JPH11135005A - Manufacture of plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a plasma display panel having a high aspect ratio and a high precision barrier rib. SOLUTION: In a manufacturing method for a plasma display panel having a barrier rib on a substrate, photosensitive paste comprising an organic component containing inorganic particulates, a photosensitive compound, and a polymerization inhibitor as essential components is applied onto the substrate. Thereafter, the same is exposed via a photomask, and the portion not exposed is eluted by development so as to form a pattern. Thereafter, the organic component is removed by burning so as to form the barrier rib.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a plasma display such as a plasma display and a plasma addressed liquid crystal display.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of circuit materials and displays have been advanced, and accordingly, improvement of pattern processing technology has been desired. In particular, partition walls formed of an inorganic material such as glass with high precision and a high aspect ratio are desired for a plasma display panel.

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 354292/1993 propose a method of forming a pattern by a photolithography technique using a photosensitive paste.

Usually, a photosensitive paste is composed of an organic component containing inorganic fine particles and a photosensitive compound, and is formed by baking after forming a pattern by photolithography using the photosensitive organic component to form an inorganic pattern. .

[0006] Monomers and polymers, which are inorganic fine particles and organic components having photosensitivity, do not themselves absorb the energy of actinic rays such as ultraviolet rays, and therefore do not cause photoreaction. In order to cause a photoreaction, a photopolymerization initiator or a sensitizer for absorbing light energy and initiating a reaction with a photosensitive functional group is required. The photopolymerization initiator or sensitizer acts to absorb the irradiated light energy to directly generate an active radical, or to transfer the absorbed energy to accelerate the reaction. By these actions, the organic components in the photosensitive paste react, photocuring proceeds, and the portion becomes insoluble in the developing solution to form a pattern.

In order to promote the photo-curing of the coating film of the photosensitive paste, light having a wavelength that can be absorbed by a photopolymerization initiator or a sensitizer may be applied. , It is difficult to avoid internal light scattering, and it is easy to cause thickening of pattern shapes and filling between patterns (residual film formation),
There is a problem that a partition having a high aspect ratio and high definition cannot be obtained. Further, even when a pattern is obtained, the range in which the pattern can be obtained is limited depending on the amount of light, and the pattern cannot be formed stably, which has been a major obstacle in manufacturing a plasma display panel.

The inventors of the present invention have intensively studied measures for improving the state of the art, and as a result, the use of a photosensitive paste containing a polymerization inhibitor has reduced light scattering inside the photosensitive paste. The present inventors have found that a partition wall having no resulting pattern shape thickening or burying between patterns can be obtained, and the present invention has been achieved.

[0009] The addition of a polymerization inhibitor to the photosensitive paste is described in JP-A-8-50811, but these objects are to improve the thermal stability during storage. There is no description of preventing light scattering during exposure.

[0010]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for stably manufacturing a partition for a plasma display panel having a pattern with a high aspect ratio and a high precision.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to apply a photosensitive paste comprising inorganic fine particles and an organic component containing a photosensitive compound and a polymerization inhibitor as essential components on a substrate, and then apply the same through a photomask. This is achieved by a method for manufacturing a plasma display panel, comprising: performing exposure, forming a pattern by eluting a non-exposed portion by development to form a pattern, and removing organic components by firing to form a partition on a substrate. You.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A plasma display panel according to the present invention generates a plasma discharge between opposing anode and cathode electrodes in a discharge space provided between a front glass substrate and a back glass substrate, and generates the plasma discharge in the discharge space. The display is performed by irradiating the ultraviolet light generated from the gas sealed in the inside to the phosphor provided in the discharge space. In this case, the width of the discharge is suppressed to a certain area, and the display is performed in a specified cell, and at the same time, in order to secure a uniform discharge space, the width is about 30 to 80 μm and the height is 50 to
A 200 μm partition is provided.

