JPH1184638A - Photosensitive glass paste and production of plasma display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a paste coating layer having a uniform thickness by specifying the b.p. difference between at least two or more kinds of org. solvents contained in a photosensitive glass paste. SOLUTION: The photosensitive glass paste consists of glass powder, a photosensitive org. component and two or more org. solvents and the b.p. difference between at least two of the org. solvents is >=20 deg.C. The amts. of the low and high b.p. org. solvents are 10-90 wt.% each of the total amt. of the org. solvents. The total amt. of the org. solvents is 1-50 wt.% of the amt. of the entire photosensitive glass paste. An oligomer or polymer having carboxyl groups and/or unsatd. double bonds in one molecule and a wt. average mol.wt. of 500-100,000 is essentially contained in the photosensitive org. component by 10-90 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive glass paste used for a plasma display, a plasma addressed liquid crystal display, and the like, and a method for manufacturing a plasma display using the same.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Are capable of high-speed display compared to liquid crystal panels, and are easy to increase in size, and thus have permeated OA equipment and public information display devices. Further, progress in the field of high-definition television is highly expected.

[0003] With the expansion of such applications, attention has been paid to color PDPs having delicate and numerous display cells. This color PDP generates a plasma discharge between opposing anode and cathode electrodes in a discharge space provided between a front glass substrate and a rear glass substrate, and is generated from a gas sealed in the discharge space. The display is performed by irradiating ultraviolet light to a phosphor provided in the discharge space. In this case, a partition (also referred to as a barrier or a rib) is provided in order to suppress the spread of the discharge to a certain area and perform display in a specified cell, and to secure a uniform discharge space. The shape of this partition is a high definition PD
For P, about 20-80 μm width and 60-200 μm height
The partition is formed by applying a photosensitive glass paste made of glass to a front glass substrate or a rear glass substrate, drying, exposing, developing and firing.

A screen printing method is known as a method for forming a partition layer. However, in this method, 1
60-200 μm in height due to several tens of μm
In order to form the partition layer, it is necessary to repeat printing / drying many times, generally ten times or more, and there is a problem that productivity is extremely poor. In order to solve this problem, as a method of applying the paste at one time, there is a method of applying the paste by a doctor blade method, a slit die coating method, or the like. However, in the case of this one-time application, especially in the case of doctor blade application, after the paste is applied and dried, the edge portion of the paste application layer (partition formation layer) rises by about 30 μm to form an application layer having a uniform film thickness. There was a problem that it was not possible.

[0005]

SUMMARY OF THE INVENTION According to the present invention, when a photosensitive glass paste is applied and dried, a swelling of an edge portion of the paste applied layer is small and a paste applied layer having a uniform film thickness is formed. It is an object to provide a photosensitive glass paste capable of being used.

Another object of the present invention is to provide a method of manufacturing a high quality plasma display using such a photosensitive glass paste.

[0007]

Means for Solving the Problems To solve the above-mentioned problems, a photosensitive glass paste of the present invention is a photosensitive glass paste comprising a glass powder, a photosensitive organic component and an organic solvent, wherein two or more kinds of the organic solvent are used. And at least two of the organic solvents have a boiling point difference of 2
The temperature is set to 0 ° C. or higher, and the present invention further includes the following preferred embodiments.

(A) The content of the organic solvent on the low boiling point side and the high boiling point side in the organic solvent is in the range of 10 to 90% by weight based on the total amount of the organic solvent.

(B) The total content of the organic solvent is in the range of 1 to 50% by weight based on the whole photosensitive glass paste.

(C) As an essential component of the photosensitive organic component, an oligomer or polymer having a carboxyl group in the molecule and / or an unsaturated double bond in the molecule and having a weight molecular weight of 500 to 100,000 is included in the amount of the photosensitive organic substance. 1 for
0-90% by weight.

(D) The photosensitive organic component contains an organic dye in an amount of 0.05 to 2% by weight based on the weight of the photosensitive organic substance.

