JP2002023383A - Photosensitive paste, member for display using the same and method for producing member for display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive paste comprising inorganic fine particles and an organic component and capable of homogeneously forming a thicker pattern. SOLUTION: The photosensitive paste comprises inorganic fine particles and an organic component in a specified ratio and the total light transmittance T(%) of a paste film after coating and drying at a specified wavelength satisfies the relation of T>=90-0.25d to the film thickness (d) (μm) after drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive paste and a method for manufacturing a display member using the same, and various displays and circuits including a plasma display, a plasma addressed liquid crystal display, and a field emission display. Used for pattern processing of materials and the like and its manufacture.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of circuit materials and displays have been promoted, and a pattern processing technique capable of coping with this has been demanded. In particular, a material capable of patterning an inorganic material such as glass with high precision and a high aspect ratio is desired for forming a partition of a plasma display.

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. 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).

Japanese Patent Application Laid-Open No. 10-333324 discloses a photosensitive paste having a total light transmittance of 50% or more in a g-line wavelength region when measured at a film thickness of 50 μm after drying. On the other hand, since the total light transmittance of the photosensitive paste layer having a thickness of more than 250 μm after drying was insufficient, it was not possible to form a pattern by irradiating with active light. Further, even when the film thickness after drying is about 180 μm, the light transmittance is insufficient, and the degree of curing is different due to the difference in the amount of light reaching the upper and lower portions of the photosensitive paste layer, and uniform curing is obtained. Did not. As a result, there is a problem that the meandering of the pattern easily occurs during development.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive paste which enables high-aspect-ratio and high-definition pattern processing in a single processing step, focusing on the above-mentioned problems of the prior art. Accordingly, it is an object of the present invention to provide a photosensitive paste that can form a thick film pattern exceeding 250 μm after drying, does not meander, and can be cured uniformly in the thickness direction.

[0007]

Means for Solving the Problems To solve the above problems, the photosensitive paste of the first invention of the present invention has the following constitution. That is, the photosensitive paste is composed of 40 to 90% by weight of inorganic fine particles and 60 to 10 parts by weight of an organic component. When the film thickness d (μm) is d ≧ 10
It is characterized by having a relationship of T ≧ 90−0.25d at 0.

The photosensitive paste of the second invention of the present invention is a photosensitive paste comprising 40 to 90% by weight of inorganic fine particles and 60 to 10 parts by weight of an organic component, and is a paste film after being applied and dried. Is characterized in that the total light transmittance with respect to the g-line is 50% or more at a film thickness of 200 μm after drying.

[0009] Further, there is provided a member for a plasma display and a method for manufacturing a plasma display, wherein the photosensitive paste is applied on a substrate, a pattern is formed through exposure and development, and baked.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. The photosensitive paste of the first invention of the present invention is composed of 40 to 90% by weight of inorganic fine particles and 60 to 10 parts by weight of an organic component, is baked after pattern formation using photolithography, and is substantially composed of an inorganic substance. Used to form a pattern. In order to efficiently form an inorganic pattern with a smaller number of photosensitive pastes, it is preferable to use a photosensitive paste containing more inorganic substances, but on the other hand, the transmittance of light used for pattern formation is reduced. When the content of the inorganic fine particles in the photosensitive paste is less than 40% by weight, a large amount of the photosensitive paste is required to form an inorganic pattern having a desired thickness, which is industrially disadvantageous. When the content of the inorganic fine particles in the photosensitive paste exceeds 90% by weight, the light transmittance is insufficient, and a pattern cannot be formed substantially.

The organic component of the present invention means the entirety of the photosensitive paste excluding the inorganic component.
At least one selected from a reactive monomer, a reactive oligomer, and a reactive polymer, and, if necessary, a binder polymer, a photopolymerization initiator, a photoacid generator, a photobase generator, a sensitizer, and a sensitization aid. , An ultraviolet dye, an organic dye, a dispersant, a plasticizer, a thickener, an organic solvent, an acid, a base, an antisettling agent, and an antioxidant.
Here, the reactivity of the reactive monomer, the reactive oligomer, and the reactive polymer means that the reactive monomer, the reactive oligomer, and the reactive polymer are cross-linked when the photosensitive paste is irradiated with actinic rays. It means that the chemical structure is changed through reactions such as polymerization, photodepolymerization, and photodenaturation.

The term "active light" as used herein means a light in the wavelength region of 250 to 1100 nm which causes such a chemical reaction, and specifically, an ultraviolet light such as an ultra-high pressure mercury lamp or a metal halide lamp, or a halogen lamp or the like. Visible light, a laser beam of a specific wavelength such as a helium-cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide laser can be given.

As the organic component used in the present invention, a compound having an ethylenically unsaturated group is preferably used. Examples of such a polymerizable monomer include a monomer having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylates or methacrylates of alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.), and carboxylic acids (eg, propionic acid acetate) , Benzoic acid, acrylic acid, methacrylic acid, succinic acid,
Reaction products of maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidylmethexylylenediamine; amide derivatives (eg, acrylamide, methacrylamide, N-methylolacrylamide) , Methylenebisacrylamide, etc.), and a reaction product of an epoxy compound and acrylic acid or methacrylic acid. In addition, in the polyfunctional monomer,
The unsaturated group may be present as a mixture of acryl, methacryl, vinyl and allyl groups. These may be used alone or in combination.