The photosensitive paste of the present invention comprises an organic component containing inorganic fine particles, a photosensitive compound and a polymerization inhibitor. The pattern is formed by photolithography using the photosensitive organic component followed by baking to form an inorganic pattern. Is formed to obtain a partition for a plasma display. It is preferable that the photosensitive paste contains a large amount of inorganic fine particles since the shrinkage ratio during firing is small and the shape change due to firing is small. In order to irradiate the photosensitive paste containing such a large amount of inorganic fine particles with light so as to cause a chemical change efficiently, sufficient light energy is supplied to a portion to be photoreacted, and the organic component is reduced. Must be fully light cured. To do this,
It is necessary that the photosensitive paste transmit light sufficiently to reach the lower part.

It is known that in order to increase the light transmittance of a dispersion of different components, it is preferable to make the refractive indices of the components identical or approximate. Also in the photosensitive paste, it is necessary to make the refractive index of the inorganic fine particles and the refractive index of the organic component as close as possible in order to improve the light transmittance.

The average refractive index of the glass fine particles can be controlled by the composition thereof, and the average refractive index of the organic component can also be controlled by the composition of the photosensitive monomer or polymer to be used. Therefore, it is possible to match the average refractive indices of the two, and from such a viewpoint, the glass fine particle composition and the organic component composition can be selected.

The glass fine particles and the monomer or polymer which is a photosensitive organic component do not themselves absorb the energy of actinic rays such as ultraviolet rays, and do not cause a photoreaction. In order to cause a photoreaction, a photopolymerization initiator or a sensitizer for absorbing light energy and initiating a reaction with a photosensitive functional group is required. The photopolymerization initiator or sensitizer acts to absorb the irradiated light energy to directly generate an active radical, or to transfer the absorbed energy to accelerate the reaction. By these actions, the organic components in the photosensitive paste react, photocuring proceeds, and the portions become insoluble in the developer to form a pattern.

In order to promote photo-curing of the coating film of the photosensitive paste, light having a wavelength that can be absorbed by a photopolymerization initiator or a sensitizer may be applied. Since it is contained in a dispersed state, it is difficult to avoid light scattering inside, and it is difficult to obtain a high-resolution image due to the tendency of thickening of the pattern shape and burying between the patterns, which are considered to be caused by the scattering.

High resolution means that the lines and spaces of the pattern are formed with good contrast.
That is, it is desirable that the walls of the pattern be vertically cut and rectangular. Ideally, it is dissolved in the developer below a certain exposure amount, and insoluble in the developer above it. At low exposure dose due to scattered light, it dissolves in the developer, and when the thickening of the pattern shape and filling between patterns are resolved,
Even if the exposure amount is increased and the exposure is sufficient, a high resolution can be obtained.

According to the present invention, when a photosensitive paste containing a polymerization inhibitor is used, it is dissolved in a developing solution at a low exposure dose due to light scattering inside the photosensitive paste, and the pattern shape is not thickened and the pattern is not filled. This is based on the finding that a pattern with excellent resolution can be obtained with a wide range of exposure. It is especially at the bottom of the pattern that thickening of the pattern shape and filling between the patterns become a problem, so after applying a photosensitive paste containing a polymerization inhibitor to the substrate,
A photosensitive paste containing no polymerization inhibitor may be further applied thereon and used.

The weight ratio between the photopolymerization initiator and the polymerization inhibitor used is preferably from 8/1 to 1/3 in order to improve the pattern formation. If it is out of this range, problems may occur such that the pattern falls down before the unexposed portion is completely dissolved, or the pattern is buried (residual film).

Examples of the photosensitive paste that can be used in the present invention are shown below.

As the inorganic fine particles, those using glass or ceramics are preferable. Particularly useful is the case where glass powder is used as the inorganic fine particles.

As the glass powder, the glass transition point 430
When the paste contains glass powder having a glass softening point of 〜500 ° C. and a glass softening point of 470 ° C. to 580 ° C., the pattern processing can be performed on a glass substrate used for a normal display.