Further, a method of manufacturing a plasma display according to the present invention uses the above-mentioned photosensitive glass paste.
A method for manufacturing a plasma display including a step of applying the photosensitive glass paste on a substrate, pattern exposure after drying, development, and further baking to form a partition,
The photosensitive glass paste is characterized in that the thickness of one application of the photosensitive glass paste is 50 μm or more, and in the present invention, the application of the photosensitive glass paste for forming the partition is performed by a doctor blade method or a slit die coating method. Preferably, the application of the photosensitive glass paste for forming the partition can be performed once or twice.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a photosensitive glass paste comprising a glass powder, a photosensitive organic component and an organic solvent, comprising at least two kinds of the organic solvents and at least two kinds of the organic solvents. 20 ° C boiling point difference of solvent
By the above, paste application, after drying, little swelling of the edge portion of the paste application layer,
It is possible to form a paste coating layer having a uniform thickness. In the present invention, the photosensitive glass paste is usually
Glass powder, photosensitive monomer, oligomer, polymer,
It contains an organic solvent, a photopolymerization initiator, a sensitizer, a sensitization aid, a plasticizer, and the like.

As the organic solvent used in the present invention, a liquid having a boiling point at normal pressure of 20 to 250 ° C. is preferably used. Considerations when selecting an organic solvent to be added include the boiling point at normal pressure, volatility, solubility in photosensitive organic substances, miscibility, dispersion characteristics, and rheological characteristics. For example, when the boiling point at normal pressure is too high, it is necessary to raise the drying temperature, which may cause thermal decomposition or thermal polymerization of the photosensitive organic component. In addition, when a solvent having excellent volatility is used, while there is an advantage that drying is easy, the leveling property of the paste is deteriorated, and the surface flatness is deteriorated. It becomes difficult to stabilize the composition. In addition, when the solubility or dispersibility in the photosensitive organic substance is poor, problems such as the inability to form a paste coating film having a uniform film thickness occur. The organic solvent to be added is selected in consideration of these points.

The organic solvent preferably used in the present invention includes γ-butyrolactone (hereinafter referred to as γ-BL), cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, isopropyl alcohol, methyl alcohol, ethyl alcohol, butyl alcohol, normal Alcohols such as propyl alcohol, ketones such as methyl ethyl ketone, dioxane, acetone, cyclopentanone, diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl lactate, methyl acetate, ethyl acetate, isopropyl acetate,
Normal propyl acetate, isobutyl acetate,
N-pentyl acetate, iopentyl acetate, 3-methoxy-3-methyl-1-butanol, 3-
Esters such as methoxy-3-methyl-butyl acetate and propylene glycol 1-monomethyl ether-2-acetate; hydrocarbons such as hexane, cyclohexane, benzene, toluene and xylene; chlorination such as methylene chloride, chloroform and dichloromethane. Hydrocarbons and the like.

Of these organic solvents, the following Comparative Example 1
As shown in, for example, the boiling point at normal pressure is 200 to 2
When a photosensitive glass paste containing only γ-butyrolactone (γ-BL) at 08 ° C. is applied once by a doctor blade method and dried, a paste coating layer (film thickness 1 after drying) is obtained.
70μm) edge width of about 2cm, about 3cm
It rises about 0 μm. When exposed using a mask in this state, and the unexposed portion of the raised portion is to be washed away with the developing solution, the exposed portion, that is, the partition portion is excessively eroded by the developing solution, and meanders or peels off. Occurs. In other words, when the paste film thickness is not uniform, the development time varies, so that the remaining film, meandering,
A clean partition wall without peeling cannot be formed.
Therefore, it is important to make the paste application thickness as uniform as possible.

In the practice of the present invention, it is necessary that the organic solvent as an essential component contains two or more kinds of organic solvents having a boiling point difference at normal pressure. The boiling point difference of the organic solvent at normal pressure is 20-100.
℃, more preferably 30 ~
It is in the range of 60 ° C. When the difference in boiling point is small, the amount of swelling at the edge of the coated surface after drying is about 30 μm as in the case of using only one organic solvent, and the swelling amount cannot be reduced. When there is a difference in boiling point of 100 ° C. or more, it is difficult to set the drying temperature. This is because if the drying temperature is set at a temperature intermediate between the high boiling point solvent and the low boiling point solvent, a considerable amount of the high boiling point solvent will remain. In addition, when the drying temperature is set to a temperature higher than the high boiling point, there is a high possibility that the photosensitive organic substance may undergo thermal decomposition or thermal polymerization. For this reason, the boiling point difference of the organic solvent at normal pressure is preferably in the range of 20 to 100 ° C, more preferably 30 to 60 ° C.

The content of the organic solvent with respect to the entire photosensitive glass paste is preferably 1 to 60% by weight, more preferably 10 to 40% by weight. If the amount of the organic solvent is too large, the drying time is prolonged, and the productivity is deteriorated.