In the organic component, a polymer having an ethylenically unsaturated compound may be used as the compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

The polymer used as the organic component in the present invention preferably has a carboxyl group. Polymers having a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyl group-containing monomers such as vinyl acetic acid or anhydrides thereof and methacrylic acid esters, acrylic acid esters, It can be obtained by selecting a monomer such as styrene, acrylonitrile, vinyl acetate, or 2-hydroxyacrylate, and copolymerizing the monomer using an initiator such as azobisisobutyronitrile.

As the polymer having a carboxyl group, a copolymer containing (meth) acrylic acid ester and (meth) acrylic acid as a copolymer component is preferably used because of its low thermal decomposition temperature during firing. In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used.

The resin acid value of the copolymer having a carboxyl group is preferably from 50 to 150 mgKOH / g. When the acid value exceeds 150, the allowable development width becomes narrow.
On the other hand, when the acid value is less than 50, the solubility of the unexposed portion in the developing solution is reduced. If the developer concentration is increased, peeling occurs up to the exposed portion, making it difficult to obtain a high-definition pattern.

As a method for introducing an ethylenically unsaturated bond into a side chain, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid chloride with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in a polymer is used. And carboxylic acid such as methacrylic chloride or allyl chloride, and maleic acid.

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 ether, and glycidyl ether isocrotonic acid. . In particular, CH2 = CCH3C
OOCH2CHOHCH2- is preferably used.

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 molar equivalent based on the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferred to react.

The preparation of the amine compound having an ethylenically unsaturated bond includes glycidyl (meth) acrylate having an ethylenically unsaturated bond, (meth) acrylic acid chloride,
(Meth) acrylic anhydride may be reacted with an amino compound. A plurality of ethylenically unsaturated group-containing compounds may be used as a mixture.

When a binder component is required, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate copolymer, butyl methacrylate resin, etc. are used as the polymer. Can be.

The photopolymerization initiator used in the present invention is selected from those generating radical species. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-. 1-one, 4- (2-hydroxyethoxy) phenyl- (2-
(Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2
-Propanedione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl]
-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 '
-Methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo -2-propenyloxy) ethyl] benzenemethanaminium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium Chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thio Xanthene-2-yloxy) -N,
N, N-trimethyl-1-propanaminium chloride,
2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl)-
4,5,4 ', 5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-
Ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-
Cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) -1-
Yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, Dibenzyl ketone,
Fluorenone, 2,3-diethoxyacetophenone,
2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t
-Butyl anthraquinone, 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, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime,
N-phenylglycine, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile,
Examples include a combination of a photoreducing dye such as benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine.

In the present invention, one or more of these can be used. The photopolymerization initiator is added in the range of 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the amount of the photosensitive organic 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-dimethylthioxanthone, 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-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3- Carbonyl bis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyldiethanolamine, triisopropanolamine, N-phenyl-N
-Ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, benzoic acid (2-dimethylamino ) Ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. .

It is also preferable to use a sensitizing dye.
For example, coumarin dyes, ketocoumarin dyes, xanthene dyes, thioxanthene dyes, cyanine dyes,
Merocyanine dyes, rhodocyanine dyes, styryl dyes, base styryl dyes, rhodocyanine dyes, oxonol dyes, and the like can be given.

In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the amount of the photosensitive organic 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, it is preferable to add an antioxidant. The antioxidant has a radical chain inhibiting action, a triplet eliminating action, and a hydroperoxide decomposing action. Since the photosensitive paste contains many inorganic fine particle components in a dispersed state, it is difficult to avoid light scattering inside the paste due to exposure light, resulting in thickening of the pattern shape and filling between patterns (remaining film formation), which are considered to be caused by this. Likely to happen. The walls of the pattern are desirably vertically cut and rectangular. Ideally, it is dissolved in the developer below a certain exposure amount, and insoluble in the developer above it. In other words, it is preferable that even if the resin is cured at a low exposure dose due to light scattering, it is dissolved in the developing solution, the thickening of the pattern shape and the filling between the patterns are eliminated, and the resolution range is wide even if the exposure dose is increased.

When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals or returns the excited photopolymerization initiator or sensitizer to its ground state to generate ground light. An excess photoreaction is suppressed, and a photoreaction occurs rapidly at an exposure amount that cannot be suppressed by an antioxidant, so that the contrast between dissolution and insolubility in a developer can be increased.

Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone , Pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5
-Di-t-amylhydroquinone, di-t-butyl-p-
Cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene Nitrobenzene,
Picric acid, quinone dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, (2,2 ′
-Thiobis (4-t-octylphenolate) -2-ethylhexylaminonickel- (II), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-
6-t-butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t- Butyl-4-hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like, but are not limited thereto. In the present invention, one or more of these can be used.

The addition amount of the antioxidant is 0.1 to 30% by weight in the photosensitive paste, more preferably 0.5 to 20% by weight.
% Range. If the amount is less than these ranges, the contrast of dissolution and insolubility in the developing solution is small. Cannot be maintained.