Having such a glass transition point and a glass softening point, and having a refractive index of glass fine particles of 1.5 to 1.6.
It is preferable that the metal oxide component is blended so as to be 5. For example, a glass powder composed of silicon oxide: 22, aluminum oxide: 23, boron oxide: 33, lithium oxide: 9, magnesium oxide: 7, barium oxide: 4, and zinc oxide: 2 (% by weight) has a glass transition point of: 490 ° C., glass softening point: 528 ° C., and refractive index at the g-line wavelength (436 nm): 1.59. The preferred composition of the glass powder as the photosensitive paste is as follows.

Lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30 Boron oxide: 20 to 40 Barium oxide: 2 to 15 Aluminum oxide: 10 to 25 Glass powder containing 3 to 10% by weight of lithium oxide is used. This not only facilitates control of the thermal softening temperature and thermal expansion coefficient, but also makes it possible to lower the average refractive index of the glass, thereby making it easier to reduce the refractive index difference from the organic component. In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferable in terms of paste stability. In the case of using potassium oxide, there is an advantage that the refractive index can be controlled with a relatively small amount of addition. Therefore, among the alkali metal oxides, addition of lithium oxide and potassium oxide is effective. In this case, it is preferable to use a glass powder containing a total of 3 to 10% by weight of an alkali metal oxide.

The silicon oxide is preferably contained in the range of 10 to 30% by weight, and if it is less than 10% by weight, the denseness, strength and stability of the glass layer are reduced, and the coefficient of thermal expansion is a desired value. And mismatch with the glass substrate is likely to occur. Further, by setting the content to 30% by weight or less, there is an advantage that the thermal softening point is lowered and baking on a glass substrate becomes possible.

It is preferable that boron oxide is blended in the range of 20 to 40% by weight. If it exceeds 40% by weight, the stability of the glass will be reduced. Boron oxide is glass powder 800
To dissolve at a temperature of about 1200 ° C. or to impair the electrical, mechanical and thermal properties such as electrical insulation, strength, thermal expansion coefficient, and denseness of the insulating layer, even when the baking temperature of the glass paste is large for silicon oxide. It is blended in order to control the baking temperature in the range of 540 to 610 ° C. so that there is no baking. If it is less than 20% by weight, the strength of the insulating layer is reduced, and the stability of the glass is reduced.

It is preferable that barium oxide is blended in the range of 2 to 15% by weight. If it is less than 2% by weight, it is difficult to control the glass baking temperature and the electrical insulation. On the other hand, if the content exceeds 15% by weight, the stability and the denseness of the glass layer decrease.

It is preferable that aluminum oxide is blended in the range of 10 to 25% by weight. Aluminum oxide is added to increase the strain point of the glass. If it is less than 10% by weight, the strength of the glass layer is reduced. If it exceeds 25% by weight, the heat resistance temperature of the glass becomes too high, and it is difficult to bake the glass on the glass substrate. In addition, the dense insulating layer is 600
It becomes difficult to obtain at a temperature of below ° C.

It is preferable that zinc oxide is blended in a range of 1.5 to 10% by weight. At less than 1.5% by weight,
It has no effect on improving the denseness of the insulating layer. If it exceeds 10% by weight, the temperature for baking on the glass substrate becomes too low to control, and the insulation resistance is undesirably low.

It is preferable that calcium oxide is blended in the range of 2 to 10% by weight. Added to help melt the glass and control the coefficient of thermal expansion. If it is less than 2% by weight, the strain point becomes too low.

It is preferable that magnesium oxide is blended in the range of 1 to 10% by weight. Magnesium oxide is added to facilitate melting of the glass and to control the coefficient of thermal expansion. If it exceeds 10% by weight, the glass tends to be devitrified, which is not good.

The glass powder may contain titanium oxide, zirconium oxide, etc., but the amount is preferably less than 2% by weight. Zirconium oxide is effective in controlling the softening point, transition point and electrical insulation of glass.

