda lime glass, or high strain point glass (for example, Manufactured by Asahi Glass Co., Ltd.
PD-200 ″) 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, silver, aluminum, copper,
It is common to use an electrode layer formed by patterning gold, nickel, tin oxide, ITO, or the like by screen printing or photolithography using a photosensitive conductive paste. Further, a glass substrate having a dielectric layer on the electrode layer for stabilizing discharge may be used.

After coating, 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. As the exposure device, a stepper exposure device, a proximity exposure device, or the like can be used.

Performing the exposure step only once is preferable as a method for forming the partition layer with high accuracy and more easily than in the case of performing the exposure a plurality of times.

When a large area is exposed, a photosensitive paste is applied on a substrate such as a glass substrate and then exposed while being conveyed, so that a large effective area can be obtained with an exposure machine having a small effective exposure area. It 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, etc. are preferable. Among them, ultraviolet light is preferable. Etc. can be used. Among these, an ultra-high pressure mercury lamp is preferred.
Exposure conditions vary depending on the coating thickness, but 0.5 to 100
0.5 to 3 using an ultra-high pressure mercury lamp having an output of mW / cm ^2.
Exposure is performed for 0 minutes. In particular, when the exposure amount is 0.3 to 5 J / c
Exposure of about m ² is preferred.

The pattern shape can be improved by providing an oxygen shielding film on the surface of the applied photosensitive paste. As an example of the oxygen shielding film, a film such as PVA or cellulose, or a film such as polyester is used.

The PVA 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 drying at 70 to 90 ° C. for 10 to 60 minutes to evaporate the water content. Let me do it. In addition, it is preferable to add a small amount of alcohol to the aqueous solution because the coatability with the insulating film is improved and the evaporation is facilitated. A more preferable PVA solution concentration is 1 to 3% by weight. Within this range, the sensitivity is further improved. It is estimated that the reason why the PVA coating improves the sensitivity is as follows. That is, when the photosensitive component undergoes a photoreaction, it is considered that the presence of oxygen in the air interferes with the photocuring sensitivity. However, the presence of a PVA film improves the sensitivity during exposure because excess oxygen can be blocked, which is preferable. .

When a transparent film of polyester, polypropylene, polyethylene or the like is used, there is a method of sticking these films on the photosensitive paste after coating.

After exposure, development is performed using a developing solution. In this case, dipping, spraying or brushing is used. As the developing solution, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. Water may be added to the organic solvent as long as the solvent does not lose its solubility. 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, 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, 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 10% by weight.
~ 5% by weight. 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 good. The development temperature during development is preferably 20 to 50 ° C. for process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of the paste and the substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. The firing temperature is 400 to 610 ° C. When patterning is performed on a glass substrate, baking is performed at a temperature of 520 to 610 ° C. for 10 to 60 minutes. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

A heating step of 50 to 300 ° C. may be introduced into each of the above steps for the purpose of drying and preliminary reaction.

The glass substrate having the partition layer obtained by the above steps can be used on the front side or the back side of the plasma display. Further, it can be used as a substrate for discharging the address part of the plasma addressed liquid crystal display.

After applying the phosphor between the formed barrier rib layers, the front and rear glass substrates are sealed together, and helium,
By enclosing a rare gas such as neon or xenon,
The panel portion of the plasma display can be manufactured. Furthermore, by mounting a driver IC for driving,
Plasma displays can be manufactured.

In order to increase the definition of the plasma display, that is, to increase the number of pixels in a fixed screen size, it is necessary to reduce the size of one pixel. In this case, it is necessary to reduce the pitch between the partition walls. However, when the pitch is reduced, the discharge space is reduced and the coated area of the phosphor is reduced, so that the luminance is reduced. Specifically, a 42-inch HDTV (1
In order to realize an OA monitor (920 × 1035 pixels) or a 23-inch OA monitor (XGA: 1024 × 768 pixels), it is necessary to make the size of the pixels 450 μm square, and partition walls for partitioning each color are formed at a pitch of 150 μm. There is a need. In this case, if the line width of the partition is large, it is difficult to improve the luminance because a space for discharge cannot be secured or the application area of the phosphor is reduced.

The inventors have found that the width of the partition wall can be reduced by using the technique of the present invention. In particular, it is possible to obtain a plasma display in which stripe-shaped partition walls having a partition wall width of 20 to 40 μm, and preferably a partition width of 20 to 35 μm can be obtained, which is effective for improving luminance at the time of high definition.