By adding an ultraviolet absorber, the scattered light inside the paste due to the exposure light can be absorbed and the scattered light can be reduced. Examples of the ultraviolet absorber include a benzophenone-based compound, a cyanoacrylate-based compound, a salicylic acid-based compound, a benzotriazole-based compound, an indole-based compound, and inorganic fine metal oxides.
Of these, benzophenone-based compounds, cyanoacrylate-based compounds, benzotriazole-based compounds, and indole-based compounds are particularly effective. Specific examples of these include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-
2'-carboxybenzophenone, 2-hydroxy-4
-Methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4- Dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2 ′
-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
4'-n-octoxyphenyl) benzotriazole,
2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, BO as an indole-based absorbent
Examples include, but are not limited to, NASORB UA-3901 (manufactured by Orient Chemical), BONASORB UA-3902 (manufactured by Orient Chemical), and SOM-2-0008 (manufactured by Orient Chemical). Further, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

The amount of the ultraviolet absorber added is 0.001 to 10% by weight in the paste, more preferably 0.005 to 10% by weight.
５5%. Beyond these ranges, the transmission limit wavelength and the wavelength gradient width change, and the ability to absorb scattered light is insufficient, the transmittance of exposure light is reduced, and the sensitivity of the photosensitive paste is reduced.

In the present invention, an organic dye can be added as a mark for exposure and development. By adding a dye and coloring, visibility is improved, and it becomes easy to distinguish a portion where the paste remains and a portion where the paste has been removed during development. The organic dye is not particularly limited, but preferably does not remain in the insulating film after firing. Specifically,] dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes Dyes, phthalimide dyes, perinone dyes and the like can be used. In particular, it is preferable to select a material that absorbs light having wavelengths near the h-line and the i-line, for example, a carbonium-based dye such as basic blue, because the effects of the present invention can be more easily achieved. 0.001-1% by weight of organic dye
It is preferred that

An organic solvent is used to adjust the viscosity when applying the photosensitive paste to the substrate according to the application method. 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 at least one of them are used.

The inorganic fine particles in the present invention are fine particles of conductive powders such as glass, ceramics, Au, Ni, Ag, Pd, and Pt, and are particularly useful.
This is the case where glass powder is used.

As the glass powder, the glass transition point 430
It is preferable that the paste contains glass powder having a softening point of の 500 ° C. and a softening point of 470-580 ° C. in an amount of 50% by weight or more.
This is because pattern processing tends to be easily performed on a substrate used for a normal display.

The inorganic fine particles have an average refractive index of 1.5 to 1.5.
It is preferably in the range of 1.65. By using glass fine particles containing a metal oxide so that the refractive index of the glass fine particles becomes 1.5 to 1.65, the refractive index of the glass powder and the photosensitive organic component are matched to suppress the light scattering. Therefore, there is a tendency that high-precision pattern processing becomes possible. For example, silicon oxide: 22, aluminum oxide: 23, boron oxide: 33, lithium oxide: 9, magnesium oxide: 7, barium oxide: 4, and zinc oxide 2
(Wt%) has a glass transition point of 49.
0 ° C., softening point: 528 ° C. and g-line wavelength (436 nm)
Is 1.59, and can be preferably used as the inorganic fine particles of the present invention. More preferably, it is in the range of 1.53 to 1.62.

The glass powder which can be preferably used as the inorganic fine particles used in the photosensitive paste of the present invention has, for example, the following composition.

As described above, at least one of the alkali metal oxides of lithium oxide, sodium oxide and potassium oxide is used, and the total amount is preferably 3 to 15% by weight, more preferably 3 to 10% by weight. preferable.

The alkali metal oxide not only facilitates the control of the softening point under load and the thermal expansion coefficient of the glass, but also reduces the refractive index of the glass. It is easy to reduce the size. When the total amount of the alkali metal oxides is 3% by weight or more, the effect of lowering the melting point of the glass can be obtained.
When the content is not more than% by weight, the chemical stability of the glass can be maintained and the coefficient of thermal expansion can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing migration of ions.

The content of silicon oxide is preferably 5 to 30% by weight, more preferably 10 to 30% by weight. Silicon oxide is effective for improving the denseness, strength and stability of glass, and is also effective for lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent separation due to mismatch with the glass substrate. When the content is 5% by weight or more, the coefficient of thermal expansion is suppressed to a small value, and no crack occurs when the glass substrate is baked. Further, the refractive index can be kept low. When the content is 30% by weight or less, the glass transition point and the softening point under load can be kept low, and the temperature for baking on a glass substrate can be lowered.

Boron oxide is also effective in lowering the refractive index, and is preferably added in the range of 20 to 45% by weight, more preferably 20 to 40% by weight. When the content is 20% by weight or more, the glass transition point and the softening point under load are suppressed to be low, and baking on a glass substrate is facilitated. Further, when the content is 45% by weight or more, the chemical stability of the glass can be maintained.

At least one of barium oxide and strontium oxide is used, and the total amount is preferably 2 to 15% by weight, more preferably 2 to 10% by weight. These components are effective in adjusting the coefficient of thermal expansion, and are also preferable in terms of application of the baking temperature to the heat resistance of the substrate, electrical insulation, and stability and denseness of the formed partition walls. When the content is 2% by weight or more, devitrification due to crystallization can be prevented.
Further, when the content is 15% by weight or less, the coefficient of thermal expansion can be kept small, and the refractive index can be kept small. Also, the chemical stability of the glass can be maintained.

Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is also effective in extending the pot life of the paste. It is preferable to mix in the range of 10 to 25% by weight. By setting the content in this range, the glass transition point and the softening point under load can be kept low, and baking on a glass substrate can be facilitated.

Further, it is preferable that calcium oxide and magnesium oxide are blended to facilitate melting of the glass and to control the coefficient of thermal expansion. 2-15% by weight of calcium oxide and magnesium oxide in total
It is preferable to mix them. When the total amount is 2% by weight or more, devitrification of the glass due to crystallization can be prevented, and when the total amount is 15% by weight or less, the chemical stability of the glass can be maintained.