As a method for producing the glass powder, for example, lithium oxide, silicon oxide, aluminum oxide,
Boron oxide, barium oxide, zinc oxide, and the like are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., quenched, glass frit, and pulverized.
Make a fine powder of μm. As a raw material, a high-purity carbonate, oxide, hydroxide, or the like can be used. In addition, depending on the type and composition of the glass powder, ultra-high purity alkoxide or organometallic raw material of 99.99% or more is used. It is preferable because a high-strength insulating layer having few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced, and the powder has a particle diameter of 50% by weight (average particle diameter) of 2 to 2.
It is necessary that the thickness be 3.5 μm and the top size be 15 μm or less. Further, when the 10% by weight particle size is 0.6 to 1.5.
μm, 90% by weight particle size 4-8 μm, specific surface area 1.5
It preferably has a density of up to ^2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm, and the specific surface area is 1.
7 to 2.4 m ² / g. Within this range, light is sufficiently transmitted at the time of ultraviolet exposure, and a partition pattern with a small line width difference between the upper and lower portions can be obtained. If the average particle size is 2.0 μm or less and the specific surface area exceeds 2.5 m ² / g, the powder becomes too fine and light is scattered at the time of exposure to cure the unexposed portion, which is not preferable.

The organic component used in the photosensitive paste of the present invention is a portion obtained by removing the inorganic component from the paste, and occupies 5 to 50 parts by weight in the paste.

The organic component is a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, a binder, a photopolymerization initiator, an ultraviolet light absorber, a sensitizer, and a sensitization aid. , Polymerization inhibitors, plasticizers, thickeners,
It is constituted by adding additive components such as an organic solvent, an antioxidant, a dispersant, and an organic or inorganic anti-sedimentation agent as required.

As the photosensitive monomer, a compound having an active carbon-carbon double bond is often used. As the functional group, monofunctional and polyfunctional compounds having a vinyl group, an allyl group, an acrylate group, a methacrylate group, and an acrylamide group can be applied. The present invention is characterized in that a polyfunctional acrylate compound and / or a methacrylate compound are contained in an organic component in an amount of 10 to 80% by weight. Since various kinds of compounds have been developed for the polyfunctional compound having an acrylate or methacrylate functional group, it is possible to select the compound in consideration of reactivity, refractive index, and the like.

As a method for controlling the refractive index of the organic component contained in the photosensitive paste, a method for controlling the refractive index of the photosensitive monomer is simple. In particular, the refractive index is 1.55-1.
By using the photosensitive monomer of No. 8, the refractive index of the organic component can be increased.

As the photosensitive monomer to be used, it is effective to use an acrylate monomer or a methacrylate monomer containing an aromatic ring such as a benzene ring or a naphthalene ring or a sulfur atom to increase the refractive index. In particular, in order to increase the crosslink density at the time of curing by photoreaction and to improve the pattern formability, it is effective to use a polyfunctional acrylate monomer or methacrylate monomer to increase the refractive index.

Specifically, pentaerythritol triacrylate or tetraacrylate, bisphenol A di (meth) acrylate, bisphenol A-ethylene oxide adduct di (meth) acrylate, bisphenol A-propylene oxide adduct di (meth) acrylate A) acrylate, thiophenol (meth) acrylate, benzyl mercaptan (meth) acrylate, or a compound in which 1 to 5 hydrogen atoms in the aromatic ring are substituted with chlorine or bromine atoms.

As the monomer containing a sulfur atom in the molecule, a monomer having a thiol (meth) acrylate group or a monomer having a phenyl sulfide structure is used. Various monomers can be used in combination with these monomers for improving the refractive index.

As an organic component constituting the photosensitive paste, an oligomer or a polymer is used as a component that plays a role in improving the physical properties of a cured product formed by photoreaction and adjusting the viscosity of the paste. The oligomer or polymer is obtained by polymerization or copolymerization of a component selected from compounds having a carbon-carbon double bond.