By forming high-definition barrier ribs having a height of 100 to 170 μm and a pitch of 100 to 160 μm, it is possible to provide a high-definition plasma display which can be used for a high-definition television or a computer monitor.

[0090]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this. The concentrations (%) in Examples and Comparative Examples are% by weight unless otherwise specified.

In the example, a photosensitive paste containing inorganic fine particles and an organic component was prepared. The preparation procedure was as follows. First, each component of the organic component and γ-butyrolactone were dissolved while heating at 80 ° C., then inorganic fine particles were added, and the mixture was kneaded with a kneader to prepare a paste. The viscosity was adjusted by adjusting the amount of solvent. Solvent amount (γ-butyl lactone)
Was adjusted to 10 to 40% in the paste.

Next, a soda glass substrate or a quartz glass substrate of 30 cm square is applied by screen printing a plurality of times to obtain 100 μm, 150 μm, 200 μm.
After applying the coating to the coating thickness of
And dried.

Next, exposure was performed through a photomask. The following two types of masks were used.

[0094] (1) pitch 220 .mu.m, chrome negative mask (2) the pitch 150μm line width 50 [mu] m, the chrome negative mask exposure line width 20 [mu] m,. 2 to ultra-high pressure mercury lamp with an output of 50 mW / cm ²
Ultraviolet light exposure was performed at a light amount of 10 J / cm ² . afterwards,
Development was performed by immersing in a 0.5% aqueous solution of monoethanolamine.

Further, the obtained glass substrate was exposed to 80 ° C. for 1 hour.
Maximum temperature after drying for 550 ℃ or 850 ℃
Firing was performed at (maximum temperature holding time 30 minutes).

As a result of cutting the obtained sample and observing the cross section with a scanning electron microscope, the case where a good partition wall pattern was formed was evaluated as ◯, and the unexposed portion due to pattern loss / disconnection and poor development was evaluated. The case where good partition walls were not formed due to clogging or the like was evaluated as x. The results are shown in Table 3.

The refractive index of the organic component is adjusted to 436 nm at 25 ° C. by the ellipsometry method after adjusting the organic component in the paste and applying and drying.
The measurement was performed for light having a wavelength of.

Example 1 In Table 1, 75 g of the glass powder of A1 and 25 parts of the organic component of B3 were added.
g was used to make a paste. The solvent used was 1
It was 0 g. Table 3 shows the results of pattern formation and baking at 560 ° C. for 30 minutes.

On a soda glass substrate (thickness: 2.8 mm) having a size of 360 × 500 mm, a photosensitive silver paste was used and a line width was 40 μm, a pitch was 150 μm, and a thickness was 1.
After forming a stripe-shaped silver wiring of 0 μm, the paste is applied to the entire surface to a thickness of 200 μm, and a photomask having a pitch of 150 μm and a line width of 20 μm is used to perform exposure, development, and baking to perform partition Layers were formed. After that, a phosphor paste was applied by screen printing, followed by baking at 450 ° C. for 20 minutes to produce a back plate of a 23-inch plasma display. By attaching this back plate to the front plate and enclosing gas, 2
A 3 inch XGA (1024 x 768 pixels) monitor can be made.

Example 2 75 g of A2 glass powder and 25 organic components of B3 in Table 1 were added.
g was used to make a paste. The solvent used was 1
It was 5 g. Table 3 shows the results of pattern formation and baking at 560 ° C. for 10 minutes.

Example 3 70 g of the glass powder of A3 and 30 parts of the organic component of B4 in Table 1 were added.
g was used to make a paste. The solvent used was 1
It was 5 g. Table 3 shows the results of pattern formation and baking at 560 ° C. for 10 minutes.

Example 4 80 g of glass powder of A4 and 20 g of organic component of B4 in Table 1
Was used to prepare a paste. The solvent used is 7 g
Met. Table 3 shows the results of pattern formation and baking at 580 ° C. for 15 minutes.

Example 5 80 g of the glass powder of A4 and 20 g of the organic component of B2 in Table 1
Was used to prepare a paste. The solvent used was 11
g. Table 3 shows the results of pattern formation and baking at 580 ° C. for 15 minutes.

Example 6 75 g of A5 glass powder and 25 g of B1 organic component in Table 1
Was used to prepare a paste. The solvent used was 12
g. Table 3 shows the results of pattern formation and baking at 580 ° C. for 15 minutes.