Although not described in the above composition, it is preferable to include zinc oxide, titanium oxide, zirconium oxide and the like.

As a method for producing the glass powder, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, and aluminum oxide are mixed so as to have a predetermined composition and melted at 900 to 1200 ° C. It is quenched, made into a glass frit, and then crushed to a fine powder of 1 to 5 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 preferable that the thickness is 3.5 μm and the top size is 15 μm or less. Furthermore, a 10% by weight particle size is 0.6 to 1.5 μm.
m, 90% by weight particle size 4-8 μm, specific surface area 1.5-
It is preferred to have 2.5 m2 / g. More preferably, the average particle size is 2.5 to 3.5 μm, and the specific surface area is 1.7.
２2.4 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 diameter 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 unexposed portions, which is not preferable.

The sensitive paste according to the first aspect of the present invention has a total light transmittance T (%) of the paste film after coating and drying with respect to g-line and a film thickness d (μm) after drying of d ≧ 100. In the case of T <90-0.25d, it is necessary to have a relationship of T ≧ 90−0.25d. In the case of T <90−0.25d, a pattern exceeding 250 μm in thickness cannot be formed due to insufficient light transmittance. However, even if the pattern has a thickness of less than 250 μm, the amount of light reaching the top and bottom of the photosensitive paste layer is different, and the amount of light at the bottom is much smaller than that at the top. There is a large difference in degree. When the upper portion is sufficiently cured, the bottom portion is insufficiently cured, and the undercured bottom portion is largely swollen by a developing solution during development, thereby causing meandering. Such meandering,
It remains meandering even after firing and causes uneven brightness when used as a display, which is a problem.

On the other hand, if the bottom is sufficiently hardened, the width of the pattern at the top becomes excessively large, and the shape of the partition wall becomes thick at the top. In this case, a space required for light emission cannot be secured, and the light emitting device cannot be used.

In any case, the unevenness of the curing in the thickness direction increases as the thickness increases, and the problem becomes apparent. A photosensitive paste having a higher light transmittance is desirable because it has a large thickness and a pattern as designed can be obtained.

Further, the total light transmittance T (%) with respect to the i-line of the paste film after coating and drying and the film thickness d (μ) after drying are also shown.
m) is preferably a photosensitive paste having a relationship of T ≧ 90−0.25d when d ≧ 100. T
In the case of <90-0.25d, the light transmittance is insufficient, so that not only a pattern having a thickness of more than 250 μm cannot be formed, but also a pattern having a thickness of less than 250 μm, The amount of light reaching the bottom differs from the amount of light hardening at the bottom, and the amount of light at the bottom is much smaller than that at the top.
When the upper portion is sufficiently cured, the bottom portion is insufficiently cured, and the undercured bottom portion is largely swollen by a developing solution during development, thereby causing meandering. Such meandering remains as a meandering even after firing and causes a problem of uneven brightness when used as a display.

On the other hand, if the bottom is sufficiently hardened, the width of the pattern in the upper portion becomes excessively large, and the shape of the partition wall becomes thicker in the upper portion. In this case, a space required for light emission cannot be secured, and the light emitting device cannot be used.

In any case, the unevenness of the curing in the thickness direction increases as the thickness increases, and the problem becomes apparent. A photosensitive paste having a higher light transmittance is desirable because it has a large thickness and a pattern as designed can be obtained. .

The photosensitive paste of the second invention of the present invention is a photosensitive paste comprising 40 to 90% by weight of inorganic fine particles and 60 to 10 parts by weight of an organic component, and is a paste film after being applied and dried. Is required to be 50% or more at a film thickness of 200 μm after drying. The total light transmittance at a film thickness of 200 μm after drying is 5
If it is less than 0%, the light transmittance is insufficient, so that not only a pattern having a thickness exceeding 250 μm cannot be formed, but also a pattern having a thickness of less than 250 μm reaches the top and bottom of the photosensitive paste layer. Since the amount of light is different and the amount of light at the bottom is much less than at the top, there is a large difference in the degree of photocuring between the top and bottom. When the upper portion is sufficiently cured, the bottom portion is insufficiently cured, and the undercured bottom portion is largely swollen by a developing solution during development, thereby causing meandering. Such a meander remains as a meander after firing,
When used as a display, it causes brightness unevenness, which is a problem. Furthermore, i of the paste film after application and drying
Preferably, the total light transmittance with respect to the line is 50% or more at a film thickness of 200 μm after drying. In the present invention, the measurement of the total light transmittance is performed by using a UV-3101PC type recording spectrophotometer (manufactured by Shimadzu Corporation). Used. The measurement conditions are as follows.

Sample thickness: 20 to 300 μm Sample cell: quartz Slit width: 7.5 mm Measurement speed: SLOW (about 100 nm / min) Light source: halogen lamp Measurement wavelength: g-line (436 nm), h-line (405 n)
m), i-line (365 nm) White plate: BaSO4 (sample side) Secondary white plate: BaSO4 (reference side) Incident angle: 0 ° Sample chamber: Multi-purpose large sample chamber unit (Shimadzu MPC-3100 type) Integrating sphere: 60φ integration Sphere Integrating sphere window: Inlet window 12 (W) x 20 (H) mm Exit window: 12 (W) x 24 (H) mm Photomal window (lower sphere): 16 mmφ PbS cell window (upper sphere): 16 mmφ Opening ratio of integrating sphere: 12.9% Detector: Photomal and PbS cell Specifically, after a photosensitive paste is applied on a quartz cell so as to have a predetermined thickness after drying, quartz is placed on the sample. Place the cell, prepare the measurement sample, and
The total light transmittance is measured under the conditions.