Furthermore, the content of each of the organic solvents on the low boiling point side and the high boiling point side having a boiling point difference of 20 ° C. or more is preferably in the range of 10 to 90% by weight, more preferably 30 to 90% by weight, based on the total amount of the organic solvent. ７０70% by weight. In the case of two kinds of organic solvents, when the content of any one kind of organic solvent is extremely small, the effect of adding the solvent is not obtained as a result, and the amount of swelling of the edge portion of the coating layer is not reduced. . In the present invention, when three or more kinds of organic solvents are used, it is preferable that the two kinds of organic solvents on the low boiling point side and the high boiling point side are respectively in the above range, and the other organic solvents are out of the above range. It doesn't matter. Alternatively, it is preferable that the organic solvent group is divided into a low boiling point side and a high boiling point side and the respective organic solvent groups are within the above range.

In the present invention, the photosensitive organic substance means a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer. The photosensitive glass paste contains, as necessary, a photopolymerization initiator, a sensitizer, a sensitization aid, a polymerization inhibitor, a binder, a plasticizer, a leveling agent, an ultraviolet absorber, etc., in addition to these photosensitive organic substances. Can be done.

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, cyclopentynyl acrylate, cyclopentenyl acrylate, 2-ethylhexyl acrylate , Glycerol acrylate, glycidyl acrylate, heptadecafluorodisil acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene Glycol acrylate, meth Shi diethylene chip glycol acrylate, octa fluorosilicone pentyl acrylate, phenylene carboxyethyl 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, acrylate such as thiophenol acrylate and benzyl mercaptan acrylate.

In addition to the above, 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.

In the present invention, the content of the monomer as the photosensitive organic substance is preferably 5 to 30% by weight based on the sum of the glass powder and the photosensitive organic substance. A range outside these ranges is not preferred because the pattern formability tends to deteriorate and insufficient curing after curing tends to occur.

Further, as the photosensitive oligomer and the photosensitive polymer which are photosensitive organic substances, those obtained by synthesizing one or more of the above-mentioned photosensitive monomers can be used. The content of the photosensitive oligomer and the photosensitive polymer is 5 to the sum of the glass powder and the photosensitive organic substance.
~ 30% 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 tends to increase.

In the present invention, a weight-average molecular weight of 500 to 10 having a carboxyl group in the molecule and / or an unsaturated double bond in the molecule is an essential component of the photosensitive organic component.
It is preferable that the content of the 000 oligomer or polymer is 10 to 90% by weight based on the amount of the photosensitive organic substance. The proportion of the photosensitive organic component used in the photosensitive glass paste of the present invention is preferably from 5 to 35% by weight from the viewpoints of pattern formability and shrinkage after firing. Outside this range, pattern formability is not possible or the pattern becomes thicker, which is not preferable.

The glass powder used in the present invention is 5
Thermal expansion coefficient of 0~400 ℃ (α ₅₀ ~ ₄₀₀₎ 50 to 90
It is preferably × 10 ⁻⁷ . By mixing silicon oxide in the glass in the range of 3 to 60% by weight and boron oxide in the range of 5 to 50% by weight, electric, mechanical and electrical properties such as electric insulation, strength, coefficient of thermal expansion, and denseness of the insulating layer can be improved. Thermal characteristics can be improved. Glass transition temperature is 430-5
It is preferable that the softening point is 470 to 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. In addition, the glass transition temperature is 4
In the case of glass having a softening point of lower than 470 ° C. at 30 ° 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.
Preferably, the specific surface area is 1.5 μm or less, and the specific surface area is 1.5 to ⁴ cm ² / g. As a photopolymerization initiator, benzophenone, o
Methyl benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone,
Dibenzyl ketone, fluorenone, 2,2-dimethoxyacetylphenone, 2,2-dimethoxy-2-methyl-2
-Phenyl-2-phenylacetylphenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylchooxanthon, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl , Benzyldimethylmethyl ketanol, benzylmethoxyethyl 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-butanedione 2- (o-methoxycarbonyl) oxime and 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime. 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 20% by weight, more preferably in the range of 0.1 to 15% by weight, based on the photosensitive 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.

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-dimethylaminobenzyldenindanonena and the like can be mentioned. . In the present invention, one or more of these can be used. The addition amount is 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive 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, monoester compounds of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol and N-phenylnaphthylamine, chloranil, and the like. The addition amount is usually 0.001 to 1% by weight.