As a monomer to be copolymerized, the developability in an aqueous alkali solution 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 (A) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is obtained.
V) is preferably in the range of 50 to 180, more preferably 70 to 140. When the acid value exceeds 180, the allowable development width becomes narrow. Further, when the acid value is 50 or less, the solubility of the unexposed portion in the developing solution is reduced, so that the developing solution concentration is increased, peeling occurs up to the exposed portion, and it is difficult to obtain a high-definition pattern. Become.

By adding a photoreactive group to a side chain or a molecular terminal to the above-described polymer or oligomer, it can be used as a photosensitive polymer or a 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 a method in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid is added 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 ether crotonic acid and glycidyl ether isocrotonic acid. .

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

In the photosensitive paste used in the present invention, one oligomer or polymer having a weight average molecular weight of 500 to 100,000 containing a carboxyl group and an unsaturated double bond in the molecule is used.
Those containing 0 to 90% by weight in the organic component are preferred.

When a binder component is required, polyvinyl alcohol, polyvinyl butyral, a methacrylate polymer, an acrylate polymer, an acrylate-methacrylate copolymer, a butyl methacrylate resin, or the like is used as the polymer. Can be. It is also effective to increase the refractive index of the binder component to increase the refractive index of the photosensitive organic component.

The organic component of the photosensitive paste used in the present invention contains a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer or a binder, but none of these components has an ability to absorb active light energy. In order to start the reaction, it is necessary to add a photopolymerization initiator or a sensitizer.

The pattern formation by the photosensitive paste is to polymerize and crosslink the photosensitive components (monomers, oligomers, and polymers) in the exposed portions to make them insoluble in the solvent. Is a radical polymerizable, and its photopolymerization initiator is selected from those generating radical species.

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

In the photosensitive paste used in the present invention, one or more of these are used. The photopolymerization initiator is
It is preferable to add 0.05 to 10% by weight to 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 reduced.

By using a sensitizer together with the photopolymerization initiator, the sensitivity can be improved and the wavelength range effective for the reaction can be extended.

Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone,
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) iso Naphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5 -Benzoi Thiotetrazole, such as 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like.

In the photosensitive paste used in the present invention, one or more of these are used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste, the amount of the sensitizer is usually 0.05 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 reduced.

In the present invention, a photosensitive paste containing a polymerization inhibitor is used so as to dissolve in a developing solution even when cured at a low exposure dose due to light scattering and to eliminate the thickening of the pattern shape and the filling between the patterns.

The polymerization inhibitor in the present invention is not particularly limited as long as it can be used as a polymerization inhibitor. For example, p-benzoquinone, naphthoquinone, para-xyloquinone, para-toluquinone, 2,6-dichloroquinone,
2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-diaeroxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t
-Butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butylparacresol, hydroquinone monomethyl ether, α-naphthol, acetanidin acetate, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxide Zalate, phenyl-β-naphthylamine, parabenzylamininophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinonedioxime, cyclohexanoone oxime, pyrogallol, tannic acid, resormine, triethylamine Hydrochloride, dimethylaniline hydrochloride, cuperon and the like.

In the present invention, one or more of these are used. Although the amount of the polymerization inhibitor depends on the amount of the light absorbing agent, it is generally about 0.01 to 30% by weight based on the organic components of the photosensitive paste. If the amount of the light absorbing agent is not reduced, the amount of the polymerization inhibitor is preferably about 0.01 to 5% by weight, more preferably 0.03 to 3% by weight, based on the organic components of the photosensitive paste. If the amount is less than this range, the effect of inhibiting polymerization is not exhibited, and curing is performed even at a low exposure dose due to light scattering. Also, if the amount exceeds the above range, the sensitivity is lowered and a large amount of exposure is required, so care must be taken.

The photosensitive paste to which an ultraviolet absorbent is added is effective. By adding a compound having a high absorption effect of ultraviolet light or visible light, a higher aspect ratio, higher definition, and higher resolution can be obtained.