In the present invention, techniques for increasing the total light transmittance include using an organic component and an inorganic component having a high total light transmittance, making each component in the organic component more homogeneously dispersed, The light transmittance of the fine particles themselves is high, the composition inside the inorganic fine particles is uniform, and there is no uneven composition such as bubbles.

Particularly effective is to match the average refractive index of the glass fine particles used as the inorganic fine particles with the average refractive index of the organic component. Preferably, the average refractive index is 1.
A glass powder of 55 to 1.65 is used, and a polymer or a monomer containing an ethylenically unsaturated group having a refractive index of preferably 1.55 to 1.8 is used as an organic component. Is preferably close to that of the inorganic fine particles.

The photosensitive paste is usually made of an ultraviolet absorber,
Antioxidants, inorganic fine particles, photosensitive organic components, organic dyes,
Various components such as a dispersant, a light absorbing agent, and a solvent are blended so as to have a predetermined composition, and then uniformly mixed and dispersed with a three-roller 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, an anti-settling agent, etc., but the range is from 2000 to 200,000 cps.
(Centipoise). For example, when the coating on the substrate is performed by the spin coating method,
5000 cps is preferred. 50,000 to 200,000 c to obtain a film thickness of 10 to 20 μm by applying once by screen printing
ps is preferred. When using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable.

An example in which pattern processing is performed using a photosensitive paste will be described, but the present invention is not limited to this.

On the substrate, the photosensitive paste is applied entirely or partially. As a coating method, a method such as a screen printing method, a bar coater, a roll coater, a die coater, or 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 application, exposure is performed using an exposure apparatus. As an exposure apparatus, a proximity exposure machine or the like can be used. Also, when performing large area exposure,
After applying the photosensitive paste on the substrate, by performing exposure while transporting, with an exposure machine with a small exposure area,
A large area can be exposed.

After exposure, development is carried out using the difference in solubility between the exposed part and the unexposed part in the developing solution.
It is performed by a dipping method, a spray method, or a brush method. It is preferable to use an organic solvent in which an organic component in the photosensitive paste can be dissolved 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
%, More preferably 0.1 to 1% 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 is peeled. 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 usually 400 to 1000 ° C. When patterning on a glass substrate, it is usually 48
It is preferable to perform calcination while holding at a temperature of 0 to 610 ° C. for 10 to 60 minutes.

The photosensitive paste of the present invention is used for forming a pattern substantially consisting of an inorganic substance. Also,
The photosensitive paste of the present invention is used for the purpose of baking after pattern formation using photolithography to form a pattern substantially consisting of an inorganic substance.

In a display application, particularly a plasma display application, a pattern substantially composed of an inorganic substance produced by using the photosensitive paste of the present invention can be used as a partition on a back plate of a plasma display panel or an electrode on a front plate or a back plate of a plasma display panel. It is preferably used as

In the production of a plasma display, it is usually preferable to form an address electrode pattern on a glass substrate and form a dielectric layer so as to cover the address electrodes. Next, a partition is formed over the dielectric layer or the substrate over which the electrodes are formed. The height of the partition is 80 to 20
0 μm is suitable. When the thickness is 80 μm or more, the distance between the phosphor and the electrode formed on the front plate is prevented from becoming too short, and the deterioration of the phosphor due to discharge can be suppressed. Also, 20
By setting the thickness to 0 μm or less, it is possible to prevent the distance between the discharge of the scan electrode and the phosphor from being too large, and to obtain a sufficient luminance. The pitch (P) of the partition walls is 100 μm ≦ P ≦ 50
Those having a thickness of 0 μm are often used. When the thickness is 100 μm or more, the discharge space can be prevented from being narrowed, and sufficient luminance can be obtained. When the thickness is 500 μm or less, an image can be displayed with fine pixels and fine images.

The partition walls are generally formed by patterning a glass paste composed of inorganic fine particles and an organic binder into the shape of the partition walls, and then baking the glass paste at 400 to 600 ° C. to form the partition walls. As a method of forming a partition pattern using a glass paste, it can be formed by a method such as a screen printing method, a sand blast method, a photosensitive paste method, a photo embedding method, and a pressure molding method. Among them, the photosensitive paste method of the present invention is excellent in terms of high definition and simple process.

After the formation of the partition walls, a phosphor layer emitting light of each color of RGB is formed. By applying a phosphor paste containing a phosphor powder, an organic binder and an organic solvent as main components between predetermined partition walls, a phosphor layer can be formed. Examples of the method include a screen printing method in which a pattern is printed using a screen printing plate, a dispenser method in which a phosphor paste is pattern-discharged from the tip of a discharge nozzle, and a photosensitive phosphor in which a photosensitive organic component is used as an organic binder. A photosensitive paste method using a paste or the like can be employed.

The substrate on which the phosphor layer has been formed may be used as required.
By baking at 400 to 550 ° C., a back plate for a plasma display can be manufactured as an example of the display member of the present invention.