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.

In the present invention, it is preferable to add an ultraviolet absorber, so that high definition and high resolution can be obtained. Organic dyes are often used as UV absorbers. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinone dyes, and benofenone dyes can be used. The addition amount is 0.05 to glass powder.
5% by weight is preferred. If the addition amount is small, the effect of adding the ultraviolet absorber decreases, and if it is too large, the properties of the insulating film after firing may deteriorate, which is not preferable. More preferably 0.0
5 to 0.18% by weight.

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.

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

In the use of the photosensitive glass paste of the present invention, it is necessary to dry the paste after the paste is applied. However, a point to be noted in this drying is to keep the photosensitive glass paste horizontal. This is because, if it is slightly tilted, the paste flows and uneven film thickness occurs. As a drying method, a commonly used method such as a hot air oven or a hot plate, far infrared rays, natural drying and reduced pressure drying can be used, but the important point is that the photosensitive glass paste layer is moved in the depth direction. The point is that it is dried uniformly.
For example, in the case of drying using a hot plate, heat is transferred from the bottom of the paste to the top, and the bottom of the paste dries before the surface, so that there is no danger of air bubbles being trapped. Air drying takes time and productivity is poor. In addition, vacuum drying requires a vacuum device, which increases equipment costs and lowers productivity. From such a point, it is preferable to use a hot plate for drying the photosensitive glass paste.

The drying temperature may be any number as long as it is lower than the temperature at which the photosensitive organic substance does not cause thermal polymerization.
Generally, the range of 40 to 150 ° C. is preferable. Here, the drying temperature means, for example, in the case of drying using a hot plate, the temperature of the hot plate surface, and in the case of a hot air oven, the temperature of hot air.

Next, a method for preparing the photosensitive glass paste of the present invention will be described. Photosensitive glass paste is usually prepared by mixing various components such as glass powder, photosensitive monomers, oligomers and polymers, photopolymerization initiators, sensitizers, and organic solvents so as to have a predetermined composition. Mix and disperse evenly with a machine to produce. The viscosity of this paste is determined by the addition ratio of glass powder, photosensitive monomers, oligomers, polymers, organic solvents, plasticizers and the like, but the range is preferably 0.5 to 200 Pa · s.
It is. For example, application to a glass substrate is preferably 30 to 200 Pa · s by a screen printing method, 2 to 50 Pa · s by a doctor blade method or a slit die coating method, and 0.5 to 2 Pa · s by a spin coating method.

Next, an example of performing pattern processing using a photosensitive glass paste will be described. A photosensitive glass paste is applied entirely or partially on a glass substrate, a ceramic substrate, or a polymer film. Screen coating, bar coating,
General methods such as roll coating, slit die coating, doctor blade and spin coating can be used.

Here, when the photosensitive glass paste is applied on the substrate, the substrate can be treated in advance with a surface treatment liquid in order to increase the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropanetrimethoxysilane, γ- (methacryloxypropyl) ) Trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptanpropyltrimethoxysilane and the like, or an organic metal, for example, organic titanium, organic aluminum and organic zirconium And so on. A silane coupling agent or an organic metal is dissolved in an organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol and propyl alcohol, in an amount of 0.5 to 5%.
Use a solution diluted to a concentration of 1. Next, after uniformly applying this surface treatment liquid on the substrate with a spinner or the like,
Surface treatment can be performed by drying at 140 ° C. for 10 to 60 minutes.

After the application of the photosensitive glass paste, exposure is performed using an exposure device. Exposure is generally performed by a mask exposure using a photomask, as 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 red or blue laser light 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. Also,
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 exposure while transporting the photosensitive paste. In this case, as the active light source used, for example, visible light, near ultraviolet light, ultraviolet light, electron beam, X
Among them, ultraviolet rays are preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp,
A germicidal lamp or the like can be used. Among these, an ultra-high pressure mercury lamp is preferable. Exposure conditions vary depending on the coating thickness,
Exposure is preferably performed for 0.2 to 30 minutes using an ultra-high pressure mercury lamp having an output of 1 to 100 mW / cm ² .