The light absorbing agent is composed of an organic dye,
Among them, those having a high absorption coefficient in the wavelength range of 350 to 450 nm are preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes and the like can be used.
Even when an organic dye is added as a light absorbing agent, it does not remain in the insulating film after firing, so that deterioration of the insulating film characteristics can be reduced, which is preferable. Among these, azo dyes and benzophenone dyes are preferred. The amount of the organic dye added is 0.
It is preferably from 0.5 to 1% by weight. As an example of the method of adding a light absorber composed of an organic dye, a method of preparing a solution in which an organic dye is dissolved in an organic solvent in advance and kneading the solution at the time of preparing the paste, or adding inorganic fine particles in the organic solvent After mixing, a method of drying is used. By this method, a so-called capsule-like powder in which the surface of each of the inorganic fine particles is coated with an organic dye film can be produced. Thereby, irregular reflection at the interface of the glass particles is suppressed, and unnecessary photoreaction is prevented, so that it is estimated that thickening of the pattern and generation of a residual film are prevented.

If necessary, the photosensitive paste may contain a polymerization inhibitor for improving thermal stability during storage, an antioxidant for preventing oxidation of the acrylic copolymer, and other plasticizers. Can be added.

An organic solvent is used to adjust the viscosity when applying the photosensitive paste to the glass substrate according to the method of application. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol,
An organic solvent mixture containing one or more of isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyl lactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like is used. Can be

The photosensitive paste is usually prepared by mixing various components such as inorganic fine particles, a light absorbing agent, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a sensitizer, and a solvent so as to have a predetermined composition. 3. Mix and disperse uniformly with three rollers or a kneader to produce.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, a suspending agent and the like, but the range is from 2000 to 200,000 cps.
(Centipoise). For example, when the coating on the glass substrate is performed by the spin coating method, 2000 to 5000
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 using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable. The photosensitive paste is applied over the entire surface or partially over a glass substrate or a ceramic substrate. As a coating method, a known method such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste.

Here, when applying the paste on the substrate,
Surface treatment of the substrate can be performed to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacrylic acid). Roxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, or an organic metal such as , Organic titanium,
Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal 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. Used.
Next, this surface treatment liquid is uniformly applied on a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform surface treatment.

After the application, the film is dried using a known device such as a ventilation oven or a hot plate to form a film of a photosensitive paste.

After drying, a photosensitive paste containing no polymerization inhibitor in the photosensitive paste is applied and dried in the same manner.
The coating of the photosensitive paste may be formed in two layers.

Subsequently, exposure is performed using an exposure apparatus. The exposure is generally performed through a photomask, as in the case of ordinary photolithography. Also,
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. Also,
In the case of performing exposure over a large area, a photosensitive paste is applied onto a substrate such as a glass substrate, and then exposed while being transported, so that a large exposure area can be exposed with an exposure machine having a small exposure area.

The active light source used in this case includes, for example, near ultraviolet rays, ultraviolet rays, electron beams, X-rays, laser beams and the like. Of these, ultraviolet rays are most 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, and the like can be used. Among these, an ultra-high pressure mercury lamp is preferred. Although the exposure conditions vary depending on the coating thickness, exposure is performed for 0.5 to 30 minutes using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm ² .

By providing an oxygen blocking film on the surface of the applied photosensitive paste, the pattern shape can be improved. As an example of the oxygen barrier film, a film such as polyvinyl alcohol or cellulose, or a film such as polyester can be given. The polyvinyl alcohol film is formed by uniformly applying an aqueous solution having a concentration of 1 to 3% by weight on a substrate by a method such as a spinner or the like at 70 to 90 ° C.
This is performed by evaporating water by drying for 0 to 60 minutes.

The reason why the sensitivity is improved by the application of polyvinyl alcohol is estimated as follows. That is, when the photosensitive component undergoes a photoreaction, it is considered that the presence of oxygen in the air hinders the photocuring reaction, but the presence of a polyvinyl alcohol film improves the sensitivity during exposure because excess oxygen can be blocked. It is preferred. 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 paste after application.