Next, a front plate for a plasma display can be manufactured by forming a transparent electrode, a bus electrode, a dielectric, and a protective film (MgO) on a substrate in a predetermined pattern. The photosensitive paste of the present invention is also applicable to the bus electrodes on the front plate. A color filter layer may be formed at a portion corresponding to the RGB phosphor layers formed on the back plate. Further, a black stripe may be formed to improve the contrast.

After sealing the back plate and the front plate thus obtained, a discharge gas composed of helium, neon, xenon, or the like is filled in a space formed at a space between the substrates between the two members. The plasma display of the present invention can be manufactured by mounting a circuit.

[0079]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to this. Photopolymerization initiator 1: 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) butanone-1) (Irgacure 369; manufactured by Ciba Specialty Chemicals) Photopolymerization initiator 2: tetrabusilammonium (1+) n
-Butyltriphenylborate (1-) photopolymerization initiator 3: bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3-
(1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784; manufactured by Ciba Specialty Chemicals) Photopolymerization initiator 4: η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluoro Phosphate (1-) (Irgacure 261; manufactured by Ciba Specialty Chemicals) Photopolymerization initiator 5: N-phenylglycine Sensitizer 1: 2,4-diethylthioxanthone Sensitizer 2: 2- [3- (1,3-dihydro-1,3,3
-Trimethyl-2H-indole-2-ylidene) -1
-Propenyl] -1,3,3-trimethyl-3H-indolium iodide Sensitizer 3: Ketocoumarin dye Polymer 1: Styrene / methyl methacrylate / methacrylic acid copolymer (weight composition ratio 30/30/40) and copolymer 100 weight To which glycidyl methacrylate is added in an amount of 40 parts by weight (weight average molecular weight 31
000, resin acid value 114) Monomer 1: Xylylenediamine / glycidyl methacrylate = 1 mol / 4 mol adduct Monomer 2: polyoxypropylenediamine H2 NC
HCH3CH2- (OCH2CHCH3) n-NH2 (molecular weight about 400) / glycidyl methacrylate = 1 mol /
4-mol adduct Monomer 3: isopropylamine / glycidyl methacrylate = 1 mol / 2 mol adduct (Example 1) The photosensitive paste is prepared by adding inorganic fine particles coated with each component of an organic component and a light absorbing agent and kneading. It was produced by the procedure of kneading with a machine.

A sample for measuring the light transmittance is as follows:
After drying at 80 ° C. for 30 minutes on a 30 cm square quartz substrate, a photosensitive paste containing a solvent was applied so that a photosensitive paste layer having a desired thickness was formed. The light transmittance was measured using a spectrophotometer (UV-3101P, manufactured by Shimadzu Corporation).
C), g-line (436 nm), i-line (365n)
m).

A sample for pattern formation was uniformly applied on a soda glass substrate by screen printing.
Coating to avoid pinholes on the coating film,
Repeat the drying several times or more, the dry thickness is 180μm,
Alternatively, it was applied so as to have a thickness of 300 μm. Drying on the way was performed at 80 ° C. for 15 minutes. Then, it dried at 80 degreeC for 60 minutes.

A photomask (striped pattern,
Exposure was performed through a pattern pitch of 150 μm and a line width of 20 μm). At this time, in order to prevent the mask from being contaminated, a gap of 100 μm was provided between the mask and the coating film surface.
Thereafter, the monoethanolamine was kept at 35 ° C. in 0.1 mL.
Development was carried out by applying a 3% by weight aqueous solution in a shower for 120 seconds to remove a space portion that was not photocured to form a stripe-shaped partition pattern on the glass substrate. Further, the pattern was washed with water using a shower spray.

The partition pattern was observed with a microscope, and the exposure amount at which exfoliation of the exposed portion, meandering of the pattern, and burying (remaining film) between the patterns did not occur was examined. The lower limit of the exposure amount was Emin, the upper limit was Emax, and the median value was the optimum exposure amount Eav. Further, the allowable exposure amount width (%) is (Emax−Emin) /
Calculated from Eav. It can be said that the larger the value of the allowable exposure amount, the better the production stability against the fluctuation of the exposure amount during the production. When the allowable exposure amount width was 0%, it was determined that the pattern could not be formed (indicated by X in Table 1).

The glass substrate on which the partition pattern has been formed at the optimum exposure is dried at 80 ° C. for 15 minutes, and then dried at 560 ° C. for 15 minutes.
The mixture was fired for a minute to form a partition. This firing caused a shrinkage of about 30%.

The inorganic fine particles have a composition of Li 2 O:
9%, SiO2: 22%, Al2 O3: 23%, B2 O3:
Glass fine particles of 33%, BaO: 4%, ZnO: 2%, and MgO: 7% were used. The glass particles have an average refractive index of 1.586, a glass transition point and a softening point of 4 respectively.
76 ° C, 519 ° C, average particle size (D50) 2.6μ
m, D10 are 0.9 μm, D90 is 7.8 μm, and the maximum particle size is 22 μm. The specific surface area is 2.10 m2
/ G.

Glass fine particles obtained by coating a glass powder having this composition with a light absorbing agent were used. In addition, Sudan IV was used as a light absorber, and 0.10% by weight based on glass fine particles was used.

The photosensitive paste was composed of 15 parts by weight of the polymer 1, 15 parts by weight of the monomer 2 and 0.2 parts of the photopolymerization initiator 2.
Part by weight, 0.01 part by weight of sensitizer 2 (cyanine type; absorption maximum wavelength 545 nm) as a sensitizing dye, and 30 parts by weight of dipropylene glycol monomethyl ether were kneaded with 70 parts by weight of the above glass fine particles. .