On the surface of the applied photosensitive glass paste,
By providing the oxygen blocking film, the pattern shape can be improved. As an example of the oxygen barrier film, PVA
And a film of cellulose or the like, or a film of polyester or the like. The method of forming the PVA film has a concentration of 0.5.
An aqueous solution of about 5% by weight is uniformly applied on a 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, and when the concentration is in this range, the sensitivity can be further improved. The reason why the sensitivity is improved by the PVA application is presumed as follows. That is, when oxygen in the air is present when the photosensitive component undergoes a photoreaction, it is considered that the sensitivity of photocuring is impaired. However, the presence of a PVA film is considered to improve the sensitivity during exposure because excess oxygen can be blocked. . When a transparent film of polyester, polypropylene, polyethylene, or the like 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 utilizing the difference in solubility between the photosensitive portion and the non-photosensitive portion with respect to the development.
It 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 the dissolving 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 and calcium hydroxide aqueous solution is used, but it is preferable to use an organic alkali aqueous solution since the alkali component can be easily removed during firing. As the organic alkali, an amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine. 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. On the other hand, 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. The development temperature during development is 20 to 50.
It is preferable to carry out at a temperature of ° C in terms of process control.

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. The firing is performed at a temperature of 500 to 610 ° C. for 5 to 60 minutes. A particularly preferred temperature is 530-580 ° C.

A heating step at 50 to 200 ° C. may be introduced for the purpose of drying and preliminary reaction during each of the above-mentioned coating, exposure, development and baking steps. 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 drive circuit after sealing and introducing a rare gas together with the obtained rear substrate and front substrate.

[0043]

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 A photosensitive paste was prepared by adding the following glass fine particles and the following organic components at the following paste composition ratios. In the production procedure, first, each component of the organic component was dissolved while being heated to 80 ° C., and then, fine glass particles were added and kneaded with a kneader to prepare a paste.

The rise of the edge portion was measured using a surface roughness meter (Surfcom 1500A, Tokyo Seimitsu Kagaku Co., Ltd.).
The measurement was performed at a scan speed of 0.6 mm / s. Also,
The evaluation of the partition pattern was performed by observation with an electron microscope. The evaluation criteria were 〇 when a good shape (a trapezoidal shape with a slightly wider lower portion) was obtained, and × when the film meandered, peeled off, or left a residual film.

Glass powder: Li ₂ O: 8.6%, Si
O ₂ : 20.1%, B ₂ O ₃ : 31%, BaO: 3.8
_{%, Al 2 O 3: 20.6} %, ZnO: 2.1%, Mg
O: 5.9%, CaO: 4.2% composition (analytical value). The average refractive index was 1.586. This glass powder was used after coating with an ultraviolet absorbing agent.

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: 2~10 photopolymer (X-4007): 40% methacrylic acid, 30% methyl methacrylate over preparative, mosquito copolymer composed of 30% styrene A photosensitive polymer having a weight average molecular weight of 43,000 and an acid value of 95, obtained by addition polymerization of 0.4 equivalent of glycidyl methacrylate to ruboxyl group.

Photopolymerization initiator (IC-369): Irgacure-369 (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 ° C.): ethyl cellosolve (boiling point 135.6 ° C.) The calculated average refractive index of the components was about 1.59, which was very close to the glass refractive index 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: γ-butyrolactone 10.85%: Ethyl cellosolve 10.85% Next, the above photosensitive glass paste was applied onto a 100 mm square glass substrate by a doctor blade method with a clearance of 420 μm, and using a hot plate. After drying at 80 ° C. for 120 minutes, the swelling of the edge portion of the paste coating film was measured and found to be 2 μm.

Next, mask exposure was performed. As the mask, a chromium mask having a pitch of 220 μm, a line width of 60 μm, and a chromium mask designed to enable formation of a stripe-shaped partition pattern in a plasma display was used. Exposure is
0.8 J / c with an ultra-high pressure mercury lamp at an output of 30 mW / cm ²
m ² UV exposure was performed. Thereafter, shower development was performed at 35 ° C. using a 0.3% aqueous solution of monoethanolamine, and drying was performed at 80 ° C. for 10 minutes. The results are shown below.

Height of edge: 2 μm Height of partition: 179 μm Half width: 63 μm Shape: 〇 (Example 2) As shown in the following composition, γ-butyrolactone (boiling point: 200 to 208 ° C.) and ethyl lactate (organic solvent) Except that the boiling point was 154 ° C.), the procedure was the same as in Example 1.

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: γ-butyrolactone 15.85%: ethyl lactate 5.85% The results are shown below.