After exposure, development is carried out by utilizing the difference in solubility between the exposed portion and the unexposed portion in the developing solution.
It is performed by a dipping method, a spray method, or a brush method. An organic solvent in which an organic component in the photosensitive paste can be dissolved is used as the developer. In addition, water may be added to the organic solvent as long as its solvent power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkaline aqueous solution since an alkaline component can be easily removed during 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 aqueous alkali solution is usually 0.05 to 5
% By weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not good. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control. Next, firing is performed in a firing furnace.
The firing atmosphere and temperature vary depending on the type of paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

The firing temperature is 400 to 1000 ° C. When processing a pattern on a glass substrate, 520 to 610
The firing is carried out at a temperature of 10 ° C. for 10 to 60 minutes.

[0081]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to this. The concentration (%) in the examples is% by weight.

Example 1 The photosensitive paste was prepared by adding 8% of each of the organic components obtained by adding 0.5% of hydroquinone monomethyl ether to the organic components.
This was prepared by dissolving while heating to 0 ° C., adding inorganic fine particles coated with a light absorbing agent, and kneading with a kneading machine. The viscosity was adjusted by the amount of γ-butyrolactone, but the amount of the solvent in the paste was adjusted to 10 to 40%.

A photosensitive paste was uniformly applied on a soda glass substrate by screen printing. Coating and drying were repeated several times or more in order to avoid pinholes or the like on the coating film, and coating was performed so that the dry thickness became 180 μm. Drying was performed at 80 ° C. for 10 minutes.

A photomask (striped pattern,
Exposure is performed through a pattern pitch of 150 μm and a line width of 20 μm). Exposure was performed with an ultra-high pressure mercury lamp having an output of 50 mW / cm ² to perform 1.5 J / cm ² ultraviolet exposure. Thereafter, a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. is developed by applying a shower for 120 seconds, and then washed with water using a shower spray to remove a space portion that has not been photocured. Striped partition walls were formed on the substrate.

The glass substrate on which the processing of the partition pattern was completed was dried at 80 ° C. for 15 minutes and then baked at 560 ° C. for 15 minutes to form a partition. The firing causes a shrinkage of about 30%.

The composition is as follows: Li ₂ O: 9%, SiO ₂ : 22
%, Al ₂ O ₃ : 23%, B ₂ O ₃ : 33%, BaO: 4
%, ZnO: 2%, and MgO: 7%, the average refractive index of the glass fine particles is 1.586. The glass transition point and the glass softening point of these fine glass particles were 476 ° C. and 519 ° C., respectively.
° C., the average particle size is 2.6 μm. In the examples, glass fine particles obtained by coating glass powder of this composition with a light absorbing agent were used as glass fine particles. Sudan IV was used as a light absorbing agent, and 0.08% of the powder was used.

The following organic components were added to 70 parts by weight of the glass fine particles having the above composition. That is, photosensitive polymer (X-4007): 15 parts by weight, photosensitive monomer (M
GP400): 15 parts by weight, a photopolymerization initiator (IC-369): 2.4 parts by weight, and a sensitizer (D
ETX-S): 2.4 parts by weight.

The photosensitive paste coating film was exposed and
The shape of the pattern formed by the development was observed with an electron microscope. The pattern was 180 μm in height, 35 μm in half width, and rectangular.

After firing, the obtained partition walls had a height of 130 μm,
It was a good one with a half width of 24 μm.

The same pattern shape was obtained even when the exposure amount was changed by ± 0.1 J / cm ² .

Example 2 In a step of applying a photosensitive paste by screen printing, a photosensitive paste obtained by adding 0.5% of hydroquinone monomethyl ether to an organic component was dried to a thickness of 9%.
After coating to a thickness of 0 μm, a photosensitive paste containing no hydroquinone monomethyl ether was prepared, and the same procedure as in Example 1 was carried out except that the photosensitive paste was similarly coated to a thickness of 90 μm.