Evaluation was made on the thickness after coating and drying of 180 μm, 3
It was examined whether a pattern of 00 μm could be formed. In the case of good pattern formation, ○ was shown, and in the case where the pattern was peeled off during development, X was shown. Also, the measurement of the total light transmittance,
According to the method described above, the g-line and the i-line are performed at a thickness of 100 μm, 200 μm, and 300 μm, and the value of T is 90-0.25d (d is the paste thickness when dried) or more. confirmed. Table 1 shows the evaluation results.

Example 2 A photosensitive paste was prepared by using 15 parts by weight of polymer 1, 15 parts by weight of monomer 3, 0.3 part by weight of photopolymerization initiator 3, and 40 parts by weight of γ-butyrolactone. The mixture was kneaded with 60 parts by weight of the same glass fine particles as in Example 1.

Evaluation was performed in the same manner as in Example 1 except that the above-mentioned photosensitive paste was used.

(Example 3) The photosensitive paste was composed of 10 parts by weight of polymer 1, 15 parts by weight of monomer 2, 0.5 part by weight of photopolymerization initiator 4, and sensitizer 3 (ketocoumarin-based ) And 10 parts by weight of dipropylene glycol monomethyl ether were kneaded with 75 parts by weight of the same glass fine particles as in Example 1 and used.

Evaluation was performed in the same manner as in Example 1 except that the above-mentioned photosensitive paste was used.

Comparative Example 1 Glass Fine Particle 70 of Example 1
The organic components blended in parts by weight were such that polymer 1 was 10 parts by weight, monomer 1 was 20 parts by weight, and photopolymerization initiator 1 was 3.0 parts by weight.
Parts by weight and 1.8 parts by weight of sensitizer 1 were blended. The calculated value of the average refractive index of these organic components is 1.59, which is close to the average refractive index of the glass fine particles.

The light transmission spectrum of the photosensitive paste containing these glass fine particles and the organic component has a transmittance peak in the g-line wavelength region, and is measured in the g-line wavelength region measured with a photosensitive paste film having a thickness of 50 μm. Total light transmittance at 6
It was 0%. Table 1 shows the evaluation results.

(Comparative Example 2) Using the same glass fine particles as in Example 1, a coating thickness of 180 μm and 300 μm, the composition of the organic component was mixed with a paste obtained by mixing 15 parts by weight of polymer 1 and 15 parts by weight of monomer 2, 7.2 parts by weight of the photopolymerization initiator 1, 0.5 parts by weight of the polymerization inhibitor hydroquinone monomethyl ether, 0.5 parts by weight of "NOPCOSPARS" 092 (manufactured by San Nopco) as a dispersant, and 1. an ultraviolet absorber. The procedure was performed in the same manner as in Example 1 except that the amount was changed to 7 parts by weight. As an ultraviolet absorber, 1.2 parts by weight of 1,2,3-benzotriazole, "Ubinal" 3039
(Manufactured by BASF Japan) used 0.5 parts by weight. Γ-butyrolactone was used as a solvent for adjusting the viscosity of the paste. The total light transmittance in the g-line wavelength region measured with a photosensitive paste film having a thickness of 50 μm was 70%.

The sectional shape of the obtained pattern was 180 μm in height (thickness) and 36 μm in half width, and a partition pattern with a high aspect ratio was obtained. In addition, 15
Baking was performed for minutes. Observation of the partition pattern obtained after the firing showed that the cross section was rectangular and the height was 125 μm.
m, the partition wall had a half width of 25 μm.

The evaluation results are shown in Tables 1 and 2.

[0098]

[Table 1]

[0099]

[Table 2]

From the results of Tables 1 and 2, the total light transmittance T of the paste film after coating and drying with respect to g-line or i-line is shown.
(%) Is the film thickness d (μm) after drying, T> = 90−
When a photosensitive paste that satisfies the relationship of 0.25d is used, a pattern can be formed even at a film thickness of 300 μm, and even at a film thickness of 180 μm, the allowable exposure amount is wide and stable production is possible. The total light transmittance at a thickness of 50 μm of the conventional photosensitive paste shown in the comparative example is 300 μm in the photosensitive paste of this example.
It is realized in thickness. In this sense, the condition that the total light transmittance satisfies the relationship of T> = 90−0.25d is as follows.
The level is much higher than that of the prior art, and as a result, it is considered that the thick film pattern formability was improved and meandering was suppressed.

Example 4 An electrode pattern was formed on a glass substrate having a high strain point.

The photosensitive paste comprises 66 parts by weight of silver fine particles (average particle size 1.5 μm, specific surface area 1.10 m 2 / g),
7 parts by weight of polymer 2 and propoxylated trimethylolpropane triacrylate (TPA33) as a monomer.
0; Nippon Kayaku Co., Ltd., molecular weight 471, trifunctional) 7 parts by weight, and (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-) as a photopolymerization initiator.
ON) 3 parts by weight, 0.01 parts by weight of an organic dye (Basic Blue 26, absorption maximum wavelength 592 nm), 2 parts by weight of bismuth borosilicate glass particles, and 15 parts by weight of γ-butyrolactone as a solvent, and silver particles obtained by kneading. The paste was applied by screen printing to obtain a dry thickness of 6 μm.
Thereafter, exposure was performed through a photomask (striped pattern, pattern pitch 230 μm, line width 100 μm). Further, the aqueous solution of sodium carbonate kept at 35 ° C. was spray-sprayed for 60 seconds for development to obtain a striped electrode pattern. After drying the glass substrate on which the electrode pattern processing has been completed at 80 ° C. for 15 minutes, 580
Baking was performed at 15 ° C. for 15 minutes to form an electrode.