Edge bulge: 3 μm Height of partition: 181 μm Half width: 60 μm Shape: 〇 (Example 3) As the following composition, γ-butyrolactone (boiling point 200 to 208 ° C.) and 3-methoxy as an organic solvent were used. Except that -3-methyl-1-butanol (boiling point: 174 ° C.) was used, the procedure was the same as in Example 1.

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: γ-butyrolactone 16.00%: 3-methoxy-3-methyl-1-butanol 5.70% The results are shown below.

Edge bulge: 3 μm Partition height: 180 μm Half width: 62 μm Shape: 比較 (Comparative Example 1) A photosensitive glass paste in which all the ethyl cellosolve of Example 1 was replaced with γ-butyrolactone, ie, an organic solvent was used. A paste was prepared in the same manner as in Example 1 except that a paste having the following composition was prepared using only one kind of γ-butyrolactone, and this photosensitive glass paste was used.

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: γ-butyrolactone 21.70% After drying, the swelling of the edge of the paste-coated film was measured and found to be 30 μm. Next, exposure and development were performed. When the paste in the unexposed portion of the edge portion was to be washed away with the developing solution, the partition portion meandered due to excessive erosion of the developing solution into the partition portion.

Edge bulge: 30 μm Partition height: 172 μm Half width: 65 μm Shape: × (meandering) (Comparative Example 2) The ratio of ethyl cellosolve and γ-butyrolactone in Example 1 was changed as follows: That is, a photosensitive glass paste having the following composition was prepared in which the amount of ethyl cellosolve was reduced, and was carried out in the same manner as in Example 1 except that this was used.

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: γ-butyrolactone 20.00%: Ethyl cellosolve 1.70% After drying, it was 28 μm when the swelling of the edge of the paste coating film was measured. Next, exposure and development were performed, and when the paste in the unexposed portion at the edge portion was to be washed away with the developing solution, the partition wall portion meandered.

Edge swell: 28 μm Partition height: 174 μm Half width: 63 μm Shape: × (meandering)

[0059]

According to the present invention, a photosensitive glass paste comprising a glass powder, a photosensitive organic component and two or more organic solvents contains two or more organic solvents,
In addition, by making the boiling point difference of at least two kinds of organic solvents among the organic solvents 20 ° C. or more, it is possible to form a paste coating film having a uniform thickness with little swelling at the edge of the coating surface. A glass paste is obtained.

More specifically, in a state where the edge of the paste coating film is raised, exposure is performed using a mask, and when the unexposed portion of the raised portion is to be washed away with a developing solution, the exposed portion, that is, the partition wall portion is removed. Excessive erosion by the developer, meandering and peeling may cause serious problems, but by using the photosensitive glass paste of the present invention, such problems can be avoided and high-quality plasma displays can be used. Substrates and plasma displays can be manufactured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08F 299/00 C08F 299/00

Claims (7)

[Claims] 1. A photosensitive glass paste comprising a glass powder, a photosensitive organic component and an organic solvent, comprising two or more kinds of said organic solvents, wherein at least two kinds of said organic solvents have a boiling point difference of 20 or more. A photosensitive glass paste having a temperature of at least ℃. 2. Among the organic solvents, the organic solvents on the low boiling point side and the high boiling point side are each 10 to 9 relative to the total amount of the organic solvent.
2. The photosensitive glass paste according to claim 1, which contains 0% by weight. 3. The photosensitive glass paste according to claim 1, wherein the total content of the organic solvent is in a range of 1 to 50% by weight based on the entirety of the photosensitive glass paste. 4. An essential component of the photosensitive organic component,
An oligomer or polymer having a carboxyl group in the molecule and / or an unsaturated double bond in the molecule and having a weight molecular weight of 500 to 100,000 is contained in an amount of 10 to 90% by weight based on the amount of the photosensitive organic substance. The photosensitive glass paste according to any one of claims 1 to 3. 5. A method for producing a plasma display, comprising: applying the photosensitive glass paste according to claim 1 on a substrate, drying, pattern-exposing, developing, and firing to form a partition. A method for producing a plasma display, wherein the thickness of a single application of the photosensitive glass paste is 50 μm or more. 6. The method according to claim 5, wherein the application of the photosensitive glass paste for forming the partition walls is performed by a doctor blade method or a slit die coating method. 7. The method according to claim 5, wherein the application of the photosensitive glass paste for forming the partition is performed once or twice.