When the shape of the obtained pattern was observed with an electron microscope, it was found to be 180 μm in height, 37 μm in half width, and rectangular.

After firing, the obtained partition walls had a height of 130 μm,
It was a good one with a half width of 25 μm.

The same pattern shape was obtained even when the exposure amount was changed by ± 0.1 J / cm ² .

Example 3 The procedure of Example 1 was repeated, except that pt-butylcatechol was used as the polymerization inhibitor and the exposure was changed to 1.2 J / cm ² . The obtained pattern cross-section had a height of 180 μm and a half width of 38 μm, and was rectangular. Observation was performed on the partition walls obtained after firing, and the height was 128 μm.
m, and the half width was 26 μm.

The same pattern shape was obtained even when the exposure amount was changed by ± 0.1 J / cm ² .

Example 4 Cupperon was used as a polymerization inhibitor, and the exposure amount was 1.8 J / cm.
^Except that it was set to ² , it carried out similarly to Example 1. The cross-sectional shape of the obtained pattern was 180 μm in height and 36 μm in half width, and was rectangular. Observation was performed on the partition walls obtained after firing, and the height was 128 μm and the half width was 24 μm.
m.

The same pattern shape was obtained even when the exposure amount was changed by ± 0.1 J / cm ² .

Comparative Example The same procedure as in Example 1 was carried out except that a photosensitive paste containing no polymerization inhibitor was used and the exposure amount was 1.0 J / cm ² .
The cross-sectional shape of the obtained pattern was 180 μm in height and 48 μm in half width. Observation of the partition walls obtained after the baking revealed that the height was 128 μm and the half width was 32 μm, and a thin pattern as in Examples 1 to 3 was not obtained.

Further, when the exposure amount was set to 1.1 J / cm ² , filling was observed between the patterns, and the exposure amount was 0.9 J / cm ^2.
When the area was set to cm ² , collapse of the pattern was observed before the unexposed portion was completely dissolved.

(Explanation of abbreviations) X-4007: 0.4 to the carboxyl group of a copolymer composed of 40% methacrylic acid, 30% methyl methacrylate and 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 an equivalent amount of glycidyl methacrylate.

MGP400: a compound represented by the following chemical formula (I).

[0103]

Embedded image GX: a compound represented by the following chemical formula (II).

[0104]

Embedded image IC-369: Irgacure-369 (Ciba-Geigy product) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 DETX-S: 2,4-diethylthioxanthone

[0105]

According to the present invention, by using a photosensitive paste containing a polymerization inhibitor, the pattern shape becomes good, and the partition walls formed after firing can be made more excellent. As a result, it becomes possible to process a thick film such as a display or a circuit material, and to perform high-precision pattern processing, thereby improving the definition and simplifying the process. In particular, since a highly accurate partition can be easily formed, a plasma display panel can be efficiently manufactured.

Claims (3)

[Claims] 1. A method for manufacturing a plasma display panel having a partition formed on a substrate, comprising applying a photosensitive paste comprising inorganic fine particles and an organic component containing a photosensitive compound and a polymerization inhibitor as essential components to the substrate. After doing
A method of manufacturing a plasma display panel, comprising: performing exposure through a photomask, developing a pattern by developing an unexposed portion by elution, and removing an organic component by baking to form the partition. . 2. A photosensitive paste comprising inorganic fine particles and an organic component containing a photosensitive compound and a polymerization inhibitor as essential components is coated on a substrate, and then a photosensitive paste containing no polymerization inhibitor is further coated thereon. 2. The method for manufacturing a plasma display panel according to claim 1, further comprising the step of: 3. The amount of the polymerization inhibitor is 0.0
3. The method of manufacturing a plasma display panel according to claim 1, wherein the amount is in the range of 1 to 5% by weight.