A dielectric layer was further formed on the glass substrate on which the electrodes were manufactured. 60 parts by weight of low-melting glass particles containing 75% by weight of bismuth oxide, and an average particle diameter of 0.3 μm
A glass paste obtained by kneading 10 parts by weight of titanium oxide fine particles of 10 m, 15 parts by weight of ethyl cellulose, and 15 parts by weight of terpineol was applied by screen printing to a thickness of 20 μm so as to cover the address electrodes in the display area. After that, baking for 15 minutes at 570 ° C.
A back dielectric layer was formed.

A partition pattern was formed on the dielectric layer by the method of the first embodiment. The photomask has an opening line width of 30.
A μm mask was used.

Next, a phosphor layer was formed between adjacent partitions. The phosphor is applied in 256 holes (130 μm in diameter).
m) was performed by a dispenser method in which a phosphor paste was discharged from the tip of the nozzle formed with m). The phosphor layer has a thickness of 25 μm after firing on the side wall of the partition, and has a thickness of 25 μm after firing on the dielectric layer.
After coating to a thickness of μm, baking was performed at 500 ° C. for 10 minutes to complete a back plate for a plasma display as a display member of the present invention.

Next, a front plate was prepared. A pitch of 375 μm and a line width of 15 are formed on a soda glass substrate using ITO.
A scan electrode of 0 μm was formed. Also, after applying the photosensitive paste used for forming the address electrodes of the back plate on the substrate, mask exposure through a photomask was performed.
Development using an aqueous solution of sodium carbonate by weight at 580 ° C. for 15 minutes, followed by a line width of 50 μm and a thickness of 3 μm
Was formed.

Next, a glass paste obtained by kneading 70 parts by weight of low-melting glass particles containing 75% by weight of lead oxide, 20 parts by weight of ethylcellulose, and 10 parts by weight of terpineol was screen-printed by screen printing. The coating was applied with a thickness of 20 μm so as to cover the bus electrode, and then baked at 570 ° C. for 15 minutes to form a front dielectric.

A magnesium oxide layer having a thickness of 0.5 μm was formed on the substrate on which the dielectric layer was formed by electron beam evaporation to produce a front plate.

The front plate and the back plate thus obtained are sealed with a sealing glass, a Ne gas containing 5% of Xe is sealed so as to have an internal gas pressure of 66500 Pa, and a driving circuit is mounted to implement a plasma display. Produced.

When a display was performed by applying a voltage to this plasma display, all the cells showed good display states.

[0111]

The photosensitive paste of the present invention has a very high light transmittance, so that a thicker pattern can be formed more uniformly. Therefore, high-precision pattern processing of a display, circuit material, and the like can be performed, which is useful for improving definition and productivity. In particular, it is suitable for the case where the partition walls of the plasma display panel are manufactured at low cost and with good yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) // C03C 8/16 C03C 8/16 F term (reference) 2H025 AA03 AB20 AC01 AD01 BC13 BC31 BJ00 CA00 CC08 CC20 FA29 2H096 AA26 AA27 BA05 BA06 BA20 EA02 GA08 HA01 JA04 LA17 4G062 AA09 BB05 DA04 DB04 DC05 DD01 DE03 DF01 EA03 EB01 EC01 ED03 EE01 EF01 EG03 FA01 FA10 FB01 FC01 FD01 FE01 FF01 H01 G01 F01 H01 G01 F01 H01 G01 F0101 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM12 MM23 NN32 PP13 5C027 AA09 5C040 GF19

Claims (9)

[Claims] (1) 40 to 90% by weight of inorganic fine particles and 60 to 1
A photosensitive paste comprising 0 parts by weight of an organic component,
The total light transmittance T (%) of the paste film after coating and drying with respect to g-line and the film thickness d (μm) after drying have a relationship of T ≧ 90−0.25d when d ≧ 100. Photosensitive paste. 2. The total light transmittance T (%) with respect to the i-line of the paste film after application and drying, and the thickness d (μm) after drying.
Has a relationship of T ≧ 90−0.25d when d ≧ 100, wherein the photosensitive paste according to claim 1. 3. An inorganic fine particle of 40 to 90% by weight and 60 to 1% by weight.
A photosensitive paste comprising 0 parts by weight of an organic component,
A photosensitive paste, wherein the total light transmittance of the paste film after coating and drying with respect to g-line is 50% or more at a film thickness of 200 µm after drying. 4. The coated and dried paste film has a total light transmittance for i-rays of 5 μm at a film thickness of 200 μm after drying.
The photosensitive paste according to claim 3, wherein the content is 0% or more. 5. An inorganic fine particle having an average refractive index of 1.5 to 1.6.
5. The photosensitive paste according to claim 1, wherein a glass powder having a range of 5 is used. 6. A display member produced by using the photosensitive paste according to claim 1. 7. A member for a plasma display, manufactured using the photosensitive paste according to claim 1. 8. A method of manufacturing a partition for a plasma display, comprising applying the photosensitive paste according to claim 1 onto a substrate, forming a pattern through exposure and development, and further firing. Method. 9. A method for manufacturing a plasma display, comprising the step of forming a partition on a substrate by the method according to claim 8.