Example 7 75 g of A6 glass powder and 25 g of B3 organic component in Table 1
Was used to prepare a paste. The solvent used was 10
g. Table 3 shows the results of pattern formation and baking at 850 ° C. for 15 minutes.

Example 8 60 g of A1 glass powder and 15 A6 glass powder in Table 1
After mixing g, a paste was prepared using 25 g of the organic component of B3. The solvent used was 10 g. Table 3 shows the results of pattern formation and baking at 580 ° C. for 30 minutes.

Comparative Example 1 75 g of glass powder of A3 and 25 g of organic component of B2 in Table 1
Was used to prepare a paste. The solvent used was 10
g. Table 3 shows the results of pattern formation and baking at 560 ° C. for 10 minutes.

Comparative Example 2 75 g of A4 glass powder and 25 g of B4 organic component in Table 1
Was used to prepare a paste. The solvent used was 10
g. Table 3 shows the results of pattern formation and baking at 580 ° C. for 15 minutes.

[0109]

[Table 1]

[Table 2]

[Table 3] Abbreviations in the table are shown below.

(The numbers in the structures of Polymers 1 to 3 represent the constituent molar ratios of the respective monomers) TMPTA: trimethylolpropane triacrylate TBPMA: tribromophenyl methacrylate TBB-ADA: tetrabromobisphenol A diacrylate BMEXS- MA:

Embedded image MPS-MA:

Embedded image PVA: Polyvinyl alcohol Sudan: Azo red dye, C ₂₄ H ₂₀ N ₄ O-Upinal D-50: Benzophenone dye (Upinard D-50) C ₁₃ H ₁₀ O ₅ MTPMP: 2-Methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1 EPA: p-dimethylaminobenzoic acid ethyl ester DET: 2,4-diethylthioxanthone γ-BL: γ-butyrolactone polymer 1:

Embedded image (Weight average molecular weight: 43000, acid value: 90) Polymer 2:

Embedded image (Weight average molecular weight: 32000, acid value: 95) Polymer 3:

[Chemical 6] (Weight average molecular weight: 30,000, acid value: 101)

[0111]

The present invention relates to a plasma display having high-precision partition walls, and can provide a plasma display capable of high definition.

 ─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 8-61048 (32) Priority date Hei 8 (1996) March 18 (33) Priority claim country Japan (JP)

Claims (11)

[Claims] 1. The average refractive index of the partition wall material is 1.5 to
A plasma display using a glass component of 1.7. 2. The plasma display according to claim 1, wherein a glass component having an average refractive index of 1.55 to 1.65 is used. 3. A glass component having a heat softening temperature of 350 to 350.
The plasma display according to claim 1, wherein a glass component at 600 ° C. is used in an amount of 60% by weight or more. 4. A glass component containing at least one of potassium oxide, sodium oxide, and lithium oxide, and the total amount of them is 3 to 20% by weight, as a glass component. The plasma display described. 5. Lithium oxide 3-1 as a glass component.
The plasma display according to claim 1, wherein a glass component containing 5% by weight is used. 6. A glass component containing at least one kind of potassium oxide, sodium oxide and lithium oxide, the total amount of which is 1 to 20% by weight, and bismuth oxide of 5 to 30% by weight. The plasma display according to claim 1, wherein the glass component is used. 7. The plasma display according to claim 1, wherein a glass component containing 3 to 60% by weight of silicon oxide and 5 to 50% by weight of boron oxide is used as the glass component. 8. As a glass component, 3 to 60% by weight of silicon oxide, 5 to 50% by weight of boron oxide, and 1% of barium oxide are used.
The plasma display according to claim 1, wherein a glass component containing 30 to 30% by weight and 1 to 30% by weight of aluminum oxide is used. 9. A glass component containing 15 to 50 silicon oxide.
% Of boron oxide, 2 to 10% by weight of barium oxide, 6 to 25% by weight of aluminum oxide, and 1 to 15% by weight of lithium oxide are used. Item 2. A plasma display according to item 1. 10. The plasma display according to claim 1, wherein the partition layer has a stripe shape with a line width of 20 to 40 μm. 11. The plasma display according to claim 1, wherein the partition layer has a stripe shape with a line width of 20 to 40 μm, a height of 100 to 170 μm, and a pitch of 100 to 160 μm.